Production method of cyclic compounds by olefin metathesis reaction and use of ruthenium catalysts in production of cyclic defines by olefin metathesis reaction

The invention relates to a method for preparation of cyclic compounds by the olefin metathesis reaction and the use of ruthenium catalysts for the preparation of cyclic olefins by olefin metathesis reactions The invention is applicable in the broadly understood organic synthesis using the ring closing metathesis (RCM) reaction.

Background art

A number of ruthenium complexes are known in the art that allow obtaining of internal olefins [R. H. Grubbs (Ed.), A. G. Wenzel (Ed.), D. J. O'Leary (Ed.), E. Khosravi (Ed.), Handbook of Olefin Metathesis, 2nd edition, 3 Volumes, 2015, John Wiley & Sons, Inc. 1 608 pages], among which one should note the 1 st (Ru-I), 2nd (Ru-ll) and 3rd (Ru-lll) generation complexes and complexes comprising two, identical or different, /V-heterocyclic carbene ligands (NHCs). In ruthenium complexes, the active, 14-electron catalyst form comprises a neutral ligand that is a phosphine or NHC [(i) Chem. Rev., 2010, 110, 1746-1787; (ii) Chem. Commun. 2014, 50, 1 0355-10375]. The complexes of the 2nd generation are the most universal and effective, namely so-called Grubbs (Gru-ll), Hoveyda-Grubbs (Hov-ll) and indenylidene (lnd-ll) catalysts.

NHC ligands having various types, more or less complex steric hindrances and modified electronicic properties are known from the literature [Chem. Rev., 2011 , 111, 2705-2733] In general, these may be grouped into carbene imidazole and imidazolidine NHC ligands. Nitrogen atoms in carbene heterocycles of NHC ligands are mostly bound to aromatic substituents, e.g. 2,4,6-trimethylphen-1 -yl (Mes) or 2,6- diisopropylphen-1 -yl (Dipp). Literature reports on ruthenium complexes containing NHC ligands with N- alkyl substituents, but only scarcely. Therefore, our focus is on ruthenium compounds containing N-aryl substituents or a mixed system with A/-aryl and /V-aralkyl substituents in NHC ligands.

The olefin metathesis reaction can often shorten the path of synthesis, reducing the number of necessary steps and lowering the costs of the target product in preparation process, as it was in the course of the optimisation of macrocyclic HCV protease inhibitor known under the trade name Ciluprevir (BILN 2061 ) [(i) Org. Process Res. Dev., 2009, 13, 250-254; (ii) Org. Lett, 2008, 10, 1303-1306].

m mi -ttm jintM} {ίαύ-ίή (IntWlfi (Hemtijnn)

Despite multifarious advantages of the olefin metathesis reaction, its industrial application encounters many difficulties, especially in the preparation processes of macrocyclic rings in the RCM reaction. The first one is related to the thermodynamics of RCM reaction, as it is an equilibrium process [ Chem. Rev., 2009, 109, 3783-3816]. The equilibrium of the metathesis reaction may be shifted towards the formation of products by removing gaseous products, e.g. ethylene, propene or butene, by conducting the reaction under reduced pressure or by using inert gas bubbling to flush out the gaseous products [WO2013048885A1 ].

The second major challenge of the RCM reaction is the lack of selectivity and the competition in the process of obtaining a cyclic product with polymers and oligomeric products [J. Am. Chem. Soc, 2007, 129, 1024-1025]. It is not a prevalent problem in case of the reactions yielding small cyclic olefins (5-6 membered rings), whereas RCM reactions yielding large macrocyclic rings (8-membered rings and larger) require high dilution (from C = 20 mM to C = 0.5 mM) to be used, which significantly hampers and clearly increases the cost of the process due to the large volumes of solvents [(i) Synthesis, 1997, 792-803; (ii) Synlett, 2002, 1302-1304; (iii) Eur. J. Org. Chem., 2004, 2053-2056]. Sometimes it is possible to inhibit processes that are competitive to the RCM reaction and restrict the formation of dimers and oligomers by forcing a favourable conformation/orientation of the substrate through the application of sterically expanded Lewis acids [Org. Lett, 2008, 10, 5613-5615].

The third problem of the metathesis reaction is the migration process of the C=C double bond both within the substrates and the target product [(i) J. Am. Chem. Soc, 2004, 126, 7414-7415; (ii) J. Am. Chem. Soc, 2007, 129, 7961 -7968]. This phenomenon happends due to side reactions that are caused by ruthenium hydrides resulting from the decomposition of the olefin metathesis catalyst. This problem can be partly eliminated by using quinones or other ruthenium hydride inhibitors [J. Am. Chem. Soc, 2005, 127, 17160-1 7161 ].

The fourth hindrance of the use of olefin metathesis in an industrial scale results from the necessity to use a substantial volume of homogeneous ruthenium catalyst, often up to 20 mol% and more. There are already literature reports known where an olefin metathesis catalyst was used in an amount of up to 1 ppm [(i) Adv. Synth. Catal., 2002, 344, 671 -677; (ii) Angew. Chem. Int. Ed., 2017, 56, 981 -986]. However, it should be emphasised that the substrates of these conversions are simple (non-functionalised) olefins, possibly their esters in cross-metathesis or RCM reactions yielding small rings, but not harder-forming macrocyclic products.

A valuable group of compounds classified as components of musk (widely used in the perfume and scents industry) are macrocyclic compounds such as Cyclopentadecanolide, Civetone, Muscone and Astrotone. Attempts to selectively and efficiently prepare these compounds are conducted from the early stages of the development of olefin metathesis reactions [(i) Tetrahedron Lett., 1980, 21, 1 715-171 8; (ii) Tetrahedron Lett, 1980, 21, 2955-2958]. The latest literature reports mainly concern the improvement of diastereoselectivity (E/Z) of the C=C double bond produced during macrocyclisation in the RCM reaction [(i) J. Am. Chem. Soc, 2013, 135, 94-97; (ii) Nature, 2017, 541, 380-385; (iii) WO20121 671 71 A2; (iv) J. Am. Chem. Soc, 2017, 139, 1532-1537]. (a

(b) J. A m. Chem. Soc. _: 2010. J¾ 15179- 15181

On the other hand, a few literature reports are known in which use of an additional substituent (e.g. phenyl) in the vicinal position increases the efficiency of the process, or even allows for obtaining the desired product. Such a strategy has been used by Grubbs et al. to conduct metathesis reactions in polar solvents, alcohols and water-alcohol mixtures [J. Org. Chem., 1998, 63, 9904-9909]. Dorta et al., in turn, used such a strategy to conduct the RCM reaction of vinyl bromides [J. Am. Chem. Soc, 2010, 132, 1 5179-15181 ].

Technical problem

In the summary of prior art, similar technical problems regarding the synthesis of macrocyclic compounds by the RCM reaction appear in further reports. These include: (a) the equilibrium nature of the olefin metathesis reaction - thermodynamic products are yielded as a result of shifting the equilibrium of the reaction towards the desired products by removing one of the products from the reaction environment; (b) high dilution of reagents in the reaction environment (low concentration), which requires the use of large volumes of solvents (which significantly increases the cost of the process and also makes it necessary to use larger, and therefore more expensive reactors); (c) decomposition of the ruthenium reaction catalyst and the resulting migration of the double bond in reaction substrates and products, reducing the selectivity of the process; (d) high load of homogeneous olefin metathesis catalysts based on costly ruthenium.

Solution to the problem

During conducting meticulous optimisation of the conditions of the diene macrocyclization process by RCM reaction, it was surprisingly found that use of substrates with suitably substituted C=C double bonds, use of a low load of a suitable catalyst, addition of adjuvant reagents, use of a suitable solvent and reduction of pressure leads to obtaining the desired macrocyclization product with high yield and selectivity. Disclosure of the essence of the invention

This invention relates to the use of a compound of formula 1 ,

1

wherein:

X ¹ and X ² are each independently an anionic ligand selected from such as halogen atoms, -CN, -SCN, -OR', -SR', -0(C=0)R', -0(S0 ₂ )R', -OSi(R') ₃ group, wherein R' is C -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyi, CrC^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom ;

R ^{1 1} , R ¹² are each independently a hydrogen atom, a halogen atom, optionally substituted C^C^ alkyl, optionally substituted C^C^ perfluoralkyl, optionally substituted C ₂ -C ₂₅ alkene, optionally substituted C3-C7 cycloalkyl, optionally substituted C ₂ -C ₂₅ alkenyl, optionally substituted C ₃ -C ₂₅ cycloalkenyl, optionally substituted C ₂ -C ₂₅ alkinyl, optionally substituted C ₃ -C ₂₅ cycloalkinyl, optionally substituted Ci-C ₂₅ alkoxy, optionally substituted C ₅ -C ₂₄ aryloxy, optionally substituted C ₅ -C ₂₀ heteroaryloxy, optionally substituted C ₅ -C ₂₄ aryl, optionally substituted C ₅ -C ₂₀ heteroaryl, optionally substituted C ₇ -C ₂₄ aralkyl, optionally substituted C ₅ -C ₂₄ perfluoroaryl, optionally substituted 3-12-membered heterocycle;

wherein the substituents R ^{1 1} and R ¹² may be interconnected to form a ring selected from the group consisting of C ₃ -C ₇ cycloalkyl, C ₃ -C ₂₅ cycloalkenyl, C ₃ -C ₂₅ cycloalkinyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, each of which may be substituted with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, Ci-C ₂₅ alkyl, Ci-C ₂₅ perfluoroalkyi, C ₂ -C ₂₅ alkene, C ₃ -C ₇ cycloalkyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkinyl, C ₃ -C ₂₅ cycloalkinyl, C^C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, in which case the dotted line between G and R ¹² is not a chemical bond;

wherein the substituents R ^{1 1} i R ¹² preferably are a hydrogen atom or aryl independently substituted with the following groups: alkoxy (-OR'), sulfide (SR'), sulfoxide (-S(O)R'), sulfonium (-S ⁺ R' ₂ ), sulphonic (-S0 ₂ R'), sulfonamide (-S0 ₂ NR' ₂ ), amino (-NR' ₂ ), ammonium (-N ⁺ R' ₃ ), nitro (-N0 ₂ ), cyano (-CN), phosphonium (-P(0)(OR') ₂ ), phosphinium (-P(O)R'(OR')), phosphonous (-P(OR') ₂ ), phosphine (-PR' ₂ ), phosphine oxides (-P(0)R' ₂ ), phosphonium (-P ⁺ R' ₃ ), carboxy (-COOH), ester (-COOR'), amide (-CONR' ₂ ), amide (-NR'COR"), formyl (-CHO), ketone (-COR'), in which groups R' is C^Cs alkyl, d-Cs perfluoroalkyi, C ₅ -C ₂₄ aryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl;

L is selected from such as:

a)

wherein :

R ¹ is a heteroaryl group;

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently a hydrogen atom, a C1 -C25 alkyl group, a C1 -C25 alkoxy group or a C ₂ -C ₂₅ alkenyl group, wherein the substituents R ² , R ³ , R ⁴ , R ⁵ , R ⁶ may be interconnected to form a substituted or unsubstituted cyclic C ₄ -C ₁₀ or polycyclic C ₄ -C ₁₂ system ;

R ⁷ , R ⁸ , R ⁹ , i R ¹⁰ are each independently a hydrogen atom or a C C ₂ 5 alkyl group, or R ⁷ and/or R ⁸ can be connetced with R ⁹ and/or R ¹⁰ to form a cyclic system ;

n is 0 or 1 ;

b)

wherein :

Ar is an aryl group which is substituted with hydrogen atoms or is optionally substituted with at least one of the following groups: C^C^ alkyl, C C^ perfluoroalkyl, C C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₂ -C ₂₀ heterocycle, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, or a halogen atom ;

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or one of the following groups: C1 -C25 alkyl, C ₃ -Ci ₂ cycloalkyl, C1 -C5 perfluoroalkyl, C ₂ -Ci ₂ alkenyl , C ₅ -C ₂ o aryl, C ₅ -C ₂₄ aryloxy, C ₂ -C ₂ o heterocyclo, C ₄ -C ₂ o heteroarylo, C ₅ -C ₂ o heteroaryloxy, C ₇ --C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, which are optionally substituted with at least one C1 -C12 alkyl, C1 -C12 perfluoroalkyl, C1 -C12 alkoxy, C ₅ -C ₂₄ aryloxy, C ₄ -C ₂ o heteroaryl, C ₅ -C ₂₀ heteroaryloxy, or a halogen atom ; moreover, R ⁵ and R ⁶ and/or R ⁷ i R ⁸ may be interconnected to form a cyclic system ;

wherein :

the combination A ⁺ X ^" and D is a hydrogen atom, or

A is independently a substituent containing a tertiary amine group or a quaternary ammonium group, which may be a N(R ¹ )(R ² ) or N ⁺ (R ¹ )(R ² )(R ³ ) group, wherein R ¹ , R ² and R ³ are each independently one of the following groups: C1 -C25 alkyl, C1 -C12 perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C1 -C25 alkoxy, C ₅ -C ₂ o aryl , C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂ o heteroaryl ; alternatively, A is one of the following groups: Ci-,C ₂ 5 cycloaminoalkyl, C1 -C25 cyclodiaminoalkyl, C1 -C25 cyclotriaminoalkyl, C1 -C25 cyclotetraaminoalkyl, C1 -C25 cycloaminoammonioalkyi, wherein the at least one nitrogen atom is independently substituted with at least one R ¹ group, wherein R ¹ is independently one of the following groups: C C ₂ 5 alkyl, C C^ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, Ci-,C ₂ s alkoxy, C ₅ -C ₂ o aryl, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂ o heteroaryl so that at least one nitrogen atom in the ring forms a quaternary ammonium group; X is independently a halogen atom, or CF ₃ S0 ₃ ^~ , BF ₄ ^~ , PF ₆ ^" , and CI0 ₄ ^~ ;

D is independently one of the following groups: C1 -C25 alkyl, C1 -C12 perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C1 -C25 alkoxy, C5-C20 aryl, C5-C24 aryloxy, C5-C24 perfluoroaryl, C ₅ -C ₂ o heteroaryl, or C2--C25 alkenyl, C C ₂₅ α,ω-dialkoxy, (CH ₂ CH ₂ 0) _n , polyether, where n comprises from 1 to 25, a C C ₂₅ thioalkyl group, a C C ₂₅ α,ω-dithioalkyl group, a C C ₂₅ α,ω-diheteroalkyl group, a C C ₂₅ aminoalkyl group;

E is a single bond or independently a C1 -C25 alkyl group, a C1 -C12 perfluoroalkyl group, a C ₃ -C ₇ cycloalkyl group, a C1 -C25 alkoxy group;

X ^I and X ² are each independently an anion ligand selected from such as halogen atoms;

R ² , R ² , R ³ , R ³ i R ⁴ are each independently a hydrogen atom, a halogen atom, a C C ₂₅ alkyl group, a C ₃ -C ₇ cycloalkyl group, a C C ₂₅ alkoxy group, a C ₅ -C ₂₄ perfluoroaryl group, a C ₅ -C ₂₀ heteroaryl group or a C ₂ -C ₂₅ alkenyl group, wherein the substituents R ² , R ² , R ³ , R ³ and R ⁴ may be interconnected to form a substituted or unsubstituted cyclic C ₄ -Ci ₀ or polycyclic C4-C12 system ;

and

G is selected from the substituents L listed above or G is a heteroatom selected from the group comprising an oxygen, nitrogen, sulphur, phosphorus, fluorine, chlorine, bromine and iodine atom, optionally substituted with a group selected from such as hydrogen atom, C C ₂₅ alkyl, C C ₂₅ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂₀ heteroaryl, C ₇ -C ₂₄ aralkyl, 3-12 membered heterocycle, from the following groups: -COR' acyl, (-CN) cyano, (-COOH) carboxy, (-COOR') ester, (-CONR' ₂ ) amide, (-S0 ₂ R') sulfonic, (-CHO) formyl, (-S0 ₂ NR' ₂ ) sulfonamide, (-COR') ketone, wherein the R' group is C^Cs alkyl, C1 -C5 perfluoroalkyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₄ perfluoroaryl, C ₇ -C ₂₄ aralkyl, in which case the dotted line is a direct bond between the heteroatom and the R ¹² substituent, in the form of an aryl optionally substituted by 1 -4 substituents independently selected from the group comprising a hydrogen atom, a halogen atom, C1 -C25 alkyl, C1 -C25 perfluoroalkyl, C ₂ -C ₂ 5 alken, C ₃ -C ₇ cycloalkyl, C ₂ -C ₂ 5 alkenyl, C ₃ -C ₂ s cycloalkenyl, C2-C25 alkinyl, C ₃ -C ₂ s cycloalkinyl, C ₅ -C ₂₄ aryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂ o heteroaryl, 3-12-membered heterocycle, one of the following groups: (-OR') alkoxy, (-SR') sulfide, (-N0 ₂ ) nitro, (-CN) cyano, (-COOH) carboxy, (-COOR') ester, (-CONR' ₂ ) amide, (-CONR'COR') imide, (-NR' ₂ ) amino, (-N ⁺ R' ₃ ) ammonium, (-NR'COR') amide, (-NR'S0 ₂ R'), sulfonamide (-S0 ₂ R'), sulfonic (-CHO), formyl (-S0 ₂ NR' ₂ ), sulfonamide (-COR'), ketone, in which groups R' is as follows: C C ₅ alkyl, C^Cs perfluoroalkyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₄ perfluoroaryl, C ₇ -C ₂₄ aralkyl ;

in olefin metathesis reactions involving contacting olefins with the formula Dx

wherein:

AB and CD are each independently a group selected from such as a hydrogen atom, C^C^ alkyl, C^C^ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C2-C25 alkenyl, C2-C25 perfluoroalkenyl, C ₃ -C ₂ s cycloalkenyl, C2-C25 alkinyl, C2-C25 perfluoroalkinyl, C ₃ -C ₂ s cycloalkinyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂ o heteroaryl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, which may be optionally substituted independently with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C1 -C25 alkyl, C1 -C25 perfluoroalkyl, C2-C25 alkene, C ₃ -C ₇ cyckloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkinyl, C3-C25 cycloalkinyl, C1 -C25 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, C5-C24 aryl, C ₅ -C ₂ o heteroaryl, C7-C24 aralkyl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle;

G F is an ether (-0-), ester (-C(O)O-), carbonyl (-C(O)-), amido (-C(O)NR-), malonate (-C(COOR) ₂ -) group, wherein R is independently a hydrogen atom, C1 -C12 alkyl, C3-C12 cycloalkyl, C ₂ -Ci ₂ alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1 -C12 alkyl, C1 -C12 perfluoroalkyl, C1 -C12 alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom;

R ^a , R ^b , R ^c i R ^d are each independently C^C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyl, C^C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom ;

or olefins Dy with the formula

wherein:

AB and CD are each independently a group selected from such as C^C^ alkyl, C^C^ perfluoroalkyl, C3-C7 cycloalkyl, C ₂ -C ₂₅ alkenyl, C ₂ -C ₂₅ perfluoroalkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkinyl, C ₂ -C ₂₅ perfluoroalkinyl, C ₃ -C ₂₅ cycloalkinyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, which may be optionally substituted independently with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C1 -C25 alkyl, C1 -C25 perfluoroalkyl, C2-C25 alkene, C ₃ -C ₇ cyckloalkyl, C2-C25 alkenyl, C ₃ -C ₂ s cycloalkenyl, C2-C25 alkinyl, C ₃ -C ₂ s cycloalkinyl, C1 -C25 alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle;

G F is an ether (-0-), ester (-C(O)O-), carbonyl (-C(O)-), amido (-C(O)NR-), malonate (-C(COOR) ₂ -) group, wherein R is a independently hydrogen atom, C1 -C12 alkyl, C ₃ -Ci ₂ cycloalkyl, C ₂ -Ci ₂ alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1 -C12 alkyl, C1 -C12 perfluoroalkyl, C1 -C12 alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom;

R ^a , R ^b , R ^c i R ^d are each independently a hydrogen atom, C^C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C5-C20 aryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyl, C^C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom ;

with the compound with the formula 1 in the presence of other additives, wherein the main product is obtained in the form of at least one cyclic compound Mx comprising at least one non-terminal double C=C bond,

Mx wherein:

AB and CD are each independently a group selected from such as C1 -C10 alkyl, C1 -C10 perfluoroalkyl, C3-C7 cycloalkyl, C2-C25 alkenyl, C ₂ -C ₂ 5 perfluoroalkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkinyl, C ₂ -C ₂₅ perfluoroalkinyl, C ₃ -C ₂₅ cycloalkinyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, which may be substituted independently with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C^C^ alkyl, C^C^ perfluoroalkyl, C ₂ -C ₂₅ alkene, C3-C7 cyckloalkyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkinyl, C ₃ -C ₂₅ cycloalkinyl, Ci -C ₂₅ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle;

G F is an ether (-0-), ester (-C(O)O-), carbonyl (-C(O)-), amido (-C(O)NR-), malonate (-C(CCOR) ₂ -) group, wherein R is independently a hydrogen atom, C^C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one Ci -Ci ₂ alkyl, Ci -Ci ₂ perfluoroalkyl, Ci -Ci ₂ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom.

Preferably, compound 1 is compou

wherein:

X ¹ , X ² are a halogen atom;

R ¹ is a heteroaryl selected from the group comprising furan, thiophene, benzothiophene, benzofuran; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently a hydrogen atom, methyl, isopropyl, a halogen atom ;

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently a hydrogen atom or methyl;

n is 0 or 1 ;

R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom, one of the following groups: C^C^ alkyl, C^C^ alkylamino, C^C^ alkylammonium, C^C^ perfluoroalkyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₇ cycloalkyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkynyl, C ₃ -C ₂₅ cycloalkynyl, Ci -C ₂₅ alkoxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₃ -Ci ₂ heterocycle, 3-12-membered heterocycle, a sulfide (-SR'), ester (-COOR'), amido (-CONR' ₂ ), sulfonic (-S0 ₂ R'), sulfonamide (-S0 ₂ NR' ₂ ) or ketone (-COR'), group, wherein R' is a C^Cs alkyl, C1 -C5 perfluoroalkyl, C ₅ -C ₂₅ aryl or C ₅ -C ₂₅ perfluoroaryl group. Preferably, compound 1 is compound 1 b

wherein:

X ¹ , X ² are a halogen atom;

R ¹ is a heteroaryl selected from the group comprising furan, thiophene, benzothiophene, benzofuran; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently a hydrogen atom, methyl, isopropyl, a halogen atom ;

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently a hydrogen atom or methyl;

n is 0 or 1 ;

R ^{1 1} is a hydrogen atom;

R ²³ , R ²⁴ , R ²⁵ , R ²⁶ are each independently a hydrogen atom, a halogen atom, C C ₂ 5 alkyl, C C ₂ 5 perfluoroalkyl, C ₂ -C ₂₅ alkene, C ₃ -C ₇ cycloalkyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkynyl, C ₃ -C ₂₅ cycloalkynyl, C ₅ -C ₂₄ aryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂₀ heteroaryl, 3-12 membered heterocycle, one of the following groups: alkoxy (-OR'), sulfide (-SR'), nitro (-N0 ₂ ), cyano (-CN), carboxy (-COOH), ester (-COOR'), amido (-CONR' ₂ ), imido (-CONR'COR'), amino (-NR' ₂ ), ammonium (-N ⁺ R' ₃ ), amide (-NR'COR'), sulfonamide (-NR'S0 ₂ R'), sulfonate (-S0 ₂ R'), formyl (-CHO), sulfonamide (-S0 ₂ NR' ₂ ), ketone (-COR'), in which R' groups are as follows: C C ₅ alkyl, C C ₅ perfluoroalkyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₄ perfluoroaryl, C ₇ -C ₂₄ aralkyl, wherein R ²³ , R ²⁴ , R ²⁵ , R ²⁶ are preferably a hydrogen atom ;

G is a halogen atom or a substituent selected from the group comprising OR', SR', S(0)R', S(0) ₂ R' N(R')(R"), P(R')(R"), wherein R' and R" are the same or different C^C^ alkyl group, C ₃ -Ci ₂ cycloalkyl group, Ci-C ₂₅ alkoxy group, C ₂ -C ₂₅ alkenyl group, Ci-Ci ₂ perfluoroalkyl group, C ₅ -C ₂₀ aryl group, C ₅ -C ₂₄ aryloxy group, C ₂ -C ₂₀ heterocyclic group, C ₄ -C ₂₀ heteroaryl group, C ₅ -C ₂₀ heteroaryloxy group, or which may be interconnected to form a substituted or unsubstituted cyclic C ₄ -C ₁₀ or polycyclic C ₄ -C ₁₂ system, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyl, C^C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₂ -C ₂₀ heterocycle, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, which can also be substituted with an ester (-COOR'), amide (-CONR' ₂ ), formyl (-CHO), ketone (-COR'), hydroxamic (-CON(OR')(R')) groups, wherein R' is a Ci-Ci ₂ alkyl, C ₃ -Ci ₂ cycloalkyl, C ₂ -Ci ₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one Ci-Ci ₂ alkyl, Ci-Ci ₂ perfluoroalkyl, Ci-Ci ₂ alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₇ -C ₂₄ aralkyl, C ₂ -C ₂₀ heterocycle, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, or a halogen atom;

Preferably, compound 1 is compound 1c ⁵

X ¹ , X ² are a halogen atom;

G is a halogen atom or a substituent selected from the group OR', SR', S(0)R', S(0) ₂ R' N(R')(R"), P(R')(R"), wherein R' and R" are the same or different C _r C ₂ 5 alkyl group, C ₃ -C ₁₂ cycloalkyl group, C^C^ alkoxy group, C ₂ -C ₂₅ alkenyl group, C^C^ perfluoroalkyi group, C ₅ -C ₂₀ aryl group, C ₅ -C ₂₄ aryloxy group, C ₂ -C ₂₀ heterocyclic group, C ₄ -C ₂₀ heteroaryl group, C ₅ -C ₂₀ heteroaryloxy group, or which may be interconnected to form a substituted or unsubstituted cyclic C ₄ -C ₁₀ or polycyclic C ₄ -C ₁₂ system, which are optionally substituted with at least one Ci -Ci ₂ alkyl, Ci -Ci ₂ perfluoroalkyi, Ci -Ci ₂ alkoxy, C ₅ -C ₂₄ aryloxy, C ₂ -C ₂₀ heterocycle, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, which can also be substituted with an ester (-COOR'), amide (-CONR' ₂ ), formyl (-CHO), ketone (-COR'), hydroxamic (-CON(OR')(R')) groups, wherein R' is a Ci -Ci ₂ alkyl, C ₃ -Ci ₂ cycloalkyl, C ₂ -Ci ₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyi, C^C^ alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₇ -C ₂₄ aralkyl, C ₂ -C ₂₀ heterocycle, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, or a halogen atom ;

R ¹ , R ² , R ³ , R ⁴ are each independently a hydrogen atom, a sulfoxide group (-S(O)R'), a sulfonamide group (-S0 ₂ NR' ₂ ), a nitro group (-N0 ₂ ), an ester group (-COOR'), a ketone group (-COR'), a -NC(0)R' ammonium group, a (-OMe) alkoxy group, in which groups R' is C C ₅ alkyl, C1 -C5 perfluoroalkyi, C ₅ -C ₂₄ aryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl;

R ⁵ , R ⁶ , R ⁷ , i R ⁸ are each independently a hydrogen atom or a C^C^ alkyl group, a C ₅ -C ₂₀ aryl group, which are optionally substituted with at least one Ci -Ci ₂ alkyl, Ci -Ci ₂ perfluoroalkyi, Ci -Ci ₂ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom ; moreover, R ⁵ and R ⁶ and/or R ⁷ and R ⁸ may be interconnected to form a cyclic system.

R ¹³ and R ³ are each independently methyl or ethyl;

R ¹⁴ , R ⁴ , R ¹⁵ are each independently a hydrogen atom, a C^C^ alkyl group.

Preferably, compound 1 is compound 1d

wherein:

the combination A ⁺ X ^" and D is a hydrogen atom, or

A is independently a substituent containing a tertiary amine group or a quaternary ammonium group, which may be a N(R ¹ )(R ² ) or N ⁺ (R ¹ )(R ² )(R ³ ) group, wherein R ¹ , R ² and R ³ are each independently one of the following groups: C C ₂ 5 alkyl, C C^ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C C ₂₅ alkoxy, C ₅ -C ₂₀ aryl, C5-C24 aryloxy, C ₅ -C ₂ 4 perfluoroaryl, C ₅ -C ₂ o heteroaryl ; alternatively, A is one of the following groups: Ci -,C ₂ 5 cycloaminoalkyl, Ci -C ₂₅ cyclodiaminoalkyl, Ci -C ₂₅ cyclotriaminoalkyl, Ci -C ₂₅ cyclotetraaminoalkyl, Ci -C ₂₅ cycloaminoammonioalkyi, wherein the at least one nitrogen atom is independently substituted with at least one R ¹ group, wherein R ¹ is independently one of the following groups: C^C^ alkyl, C C^ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C ,C ₂ 5 alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂₀ heteroaryl so that at least one nitrogen atom in the ring forms a quaternary ammonium group;

X is independently a halogen atom, or CF ₃ S0 ₃ ^~ , BF ₄ ^~ , PF ₆ ^" , and CI0 ₄ ^~ ;

D is independently one of the following groups: Ci -C ₂₅ alkyl, Ci -Ci ₂ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, Ci -C ₂₅ alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂₀ heteroaryl, or C ₂ .-C ₂₅ alkenyl, C C ₂ 5 α,ω-dialkoxy, (CH ₂ CH ₂ 0) _n , polyether, where n comprises from 1 to 25, a C^C^ thioalkyl group, a C C ₂ 5 α,ω-dithioalkyl group, a C^C^ α,ω-diheteroalkyl group, a C^C^ aminoalkyl group;

E is independently a C^C^ alkyl group, a C^C^ perfluoroalkyl group, a C ₃ -C ₇ cycloalkyl group, a C^C^ alkoxy group, or a single bond;

X ^I and X ² are each independently an anion ligand selected from halogen anions;

R ¹ is independently a Ci -C ₂₅ alkyl group, a C ₃ -C ₇ cycloalkyl group, a C ₅ -C ₂₄ aryl group, a C ₅ -C ₂₀ heteroaryl group;

R ² , R ² , R ³ , R ³ i R ⁴ are each independently a hydrogen atom, a halogen atom, a C^C^ alkyl group, a C ₃ -C ₇ cycloalkyl group, a Ci -C ₂₅ alkoxy group, a C ₅ -C ₂₄ perfluoroaryl group, a C ₅ -C ₂₀ heteroarylgroup or a C ₂ -C ₂₅ alkenyl group, wherein the substituents R ² , R ² , R ³ , R ³ and R ⁴ may be interconnected to form a substituted or unsubstituted cyclic C ₄ -Ci ₀ or polycyclic C ₄ -Ci ₂ system ;

R ⁵ is a hydrogen atom, a Ci -C ₂₅ alkyl group, a C ₃ -C ₇ cycloalkyl group;

R ⁶ , R ⁷ , R ⁸ , R ⁹ are each inpendently a hydrogen atom, a halogen atom, C^C^ alkyl, C^C^ perfluoroalkyl, C ₂ -C ₂₅ alkene, C ₃ -C ₇ cycloalkyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkynyl, C ₃ -C ₂₅ cycloalkynyl, C ₅ -C ₂₄ aryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂₀ heteroaryl, 3-12 membered heterocycle, one of the following groups: alkoxy (-OR'), sulfide (-SR'), nitro (-N0 ₂ ), cyano (-CN), carboxy (-COOH), ester (-COOR'), amido (-CONR' ₂ ), imido (-CONR'COR'), amino (-NR' ₂ ), ammonium (-N ⁺ R' ₃ ), amide (-NR'COR'), sulfonamide (-NR'S0 ₂ R'), sulfonate (-S0 ₂ R'), formyl (-CHO), sulfonamide (-S0 ₂ NR' ₂ ), ketone (-COR'), in which R' groups are as follows: C^Cs alkyl, C1 -C5 perfluoroalkyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₄ perfluoroaryl, C ₇ -C ₂₄ aralkyl, wherein R ²³ , R ²⁴ , R ²⁵ , R ²⁶ are preferably a hydrogen atom ;

G is a halogen atom or a substituent selected from the group OR', SR', S(0)R', S(0) ₂ R' N(R')(R"), P(R')(R"), wherein R' and R" are the same or different C _r C ₂₅ alkyl group, C ₃ -C ₁₂ cycloalkyl group, C^C^ alkoxy group, C ₂ -C ₂₅ alkenyl group, Ci -Ci ₂ perfluoroalkyl group, C ₅ -C ₂₀ aryl group, C ₅ -C ₂₄ aryloxy group, C ₂ -C ₂₀ heterocyclic group, C ₄ -C ₂₀ heteroaryl group, C ₅ -C ₂₀ heteroaryloxy group, or which may be interconnected to form a substituted or unsubstituted cyclic C ₄ -Ci ₀ or polycyclic C ₄ -Ci ₂ system, which are optionally substituted with at least one C1 -C12 alkyl, C1 -C12 perfluoroalkyl, C1 -C12 alkoxy, C ₅ -C ₂ 4 aryloxy, C2-C20 heterocycle, C ₄ -C ₂ o heteroaryl, C ₅ -C ₂ o heteroaryloxy, which can also be substituted with an ester (-COOR'), amide (-CONR' ₂ ), formyl (-CHO), ketone (-COR'), hydroxamic (-CON(OR')(R')) groups, wherein R' is a C^C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyl, C^C^ alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₇ -C ₂₄ aralkyl, C ₂ -C ₂ o heterocycle, C ₄ -C ₂ o heteroaryl, C ₅ -C ₂ o heteroaryloxy, or a halogen atom ;

Preferably, compound 1 is compoun

1f

wherein:

X ¹ and X ² are each independently an anionic ligand selected from such as halogen atoms, -CN, -SCN, -OR', -SR', -0(C=0)R', -0(S0 ₂ )R', -OSi(R') ₃ group, wherein R' is Cr-C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyl, CrC^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy, or a halogen atom ;

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a C1 -C25 alkyl group, R ⁷ and/or R ⁸ may be interconnected with R ⁹ and/or R ¹⁰ to form a cyclic system, they also may be independently the following groups: C^-C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, C^Cs perfluoralkyl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyl, CrC^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom ;

R ^{1 1} , R ¹² are each independently a hydrogen atom, a halogen atom, optionally substituted C1 -C25 alkyl, optionally substituted C1 -C25 perfluoralkyl, optionally substituted C ₂ -C ₂ 5 alkene, optionally substituted C ₃ -C ₇ cycloalkyl, optionally substituted C ₂ -C ₂ 5 alkenyl, optionally substituted C ₃ -C ₂ s cycloalkenyl, optionally substituted C ₂ -C ₂ 5 alkinyl, optionally substituted C ₃ -C ₂ s cycloalkinyl, optionally substituted C C ₂ 5 alkoxy, optionally substituted C ₅ -C ₂₄ aryloxy, optionally substituted C ₅ -C ₂₀ heteroaryloxy, optionally substituted C ₅ -C ₂₄ aryl, optionally substituted C ₅ -C ₂₀ heteroaryl, optionally substituted C ₇ -C ₂₄ aralkyl, optionally substituted C ₅ -C ₂₄ perfluoroaryl, optionally substituted 3-12-membered heterocycle;

wherein the substituents R ^{1 1} and R ¹² may be interconnected to form a ring selected from the group consisting of C ₃ -C ₇ cycloalkyl, C ₃ -C ₂ s cycloalkenyl, C ₃ -C ₂ s cycloalkinyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂ o heteroaryl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, each of which may be substituted with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C1 -C25 alkyl, C1 -C25 perfluoroalkyl, C2-C25 alkene, C ₃ -C ₇ cycloalkyl, C2-C25 alkenyl, C ₃ -C ₂ s cycloalkenyl, C2-C25 alkinyl, C ₃ -C ₂ s cycloalkinyl, C1 -C25 alkoxy, C ₅ -C ₂₄ aryloxy, C5-C20 heteroaryloxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂ oheteroaryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂ 4 perfluoroaryl, 3-12-membered heterocycle;

R ¹³ and R ³ are each independently methyl or ethyl;

R ¹⁴ , R ⁴ , R ¹⁵ are each independently a hydrogen atom, a C ₁ -C ₂₅ alkyl group.

Preferably, com ound 1 is represented by a formula with a structure selected from such as:

(Grubbs 2) (Bertrand) (LatMet)

(FixCat ^M0F )

Preferably, compound 1 is deposited on a solid support selected from the group comprising silica gel (Si0 ₂ ), aluminium oxide (Al ₂ 0 ₃ ), zeolites, celite, or MOF (Metal Organic Framework)-like materials, i.e. potentially porous coordination polymers.

Preferably, in said reaction, quinone derivatives are used as an additive in an amount from 5 mol% to 0.05 mol%, preferably such as quinone, anthraquinone, tetrafluoroquinone, tetrachloroquinone and the like.

Preferably, the reaction is conducted in an organic solvent such as toluene, benzene, mesitylene, dichloromethane, ethyl acetate, methyl acetate, tert-butyl methyl ether, cyclopentyl methyl ether, paraffin oil, paraffin wax, ionic liquid, polyethylene, PAO polyalphaolefins, preferably PAO 6 and PAO 4, or without any solvent.

Preferably, olefins Dx and/or olefin Dy at a concentration of between 1 mM and 1 M are used in the reaction.

Preferably, the reaction is conducted at a temperature of between 20 and 200°C for between 5 minutes and 24 hours.

Preferably, compound 1 is used in an amount between 2 mol% and 0.0005 mol%.

Preferably, compound 2 is added to the reaction mixture in portions and/or continuously using a pump, as a solid and/or as a solution in an organic solvent.

Preferably, olefin Dx or olefin Dy is added to the reaction mixture in portions and/or continuously using a pump.

Preferably, during the reaction, the reaction product that is gaseous in the reaction conditions is actively removed from the reaction mixture using inert gas or vacuum.

Preferably, the reaction is conducted at a pressure below the atmospheric pressure, more preferably at a pressure of between 1 bar and 1 -10 ⁶ mbar.

The invention also relates to a method for producing a cyclic compound Mx that contains at least one non-terminal C=C double bond,

G

AB CD

Mx

wherein:

AB and CD are each independently a group selected from such as Ci-Ci ₀ alkyl, Ci-Ci ₀ perfluoroalkyl, C3-C7 cycloalkyl, C ₂ -C ₂₅ alkenyl, C ₂ -C ₂₅ perfluoroalkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkinyl, C ₂ -C ₂₅ perfluoroalkinyl, C ₃ -C ₂₅ cycloalkinyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, which may be substituted independently with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C1 -C25 alkyl, C1 -C25 perfluoroalkyl, C2-C25 alkene, C3-C7 cyckloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkinyl, C3-C25 cycloalkinyl, C1 -C25 alkoxy, C5-C24 aryloxy, C ₅ -C ₂₀ heteroaryloxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle;

GF is an ether (-0-), ester (-C(O)O-), carbonyl (-C(O)-), amido (-C(O)NR-), malonate (-C(COOR) ₂ -) group, wherein R is independently a hydrogen atom, C1 -C12 alkyl, C3-C12 cycloalkyl, C ₂ -Ci ₂ alkenyl, C5-C20 aryl, which are optionally substituted with at least one C^C^ alkyl, C C^ perfluoroalkyl, C^C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom;

characterised in that the olefin Dx with the following formula

wherein:

AB and CD are each independently a group selected from such as a hydrogen atom, C^C^ alkyl, C^C^ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C ₂ -C ₂₅ alkenyl, C ₂ -C ₂₅ perfluoroalkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkinyl, C ₂ -C ₂₅ perfluoroalkinyl, C ₃ -C ₂₅ cycloalkinyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, which may be optionally substituted independently with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C1 -C25 alkyl, C1 -C25 perfluoroalkyl, C2-C25 alkene, C ₃ -C ₇ cyckloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkinyl, C3-C25 cycloalkinyl, C1 -C25 alkoxy, C ₅ -C ₂₄ aryloxy, C5-C20 heteroaryloxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂ o heteroaryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle;

R ^a , R ^b , R ^c i R ^d are each independently a C1 -C12 alkyl, C3-C12 cycloalkyl, C ₂ -Ci ₂ alkenyl, C ₅ -C ₂ o aryl, which are optionally substituted with at least one C1 -C12 alkyl, C1 -C12 perfluoroalkyl, C1 -C12 alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂ o heteroaryloxy or a halogen atom;

GF is an ether (-0-), ester (-C(O)O-), carbonyl (-C(O)-), amido (-C(O)NR-), malonate (-C(COOR) ₂ -) group, wherein R is independently a hydrogen atom, C^C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C5-C20 aryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyl, C^C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom;

or the olefin Dy with the formula

wherein:

AB and CD are each independently a group selected from such as a hydrogen atom, C^C^ alkyl, C^C^ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C2-C25 alkenyl, C2-C25 perfluoroalkenyl, C3-C25 cycloalkenyl, C2-C25 alkinyl, C ₂ -C ₂₅ perfluoroalkinyl, C ₃ -C ₂₅ cycloalkinyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, which may be optionally substituted independently with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C1 -C25 alkyl, C1 -C25 perfluoroalkyl, C ₂ -C ₂ 5 alkene, C ₃ -C ₇ cyckloalkyl, C2-C25 alkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkinyl, C ₃ -C ₂₅ cycloalkinyl, C^C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle;

R ^a , R ^b , R ^c i R ^d are each independently a Ci -Ci ₂ alkyl, C ₃ -Ci ₂ cycloalkyl, C ₂ -Ci ₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one Ci -Ci ₂ alkyl, Ci -Ci ₂ perfluoroalkyl, Ci -Ci ₂ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom;

GF is an ether (-0-), ester (-C(O)O-), carbonyl (-C(O)-), amido (-C(O)NR-), malonate (-C(COOR) ₂ -) group, wherein R is independently a hydrogen atom, C^C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyl, C^C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom;

are subjected to olefin metathesis reaction with the compound of the formula 1 ,

1

wherein:

X ¹ and X ² are each independently an anionic ligand selected from such as halogen atoms, -CN, -SCN, -OR', -SR', -0(C=0)R', -0(S0 ₂ )R', -OSi(R') ₃ group, wherein R' is Cr-C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one Ci -Ci ₂ alkyl, Ci -Ci ₂ perfluoroalkyl, Ci -Ci ₂ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy, or a halogen atom;

R ^{1 1} , R ¹² are each independently a hydrogen atom, a halogen atom, optionally substituted Ci -C ₂₅ alkyl, optionally substituted C^C^ perfluoralkyl, optionally substituted C ₂ -C ₂₅ alkene, optionally substituted C ₃ -C ₇ cycloalkyl, optionally substituted C ₂ -C ₂₅ alkenyl, optionally substituted C ₃ -C ₂₅ cycloalkenyl, optionally substituted C ₂ -C ₂₅ alkinyl, optionally substituted C ₃ -C ₂₅ cycloalkinyl, optionally substituted C C ₂ 5 alkoxy, optionally substituted C ₅ -C ₂₄ aryloxy, optionally substituted C ₅ -C ₂₀ heteroaryloxy, optionally substituted C ₅ -C ₂₄ aryl, optionally substituted C ₅ -C ₂₀ heteroaryl, optionally substituted C ₇ -C ₂₄ aralkyl, optionally substituted C ₅ -C ₂₄ perfluoroaryl, optionally substituted 3-12-membered heterocycle;

wherein the substituents R ^{1 1} and R ¹² may be interconnected to form a ring selected from the group consisting of C ₃ -C ₇ cycloalkyl, C ₃ -C ₂₅ cycloalkenyl, C ₃ -C ₂₅ cycloalkinyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, each of which may be independently substituted with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C C^ alkyl, C^C^ perfluoroalkyl, C ₂ -C ₂₅ alkene, C ₃ -C ₇ cycloalkyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkinyl, C ₃ -C ₂₅ cycloalkinyl, Ci -C ₂₅ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, in which case the dotted line between G and R ¹² is not a chemical bond;

wherein the substituents R ^{1 1} i R ¹² preferably are a hydrogen atom or aryl independently substituted with the following groups: alkoxy (-OR'), sulfide (-SR'), sulfoxide (-S(O)R'), sulfonium (-S ⁺ R' ₂ ), sulphonic (-S0 ₂ R'), sulfonamide (-S0 ₂ NR' ₂ ), amino (-NR' ₂ ), ammonium (-N ⁺ R' ₃ ), nitro (-N0 ₂ ), cyano (-CN), phosphonium (-P(0)(OR') ₂ ), phosphinium (-P(O)R'(OR')), phosphonous (-P(OR') ₂ ), phosphine (-PR' ₂ ), phosphine oxides (-P(0)R' ₂ ), phosphonium (-P ⁺ R' ₃ ), carboxy (-COOH), ester (-COOR'), amide (-CONR' ₂ ), amide (-NR'COR"), formyl (-CHO), ketone (-COR'), in which groups R' is C^Cs alkyl, d-Cs perfluoroalkyi, C ₅ -C ₂₄ aryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl;

L is selected from such as:

a)

wherein:

R ¹ is a heteroaryl group;

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently a hydrogen atom, a Ci-C ₂₅ alkyl group, a Ci-C ₂₅ alkoxy group or a C ₂ -C ₂₅ alkenyl group, wherein the substituents R ² , R ³ , R ⁴ , R ⁵ , R ⁶ may be interconnected to form a substituted or unsubstituted cyclic C ₄ -C ₁₀ or polycyclic C ₄ -C ₁₂ system ;

R ⁷ , R ⁸ , R ⁹ , i R ¹⁰ are each independently a hydrogen atom or a C^C^ alkyl group, or R ⁷ and/or R ⁸ can be connetced with R ⁹ and/or R ¹⁰ to form a cyclic system;

n is 0 or 1 ;

b)

wherein:

Ar is an aryl group which is substituted with hydrogen atoms or is optionally substituted with at least one of the following groups: Ci-Ci ₂ alkyl, Ci-Ci ₂ perfluoroalkyi, Ci-Ci ₂ alkoxy, C ₅ -C ₂₄ aryloxy, C ₂ -C ₂₀ heterocycle, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, or a halogen atom;

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or one of the following groups: C^C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C C ₅ perfluoroalkyi, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₂ -C ₂₀ heterocyclo, C ₄ -C ₂₀ heteroarylo, C ₅ -C ₂₀ heteroaryloxy, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, which are optionally substituted with at least one C^C^ alkyl, C C^ perfluoroalkyi, C C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, or a halogen atom ; moreover, R ⁵ and R ⁶ and/or R ⁷ i R ⁸ may be interconnected to form a cyclic system ; c)

wherein:

the combination A ⁺ X ^" and D is a hydrogen atom, or

A is independently a substituent containing a tertiary amine group or a quaternary ammonium group, which may be a N(R ¹ )(R ² ) or N ⁺ (R ¹ )(R ² )(R ³ ) group, wherein R ¹ , R ² and R ³ are each independently one of the following groups: C1 -C25 alkyl, C1 -C12 perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C1 -C25 alkoxy, C ₅ -C ₂ o aryl, C5-C24 aryloxy, C ₅ -C ₂ 4 perfluoroaryl, C ₅ -C ₂ o heteroaryl ; alternatively, A is one of the following groups: C ₁ -,C ₂₅ cycloaminoalkyl, C^C^ cyclodiaminoalkyl, C^C^ cyclotriaminoalkyl, C^C^ cyclotetraaminoalkyl, Ci -C ₂₅ cycloaminoammonioalkyi, wherein the at least one nitrogen atom is independently substituted with at least one R ¹ group, wherein R ¹ is independently one of the following groups: C^C^ alkyl, C C^ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C^C^ alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂₀ heteroaryl so that at least one nitrogen atom in the ring forms a quaternary ammonium group;

X is independently a halogen atom, or CF ₃ S0 ₃ ^~ , BF ₄ ^~ , PF ₆ ^" , and CI0 ₄ ^~ ;

D is independently one of the following groups: Ci -C ₂₅ , alkyl, Ci -Ci ₂ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, Ci -C ₂₅ alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂₀ heteroaryl, or C ₂ -C ₂₅ alkenyl, C C ₂ 5 α,ω-dialkoxy, (CH2CH20) _n , polyether, where n comprises from 1 to 25, a C^C^ thioalkyl group, a C C ₂ 5 α,ω-dithioalkyl group, a C^C^ α,ω-diheteroalkyl group, a C^C^ aminoalkyl group;

E is a single bond or independently a Ci -C ₂₅ alkyl group, a Ci -Ci ₂ perfluoroalkyl group, a C ₃ -C ₇ cycloalkyl group, a C^C^ alkoxy group;

X ^I and X ² are each independently an anion ligand selected from such as halogen atoms;

R ² , R ² , R ³ , R ³ i R ⁴ are each independently a hydrogen atom, a halogen atom, a C^C^ alkyl group, a C ₃ -C ₇ cycloalkyl group, a C^C^ alkoxy group, a C ₅ -C ₂₄ perfluoroaryl group, a C ₅ -C ₂₀ heteroarylgroup or a C ₂ -C ₂₅ alkenyl group, wherein the substituents R ² , R ² , R ³ , R ³ and R ⁴ may be interconnected to form a substituted or unsubstituted cyclic C ₄ -Ci ₀ or polycyclic C ₄ -Ci ₂ system ;

and

G is selected from the substituents L listed above or G is a heteroatom selected from the group comprising an oxygen, nitrogen, sulphur, phosphorus, fluorine, chlorine, bromine and iodine atom, optionally substituted with a group selected from such as hydrogen atom, C^C^ alkyl, C^C^ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂₀ heteroaryl, C ₇ -C ₂₄ aralkyl, 3-12 membered heterocycle, from the following groups: -COR' acyl, (-CN) cyano, (-COOH) carboxy, (-COOR') ester, (-CONR' ₂ ) amide, (-S0 ₂ R') sulfonic, (-CHO) formyl, (-S0 ₂ NR' ₂ ) sulfonamide, (-COR') ketone, wherein the R' group is C C ₅ alkyl, C C ₅ perfluoroalkyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₄ perfluoroaryl, C ₇ -C ₂₄ aralkyl, in which case the dotted line is a direct bond between the heteroatom and the R ¹² substituent, in the form of an aryl optionally substituted by 1 -4 substituents independently selected from the group comprising a hydrogen atom, a halogen atom, C1 -C25 alkyl, C1 -C25 perfluoroalkyl, C ₂ -C ₂ 5 alken, C ₃ -C ₇ cycloalkyl, C ₂ -C ₂ 5 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkinyl, C3-C25 cycloalkinyl, C5-C24 aryl, C7-C24 aralkyl, C5-C24 perfluoroaryl, C ₅ -C ₂₀ heteroaryl, 3-12-membered heterocycle, one of the following groups: (-OR') alkoxy, (-SR') sulfide, (-N0 ₂ ) nitro, (-CN) cyano, (-COOH) carboxy, (-COOR') ester, (-CONR' ₂ ) amide, (-CONR'COR') imide, (-NR' ₂ ) amino, (-N ⁺ R' ₃ ) ammonium, (-NR'COR') amide, (-NR'S0 ₂ R'), sulfonamide (-SO2R'), sulfonic (-CHO), formyl (-S0 ₂ NR' ₂ ), sulfonamide (-COR'), ketone, in which groups R' is as follows: C C ₅ alkyl, C C ₅ perfluoroalkyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₄ perfluoroaryl, C ₇ -C ₂₄ aralkyl ;

wherein the metathesis reaction is optionally carried out in the presence of other additives enhancing the process of the reaction.

Preferably, compound 1a is used as compound 1 .

wherein:

X ¹ , X ² are a halogen atom;

R ¹ is a heteroaryl selected from the group comprising furan, thiophene, benzothiophene, benzofuran; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently a hydrogen atom, methyl, isopropyl, a halogen atom;

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently a hydrogen atom or methyl;

n is 0 or 1 ;

R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom, one of the following groups: C C ₂₅ alkyl, C C ₂₅ alkylamino, C C ₂₅ alkylammonium, C C ₂₅ perfluoroalkyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₇ cycloalkyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkynyl, C ₃ -C ₂₅ cycloalkynyl, C C ₂₅ alkoxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₃ -C ₁₂ heterocycle, 3-12-membered heterocycle, a sulfide (-SR'), ester (-COOR'), amido (-CONR' ₂ ), sulfonic (-S0 ₂ R'), sulfonamide (-S0 ₂ NR' ₂ ) or ketone (-COR'), group, wherein R' is a C^Cs alkyl, C1 -C5 perfluoroalkyl, C5-C25 aryl or C5-C25 perfluoroaryl group.

wherein:

X ¹ , X ² are a halogen atom;

R ¹ is a heteroaryl selected from the group comprising furan, thiophene, benzothiophene, benzofuran; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently a hydrogen atom, methyl, isopropyl, a halogen atom ;

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently a hydrogen atom or methyl;

n is 0 or 1 ;

R ^{1 1} is a hydrogen atom;

R ²³ , R ²⁴ , R ²⁵ , R ²⁶ are each independently a hydrogen atom, a halogen atom, C1 -C25 alkyl, C1 -C25 perfluoroalkyl, C2-C25 alkene, C ₃ -C ₇ cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C ₅ -C ₂₄ aryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂₀ heteroaryl, 3-12 membered heterocycle, one of the following groups: alkoxy (-OR'), sulfide (-SR'), nitro (-N0 ₂ ), cyano (-CN), carboxy (-COOH), ester (-COOR'), amido (-CONR' ₂ ), imido (-CONR'COR'), amino (-NR' ₂ ), ammonium (-N ⁺ R' ₃ ), amide (-NR'COR'), sulfonamide (-NR'S0 ₂ R'), sulfonate (-S0 ₂ R'), formyl (-CHO), sulfonamide (-S0 ₂ NR' ₂ ), ketone (-COR'), in which R' groups are as follows: C^Cs alkyl, C1 -C5 perfluoroalkyl, C5-C24 aryl, C5-C24 perfluoroaryl, C ₇ -C ₂₄ aralkyl, wherein R ²³ , R ²⁴ , R ²⁵ , R ²⁶ are preferably a hydrogen atom ;

G is a halogen atom or a substituent selected from the group OR', SR', S(0)R', S(0) ₂ R' N(R')(R"), P(R')(R"), wherein R' and R" are the same or different C _r C ₂ 5 alkyl group, C ₃ -C ₁₂ cycloalkyl group, C _r C ₂ 5 alkoxy group, C ₂ -C ₂ 5 alkenyl group, C1 -C12 perfluoroalkyl group, C ₅ -C ₂ o aryl group, C ₅ -C ₂ 4 aryloxy group, C2-C20 heterocyclic group, C ₄ -C ₂ o heteroaryl group, C ₅ -C ₂ o heteroaryloxy group, or which may be interconnected to form a substituted or unsubstituted cyclic C ₄ -Ci ₀ or polycyclic C4-C12 system, which are optionally substituted with at least one C1 -C12 alkyl, C1 -C12 perfluoroalkyl, C1 -C12 alkoxy, C ₅ -C ₂ 4 aryloxy, C ₂ -C ₂₀ heterocycle, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, which can also be substituted with an ester (-COOR'), amide (-CONR' ₂ ), formyl (-CHO), ketone (-COR'), hydroxamic (-CON(OR')(R')) groups, wherein R' is a C^C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyl, C^C^ alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₇ -C ₂₄ aralkyl, C ₂ -C ₂ o heterocycle, C ₄ -C ₂ o heteroaryl, C ₅ -C ₂ o heteroaryloxy, or a halogen atom. Preferably, compound 1c is used as compound 1

wherein:

X ¹ , X ² are a halogen atom;

G is a halogen atom or a substituent selected from the group OR', SR', S(0)R', S(0) ₂ R' N(R')(R"), P(R')(R"), wherein R' and R" are the same or different C C ₂ 5 alkyl group, C ₃ -Ci ₂ cycloalkyl group, C1 -C25 alkoxy group, C ₂ -C ₂ 5 alkenyl group, C1 -C12 perfluoroalkyi group, C ₅ -C ₂ o aryl group, C ₅ -C ₂ 4 aryloxy group, C ₂ -C ₂₀ heterocyclic group, C ₄ -C ₂₀ heteroaryl group, C ₅ -C ₂₀ heteroaryloxy group, or which may be interconnected to form a substituted or unsubstituted cyclic C ₄ -Ci ₀ or polycyclic C ₄ -Ci ₂ system, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyi, C^C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₂ -C ₂₀ heterocycle, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, which can also be substituted with an ester (-COOR'), amide (-CONR' ₂ ), formyl (-CHO), ketone (-COR'), hydroxamic (-CON(OR')(R')) groups, wherein R' is a C^C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one Ci -Ci ₂ alkyl, Ci -Ci ₂ perfluoroalkyi, Ci -Ci ₂ alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₇ -C ₂₄ aralkyl, C ₂ -C ₂₀ heterocycle, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, or a halogen atom ;

R ¹ , R ² , R ³ , R ⁴ are each independently a hydrogen atom, a sulfoxide group (-S(O)R'), a sulfonamide group (-S0 ₂ NR' ₂ ), a nitro group (-N0 ₂ ), an ester group (-COOR'), a ketone group (-COR'), a -NC(0)R' ammonium group, a (-OMe) alkoxy group, in which groups R' is C C ₅ alkyl, C1 -C5 perfluoroalkyi, C ₅ -C ₂₄ aryl, C ₇ --C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl;

R ⁵ , R ⁶ , R ⁷ , i R ⁸ are each independently a hydrogen atom or a Ci -C ₂₅ alkyl group, a C ₅ -C ₂₀ aryl group, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyi, C^C^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom ; moreover, R ⁵ and R ⁶ and/or R ⁷ and R ⁸ may be interconnected to form a cyclic system

R ¹³ and R ³ are each independently methyl or ethyl;

R ¹⁴ , R ⁴ , R ¹⁵ are each independently a hydrogen atom, a Ci -C ₂₅ alkyl group. Preferably, compound 1d is used as compound 1

wherein:

the combination A ⁺ X ^" and D is a hydrogen atom, or

A is independently a substituent containing a tertiary amine group or a quaternary ammonium group, which may be a N(R ¹ )(R ² ) or N ⁺ (R ¹ )(R ² )(R ³ ) group, wherein R ¹ , R ² and R ³ are each independently one of the following groups: C C ₂₅ alkyl C C^ perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C C ₂ 5 alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₄ perfluoroaryl, C ₅ -C ₂₀ heteroaryl ; alternatively, A is one of the following groups: C1 -C25 cycloaminoalkyl, C C ₂ 5 cyclodiaminoalkyl, C C ₂₅ cyclotriaminoalkyl, C C ₂₅ cyclotetraaminoalkyl, C1 -C25 cycloaminoammonioalkyi, wherein the at least one nitrogen atom is independently substituted with at least one R ¹ group, wherein R ¹ is independently one of the following groups: C1 -C25 alkyl, C1 -C12 perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C1 -C25 alkoxy, C5-C20 aryl, C5-C24 aryloxy, C5-C24 perfluoroaryl, C ₅ -C ₂ o heteroaryl so that at least one nitrogen atom in the ring forms a quaternary ammonium group;

X is independently a halogen atom, or CF ₃ S0 ₃ ^~ , BF ₄ ^" , PF ₆ ^" , and CI0 ₄ ^" ;

D is independently one of the following groups: C1 -C25 alkyl, C1 -C12 perfluoroalkyl, C ₃ -C ₇ cycloalkyl, C1 -C25 alkoxy, C5-C20 aryl, C5-C24 aryloxy, C5-C24 perfluoroaryl, C ₅ -C ₂ o heteroaryl, or C2--C25 alkenyl, C1 -C25 α,ω-dialkoxy group, a (CH ₂ CH ₂ 0) _n polyether group, where n comprises from 1 to 25, a C1 -C25 thioalkyl group, a C C ₂₅ α,ω-dithioalkyl group, a C C ₂ 5 α,ω-diheteroalkyl group, a C C ₂₅ aminoalkyl group;

E is independently a C C ₂₅ alkyl group, a C^C^ perfluoroalkyl group, a C ₃ -C ₇ cycloalkyl group, a C C ₂₅ alkoxy group, or a single bond;

X ^I and X ² are each independently an anion ligand selected from such as halogen atoms;

R ¹ is independently a C1 -C25 alkyl group, a C ₃ -C ₇ cycloalkyl group, a C ₅ -C ₂ 4 aryl group, a C ₅ -C ₂ o heteroaryl group;

R ² , R ² , R ³ , R ³ i R ⁴ are each independently a hydrogen atom, a halogen atom, a C1 -C25 alkyl group, a C ₃ -C ₇ cycloalkyl group, a C C ₂₅ alkoxy group, a C ₅ -C ₂₄ perfluoroaryl group, a C ₅ -C ₂₀ heteroarylgroup or a C ₂ -C ₂₅ alkenyl group, wherein the substituents R ² , R ² , R ³ , R ³ and R ⁴ may be interconnected to form a substituted or unsubstituted cyclic C ₄ -C ₁₀ or polycyclic C ₄ -C ₁₂ system ;

R ⁵ is a hydrogen atom, a C1 -C25 alkyl group, a C ₃ -C ₇ cycloalkyl group; R ⁶ , R ⁷ , R ⁸ , R ⁹ are each independently a hydrogen atom, a halogen atom, C1 -C25 alkyl, C1 -C25 perfluoroalkyl, C2-C25 alkene, C ₃ -C ₇ cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C5-C24 aryl, C7-C24 aralkyl, C5-C24 perfluoroaryl, C ₅ -C ₂ o heteroaryl, 3-12 membered heterocycle, one of the following groups: alkoxy (-OR'), sulfide (-SR'), nitro (-N0 ₂ ), cyano (-CN), carboxy (-COOH), ester (-COOR'), amido (-CONR' ₂ ), imido (-CONR'COR'), amino (-NR' ₂ ), ammonium (-N ⁺ R' ₃ ), amide (-NR'COR'), sulfonamide (-NR'S0 ₂ R'), sulfonate (-S0 ₂ R'), formyl (-CHO), sulfonamide (-S0 ₂ NR' ₂ ), ketone (-COR'), in which R' groups are as follows: C^Cs alkyl, C1 -C5 perfluoroalkyl, C5-C24 aryl, C ₅ -C ₂₄ perfluoroaryl, C ₇ -C ₂₄ aralkyl, wherein R ²³ , R ²⁴ , R ²⁵ , R ²⁶ are preferably a hydrogen atom ;

G is a halogen atom or a substituent selected from the group OR', SR', S(0)R', S(0) ₂ R' N(R')(R"), P(R')(R"), wherein R' and R" are the same or different C _r C ₂ 5 alkyl group, C ₃ -C ₁₂ cycloalkyl group, C _r C ₂ 5 alkoxy group, C ₂ -C ₂₅ alkenyl group, C^C^ perfluoroalkyl group, C ₅ -C ₂₀ aryl group, C ₅ -C ₂₄ aryloxy group, C2-C20 heterocyclic group, C ₄ -C ₂ o heteroaryl group, C ₅ -C ₂ o heteroaryloxy group, or which may be interconnected to form a substituted or unsubstituted cyclic C ₄ -Ci ₀ or polycyclic C4-C12 system, which are optionally substituted with at least one C1 -C12 alkyl, C1 -C12 perfluoroalkyl, C1 -C12 alkoxy, C ₅ -C ₂ 4 aryloxy, C ₂ -C ₂₀ heterocycle, C ₄ -C ₂₀ heteroaryl, C ₅ -C ₂₀ heteroaryloxy, which can also be substituted with an ester (-COOR'), amide (-CONR' ₂ ), formyl (-CHO), ketone (-COR'), hydroxamic (-CON(OR')(R')) groups, wherein R' is a C^C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂₀ aryl, which are optionally substituted with at least one C^C^ alkyl, C^C^ perfluoroalkyl, C^C^ alkoxy, C ₅ -C ₂₀ aryl, C ₅ -C ₂₄ aryloxy, C ₇ -C ₂₄ aralkyl, C ₂ -C ₂ o heterocycle, C ₄ -C ₂ o heteroaryl, C ₅ -C ₂ o heteroaryloxy, or a halogen atom ;

Preferably, compound 1f is used as compound 1

1f

wherein:

X ¹ and X ² are each independently an anionic ligand selected from such as halogen atoms, -CN, -SCN, -OR', -SR', -0(C=0)R', -0(S0 ₂ )R', -OSi(R') ₃ group, wherein R' is C C _{i 2} alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₂ o aryl, which are optionally substituted with at least one C1 -C12 alkyl, C1 -C12 perfluoroalkyl, C1 -C12 alkoxy, C ₅ -C ₂ 4 aryloxy, C ₅ -C ₂ o heteroaryloxy, or a halogen atom ;

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a C C ₂₅ alkyl group, R ⁷ and/or R ⁸ may be interconnected with R ⁹ and/or R ¹⁰ to form a cyclic system, they also may be independently the following groups: C^-C^ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl C ₅ -C ₂₀ aryl, C^Cs perfluoralkyl, C ₇ --C ₂₄ aralkyl, C5-C24 perfluoroaryl, which are optionally substituted with at least one C C^ alkyl, CrC^perfluoroalkyl, CrC^ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy or a halogen atom ;

R ^{1 1} , R ¹² are each independently a hydrogen atom, a halogen atom, optionally substituted C C ₂₅ alkyl, optionally substituted C ₁ -C25 perfluoralkyl, optionally substituted C ₂ -C ₂ 5 alkene, optionally substituted C3-C7 cycloalkyl, optionally substituted C ₂ -C ₂ 5 alkenyl, optionally substituted C ₃ -C ₂₅ cycloalkenyl, optionally substituted C ₂ -C ₂₅ alkinyl, optionally substituted C ₃ -C ₂₅ cycloalkinyl, optionally substituted C C ₂ 5 alkoxy, optionally substituted C ₅ -C ₂₄ aryloxy, optionally substituted C ₅ -C ₂₀ heteroaryloxy, optionally substituted C ₅ -C ₂₄ aryl, optionally substituted C ₅ -C ₂₀ heteroaryl, optionally substituted C ₇ -C ₂₄ aralkyl, optionally substituted C ₅ -C ₂₄ perfluoroaryl, optionally substituted 3-12-membered heterocycle;

wherein the substituents R ^{1 1} and R ¹² may be interconnected to form a ring selected from the group consisting of C ₃ -C ₇ cycloalkyl, C ₃ -C ₂₅ cycloalkenyl, C ₃ -C ₂₅ cycloalkinyl, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle, each of which may be substituted with one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C^C^ alkyl, C^C^ perfluoroalkyl, C ₂ -C ₂₅ alkene, C ₃ -C ₇ cycloalkyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₂₅ cycloalkenyl, C ₂ -C ₂₅ alkinyl, C ₃ -C ₂₅ cycloalkinyl, Ci-C ₂₅ alkoxy, C ₅ -C ₂₄ aryloxy, C ₅ -C ₂₀ heteroaryloxy, C ₅ -C ₂₄ aryl, C ₅ -C ₂₀ heteroaryl, C ₇ -C ₂₄ aralkyl, C ₅ -C ₂₄ perfluoroaryl, 3-12-membered heterocycle;

R ¹³ and R ³ are each independently methyl or ethyl;

R ¹⁴ , R ⁴ , R ¹⁵ are each independently a hydrogen atom, a C^C^ alkyl group.

Preferably, compound selected from such as those below is used as compound 1 .

(NitroGrela ,'SIMes> (Hoveyda 2) (Hoveyda 2 ^SIPr )

(Smolen) (BisNHC-lnd)

(Butterfly)

(Grubbs 2) (Bertrand) (LatMet)

(HeatMet) (Starlet) (Pentyl)

Cat. 14 (FixCat)

Cat. 15

(FixCat ^M0F )

Preferably, compound 1 is used deposited on a solid support selected from the group comprising silica gel (Si0 ₂ ), aluminium oxide (Al ₂ 0 ₃ ), zeolites, celite, or MOF (Metal Organic Framework)-like materials, i.e. potentially porous coordination polymers.

Preferably, quinone derivatives are used as an additive in an amount from 5 mol% to 0.05 mol%, preferably such as quinone, anthraquinone, tetrafluoroquinone, tetrachloroquinone and the like.

Preferably, the reaction is conducted in an organic solvent such as toluene, benzene, mesitylene, dichloromethane, ethyl acetate, methyl acetate, tert-butyl methyl ether, cyclopentyl methyl ether, paraffin oil, paraffin wax, ionic liquid, polyethylene, PAO polyalphaolefins, preferably PAO 6 and PAO 4, or without any solvent.

Preferably, the reaction is conducted with olefin Dx and/or olefin Dy at a concentration of between 1 mM and 1 M.

Preferably, the reaction is conducted at a temperature of between 20 and 200°C for between 5 minutes and 24 hours.

Preferably, compound 1 is used in an amount between 2 mol% and 0.0005 mol%.

Preferably, compound 1 is added to the reaction mixture in portions and/or continuously using a pump.

Preferably, compound 1 is added to the reaction mixture as a solid and/or as a solution in an organic solvent. Preferably, olefin Dx and/or olefin Dy is added to the reaction mixture in portions and/or continuously using a pump.

Preferably, the reaction product that is gaseous in the reaction conditions is actively removed from the reaction mixture using inert gas or vacuum.

Preferably, the reaction is conducted at a pressure below the atmospheric pressure, more preferably at a pressure of between 1 bar and 1 -10 ^"6 mbar.

The invention will be presented in greater detail in preferred embodiments, with reference to the accompanying drawing, in which:

Fig. 1 shows ruthenium complexes used as catalysts and/or precatalysts with respective assays (FixCat ^M0F is a heterogeneous catalyst)

Fig. 2 shows different dienes (Dx), which, upon being subjected to the RCM reaction, yield the M11 macrocycle.

Fig. 3 shows macrocyclisations of dienes (Dx) yielding 15-, 16- and 17-membered macrocycles (Mx).

Fig. 4 shows macrocyclisations of dienes(Dx) comprising one (or both) C=C double bonds substituted with methyl (-CH ₃ ) or ethyl (-CH ₂ CH ₃ ).

Fig. 5a shows the gas chromatogram of macrocyclisation conducted by way of the RCM reaction under non-optimised conditions, wherein the large number of signals in the chromatogram indicates non- selectivity of the process (D10 => M9). Reaction conditions: oct-7-en-1 -yl oleate (D10, 0.5 g; 1 .28 mmol); catalyst Cat. 5 (4 mol%); quinone (8 mol%); paraffin oil as solvent (2 g); temperature = 150°C; reaction time = 4 hours; pressure of the order of 1 -10 ³ mbar.

Fig. 5b shows the gas chromatogram of macrocyclisation conducted by way of the RCM reaction under optimised conditions (D12 => M3). Reaction conditions: c/ ^' s-non-6-en-1 -yl oleate (D12, 0.203 g); catalyst Cat. 5 (0.5 %mol); paraffin oil as solvent (2 g); temperature = 1 10°C; reaction time = 8 hours; pressure of the order of 1 0 ^"6 mbar (during the reaction, the pressure varied between approx. 7 0 ^"6 mbar and 2-10 ^"6 mbar)

Fig. 6 shows a graph of the dependence of the RCM reaction yield and concentration by weight (depending on various conditions).

Fig 7a and 7b. Results of the analysis using the MALDI-TOF MS spectrometry method of exam

Fig 8a and 8b. Result of the analysis using the thin-layer chromatography of example XV.

Fig 9 GCMS chromatogram for the reaction of c/ ^' s-non-6-en-1 -yl oleate using Umicore M51™

Fig 10 GCMS chromatogram for the reaction of c/ ^' s-non-6-en-1 -yl oleate in PAO 6

Fig 1 1 GCMS chromatogram for the reaction of c/ ^' s-non-6-en-1 -yl oleate in PAO 4

Fig 12 GCMS chromatogram for the reaction of c/ ^' s-non-6-en-1 -yl oleate using rotary oil pump.

Fig. 13 GCMS chromatogram for the reaction of 3,7-dimethyl-oct-6-en-1 -yl.

Fig. 14 GCMS chromatogram for the reaction of (92)-1 -(((6Z)-non-6-en-1 -ylo)oxy)octadec-9-ene.

Fig. 15 GCMS chromatogram for the reaction of eikosa-1 ,8-dien-5-on. Terms

The terms used in the present description have the meanings as follows. Non-defined terms have the meaning understood by a person skilled in the art in the light of the best knowledge held, of the present disclosure, and of the context of the description of the patent application. Unless it is indicated otherwise, the following conventional chemistry terms are used the present description that have the meanings indicated in the definitions below.

The term "halogen atom" or "halogen" refers to an element selected from F, CI, Br, I.

The term "carbene" refers to a particle containing an neutral carbon atom with a valence number of two and having two unpaired (triplet state) or paired (singlet state) valence electrons. The term "carbene" also includes carbene analogs in which the carbon atom is substituted by another chemical element such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulphur, selenium and tellurium.

The term "alkyl' refers to a saturated, linear or branched hydrocarbon substituent having the indicated number of carbon atoms. Examples of alkyl substituents include -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, and -n-decyl. Representative branched -(CrC^alkyls include -isopropyl, -sec-butyl, -isobutyl, -ferf-butyl, -isopentyl, -neopentyl, -1 -methylobutyl, -2-methylobutyl, -3-methylobutyl, -1 ,1 -dimethylopropyl, -1 ,2-dimethylopropyl, -1 -methylopentyl, -2-methylopentyl, -3-methylopentyl, -4-methylopentyl, -1 -ethylobutyl, -2-ethylobutyl, -3-ethylobutyl, -1 ,1 -dimethylobutyl, -1 ,2-dimethylobutyl, 1 ,3-dimethylobutyl, -2,2-dimethylobutyl, -2,3-dimethylobutyl, -3,3-dimethylobutyl, -1 -methylohexyl, 2-methylohexyl, -3-methylohexyl, -4-methylohexyl, -5-methylohexyl, -1 ,2-dimethylopentyl, -1 ,3-dimethylopentyl, -1 ,2-dimethylohexyl, -1 ,3-dimethylohexyl, -3,3-dimethylohexyl, 1 ,2-dimethyloheptyl, -1 ,3-dimethyloheptyl, -3,3-dimethyloheptyl and the like.

The term "alkoxy" refers to an alkyl substituent as defined above bound by an oxygen atom.

The term "perfluoroalkyf refers to an alkyl group as defined above in which all the hydrogen atoms have been substituted by the same or different halogen atoms.

The term "cycloalkyf refers to a saturated mono- or polycyclic hydrocarbon substituent having the indicated number of carbon atoms. Examples of cycloalkyl substituents include -cyclopropyl, -cyclobutyl, -cyclopentyl, -cyclohexyl, -cycloheptyl, -cyclooctyl, -cyclononyl, -cyclodecyl and the like.

The term„alkenyf refers to a non-saturated, linear or branched non-cyclic hydrocarbon substituent of the indicated number of carbon atoms and containing at least one double carbon-carbon bond. Examples of alkenyl substituents include -vinyl, -allyl, -1 -butenyl, -2-butenyl, -isobutenyl, -1 -pentenyl, -2-pentenyl, -3-methylo-1 -butenyl, -2-methylo-2-butenyl, 2,3-dimethylo-2-butenyl, -1 -hexenyl, -2-hexenyl, -3-hexenyl, -1 -heptenyl, -2-heptenyl, -3-heptenyl, -1 -octenyl, -2-octenyl, -3-octenyl, -1 -nonenyl, -2-nonenyl, -3-nonenyl, -1 -decenyl, -2-decenyl, -3-decenyl and the like.

The term "cycloalkenyf refers to a non-saturated mono- or polycyclic hydrocarbon substituent of the indicated number of carbon atoms and containing at least one double carbon-carbon bond. Examples of cycloalkenyl substituents include -cyclopentenyl, -cyclopentadienyl, -cyclohexenyl, -cyclohexadienyl, -cycloheptenyl, -cycloheptadienyl, -cycloheptatrienyl, -cyclooctenyl, -cyclooctadienyl, -cyclooctatrienyl, -cyclooctatetraenyl, -cyclononenyl, -cyclopentadienyl, -cyclodecenyl, -cyclodecadienyl and the like. The term„alkinyf refers to a non-saturated, linear or branched non-cyclic hydrocarbon substituent of the indicated number of carbon atoms and containing at least one triple carbon-carbon bond. Examples of alkynyl substituents include -acetylenyl, -propynyl, -1 -butynyl, -2-butynyl, -1 -pentynyl, -2-pentynyl, -3-methyl-1 -butynyl, 4-pentynyl, -1 -hexynyl, 2-hexynyl, -5-hexynyl and the like.

The term "cycloalkynyf refers to a non-saturated mono- or polycyclic hydrocarbon substituent of the indicated number of carbon atoms and containing at least one triple carbon-carbon bond. Examples of cycloalkynyl substituents include -cyclohexyl, -cycloheptynyl, -cyclooctynyl and the like.

The term "aryf refers to an aromatic mono- or polycyclic hydrocarbon substituent having the indicated number of carbon atoms. Examples of aryl substituents include phenyl, -tolyl, -xylyl, -naphthyl, -2,4,6-trimethylphenyl, -2-fluorophenyl, -4-fluorophenyl, -2,4,6-trifluorophenyl, -2,6-difluorophenyl, -4-nitrophenyl and the like.

The term "aralkyf refers to an alkyl substituent as defined above substituted with at least one aryl as defined above. Examples of aralkyl substituents include -benzyl, -diphenylmethyl, -triphenylmethyl and the like.

The term "heteroaryf refers to an aromatic mono- or polycyclic hydrocarbon substituent having the indicated number of carbon atoms, in which at least one carbon atom is substituted by a heteroatom selected from O, N and S atoms. Examples of heteroaryl substituents include -furyl, -thienyl, -imidazolyl, -oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, -oxadiazolyl, -thiadiazolyl, -tetrazolyl, -pyridyl, -pyrimidyl, -triazinyl, -indolyl, -benzo[b]furyl, -benzo[b]thienyl, -indazolyl, -benzoimidazolyl, -azaindolyl, -quinolyl, -isoquinolyl, -carbazolyl and the like.

The term "heterocycle" refers to a saturated or partially non-saturated, mono- or polycyclic hydrocarbon substituent having the indicated number of carbon atoms, in which at least one carbon atom is substituted by a heteroatom selected from O, N and S atoms. Examples of heterocyclic substituents include furyl, thiophenyl, pyrrolyl, oxazolyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, triazinyl, pyrrolidinonyl, pyrrolidinyl, hydantoinyl, oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydrothiophenyl, quinolinyl, isoquinolinyl, chromonyl, coumarinyl, indolyl, indolizinyl, benzo[b]furanyl, benzo[b]thiophenyl, indazolyl, purinyl, 4 -/-quinolizinyl, isoquinolyl, quinolyl, phthalazinyl , naphthyridinyl, carbazolyl, β-carbolinyl and the like.

The term "neutral ligancf' refers to a non-charged substituent capable of coordinating with a metallic centre (the ruthenium atom). Examples of such ligands may include: amines, phosphines and oxides thereof, alkyl and aryl phosphites and phosphates, arsines and oxides thereof, ethers, alkyl and aryl sulphides, coordinated hydrocarbons, alkyl and aryl halides.

The term "anionic ligand' refers to a substituent capable of coordinating with a metallic centre (the ruthenium atom) with a charge capable of partially or completely compensating the charge of the metallic centre. Examples of such ligands may include fluoride, chloride, bromide, iodide, cyanide, cyanate and thiocyanate anions, carboxylic acid anions, alcohol anions, phenolic anions, thiol and thiophenol anions, delocalized charge hydrocarbon anions (e.g. cyclopentadiene), (organo)sulphuric and (organo)phosphoric acid anions and esters thereof (such as, for example, alkylsulphonic and aryl sulphonic acid anions, alkylphosphoric and arylphosphoric acid anions, sulphuric acid alkyl and aryl ester anions, phosphoric acid alkyl and aryl ester anions, alkylphosphoric and arylphosphoric alkyl and aryl ester anions). Optionally, the anionic ligand may have interconnected L ¹ , L ² and L ³ groups, such as the catechol anion, the acetylacetone anion, the salicylaldehyde anion. Anionic ligands (X ¹ , X ² ) and neutral ligands (L ¹ , L ² , L ³ ) may be interconnected to form multidentate ligands, such as a bidentate ligand (X ¹ -X ² ), a tridentate ligand (X ¹ -X ² -L ¹ ), a tetradentate ligand (X ¹ -X ² -L ¹ -L ² ), a bidentate ligand (X ¹ -L ¹ ), a tridentate ligand (X ¹ -L ¹ -L ² ), a tetradentate ligand (X ¹ -L ¹ -L ² -L ³ ), a bidentate ligand (L ¹ -L ² ), a tridentate ligand (L ¹ -L ² -L ³ ). Examples of such ligands include catechol anion, acetylacetone anion and salicylaldehyde anion.

The term "heteroatom" refers to an atom selected from the group comprising an atom of oxygen, sulphur, nitrogen, phosphorus and the like.

The term "chlorinated solvent' refers to a solvent, the structure of which comprises at least one atom of for example fluorine, chlorine, bromine and iodine; preferably more than one. Examples of such solvents include dichloromethane, chloroform, tetrachloromethane (carbon tetrachloride), 1 ,2-dichloroethane, chlorobenzene, perfluorobenzene, perfluorotoluene, freons and the like.

The term "organic non-polar solvent refers to a solvent characterised by non-existent or very low dipole momentum. Examples of such solvents include pentane, hexane, octane, nonane, decane, benzene, toluene, xylene and the like.

The term "organic polar solvent refers to a solvent characterised by a dipole momentum substantially greater than zero. Examples of such solvents include dimethylformamide (DMF), tetrahydrofuran (THF) and its derivatives, diethyl ether, dichloromethane, ethyl acetate, chloroform, alcohols (MeOH, EtOH or i- PrOH) and the like.

The term "GC refers to gas chromatography.

The term „PAO" refers to poly-alpha-olefins, a group of polymers produced using alpha-olefins as monomers, i.e. alkenes containing a terminal double bond, i.e. between 1 st and 2nd carbon atom. Commercially available poly-alpha-olefins are designated with the abbreviation PAO and a number indicating the kinematic viscosity of the polymer at a temperature of 100°C.

The term„GCMS' denotes gas chromatography-mass spectrometry.

The term "HPLC refers to high performance liquid chromatography, and solvents designated as "HPLC" solvents refer to solvents having sufficient purity for HPLC analysis.

The term "NMFt refers to nuclear magnetic resonance.

The term "NHC refers to /V-heterocycl carbene.

The term "precatalyst refers to, in relation to ruthenium complexes, a 16-electron chemical compound which, after the step of dissociation of one ligand or reorganisation of the molecule, is converted to the 14-electron olefin metathesis catalyst as such, which is active in the catalytic cycle.

The term " TFQ' denotes tetrafluoro-1 , 4-benzoquinone (CAS: 527-21 -9).

The term „diene" as used in this patent document refers to substrates used for the macrocyclization reaction by way of RCM reaction. It is not strictly used, it rather refers to compounds where the pair of C=C double bonds co-reacts in the RCM reaction, resulting in a product, i.e. a cyclic olefin . Some Dx and Dy compounds herein may contain more than two C=C double bonds. The phrase substituted with at least one substituenf means that a group may be substituted with one substituents from those specified, two such substituents or more, up to the maximum number depending on the valency of the substituted atom, provided that such substitution results in a chemically stable molecule.

The term„effective efficiency' means the weighed yield of all resulting RCM macrocyclization products obtained in the reaction based on the expected macrocyclic compound. The effective yield, then determined in % based on the GC or GCMS chromatogram of the post-reaction mixture with respect to the expected product. The effective efficiency was used only for processes with low selectivity of the reaction. The low selectivity of the reaction is associated with the C=C double bond migration process, whereby the GC-MS chromatograph has registered a series of cyclic compounds differing by their mass ± „n CH ₂ ". Comparison of fig. 5a and fig. 5b.

Embodiments of the invention

The following examples are provided solely for the purpose of illustrating the invention and for clarifying the individual aspects thereof, and not with the intention to limit it, and should not be considered to be equivalent to the total scope thereof as defined in the appended claims. In the examples below, unless otherwise indicated, standard materials and methods were employed as used in the art or it was proceeded according to the manufacturer's recommendations for particular reagents and methods.

Example I

General method for the preparation of diene esters (Dx), substrates for the RCM reaction

A suitable carboxylic acid K1 , K2, K3 or K4 (1 eq.) was dissolved in anhydrous methylene chloride under an inert gas atmosphere. A few drops of A/,/V-dimethylformamide were added, and then oxalyl chloride (1 .2 eq.) was added dropwise at room temperature. Gas emission and change of colour to yellow were observed. After an hour, substrate conversion was checked using ¹ H NMR. Methylene chloride and unreacted oxalyl chloride were evaporated using a membrane pump. A new portion of solvent was added and the reaction mixture was cooled to a temperature of -78°C. Pyridine (2 eq.) was added dropwise, followed by suitable A1 - A9 alcohol (0.9 - 1 .1 eq.). The reaction was conducted for an hour, while monitoring the progress using thin-layer chromatography (TLC). The product was purified by column chromatography with 0.5% EtOAc/n-hexane (v/v).

K1 K2

K4

K3 K5 K6

Carboxylic acids (Kx)

A1 A2 A3

A4 A5 A6

OH

A7 A8

OH

A10

Alcohols (Ax)

The procedure described above yielded the following dienes (Dx), substrates for the RCM reaction,

9-decanoic acid esters:

a) dec-9-en-1 -yl dec-9-enoate (D1 ):

D1

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.77 - 5.64 (m, 2H), 4.93 - 4.79 (m, 4H), 3.95 (t, J = 6.7 Hz, 2H), 2.19 (t, J = 7.5 Hz, 2H), 1 .97 - 1 .88 (m, 4H), 1 .56 - 1 .48 (m, 4H), 1 .30 - 1 .16 (m, 18H).

¹³ C NMR(101 MHz, CDCI ₃ ): δ (ppm) = 174.15 (CO), 139.30 (CH), 139.26 (CH), 1 14.33 (CH ₂ ), 1 14.31 (CH ₂ ), 64.54 (CH ₂ ), 34.54 (CH ₂ ), 33.92 (CH ₂ ), 29.50 (CH ₂ ), 29.34 (CH ₂ ), 29.25 (CH ₂ ), 29.24 (CH ₂ ), 29.18 (CH ₂ ), 29.08 (CH ₂ ), 29.03 (CH ₂ ), 28.99 (CH ₂ ), 28.78 (CH ₂ ), 26.06 (CH ₂ ), 25.15 (CH ₂ ).

b) dec-9-enoate octo-7-en-1 -yl (D2):

D2 ¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.86 - 5.74 (m, 2H), 5.03 - 4.89 (m, 4H), 4.05 (t, J = 6.7 Hz, 2H), 2.33-2.23 (m, 2H), 2.09- 1.98 (m, 4H), 1.68- 1.55 (m, 4H), 1.44- 1.23 (m, 14H).

¹³ C NMR(101 MHz, CDCI ₃ ): δ (ppm) = 174.13 (CO), 139.27 (CH), 139.11 (CH), 114.46 (CH ₂ ), 114.33 (CH ₂ ), 64.49 (CH ₂ ), 34.54 (CH ₂ ), 33.91 (CH ₂ ), 33.82 (CH ₂ ), 29.26 (CH ₂ ), 29.24 (CH ₂ ), 29.08 (CH ₂ ), 28.99 (CH ₂ ), 28.91 (CH ₂ ), 28.86 (CH ₂ ), 28.74 (CH ₂ ), 25.94 (CH ₂ ), 25.14 (CH ₂ ).

c) dec-9-enoate hex-5-en-1-yl (D3):

D3

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.86 - 5.74 (m, 2H), 5.05 - 4.89 (m, 4H), 4.07 (t, J = 6.6 Hz, 2H), 2.29 (t, J= 7.5 Hz, 2H), 2.14-1.98 (m, 4H), 1.70-1.54 (m, 4H), 1.52-1.22 (m, 10H).

¹³ C NMR(101 MHz, CDCI ₃ ): δ (ppm) = 174.11 (CO), 139.27 (CH), 138.51 (CH), 114.94 (CH ₂ ), 114.33 (CH ₂ ), 64.30 (CH ₂ ), 34.52 (CH ₂ ), 33.91 (CH ₂ ), 33.44 (CH ₂ ), 29.25 (CH ₂ ), 29.24 (CH ₂ ), 29.07 (CH ₂ ), 28.99 (CH ₂ ), 28.23 (CH ₂ ), 25.35 (CH ₂ ), 25.13 (CH ₂ ).

d) dec-9-enoate c/s-non-6-en-1-yl D4):

D4

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.86 - 5.74 (m, 1 H), 5.41 - 5.26 (m, 2H), 5.04 - 4.90 (m, 2H), 4.05 (t, J = 6.7 Hz, 2H), 2.29 (t, J = 7.5 Hz, 2H), 2.08 - 1.98 (m, 6H), 1.70 - 1.57 (m, 4H), 1.44 - 1.25 (m, 12H), 0.96 (t, J= 7.5 Hz, 3H).

¹³ C NMR(101 MHz, CDCI ₃ ): δ (ppm) = 174.12 (CO), 139.27 (CH), 132.00 (CH), 128.97 (CH), 114.33 (CH ₂ ), 64.48 (CH ₂ ), 34.53 (CH ₂ ), 33.91 (CH ₂ ), 29.49 (CH ₂ ), 29.26 (CH ₂ ), 29.24 (CH ₂ ), 29.07 (CH ₂ ), 28.99 (CH ₂ ), 28.71 (CH ₂ ), 27.07 (CH ₂ ), 25.71 (CH ₂ ), 25.14 (CH ₂ ), 20.67 (CH ₂ ), 14.53 (CH ₃ ).

e) dec-9-enoate 3,7-dimethyl-octo-6-en-1 -yl D5):

D5

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.87 - 5.73 (m, 1 H), 5.08 (m, 1 H), 5.03 - 4.88 (m, 2H), 4.26 - 4.01 (m, 2H), 2.35 - 2.23 (m, 2H), 2.11 -1.89 (m, 4H), 1.73 - 1.10 (m, 20H), 0.91 (d, J = 7.5 Hz, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.12 (CO), 139.27 (CH), 131.47 (C), 124.71 (CH), 114.33 (CH ₂ ), 62.91 (CH ₂ ), 37.13 (CH ₂ ), 35.62 (CH ₂ ), 34.56 (CH ₂ ), 33.91 (CH ₂ ), 29.63 (CH), 29.25 (CH ₂ ), 29.08 (CH ₂ ), 28.99 (CH ₂ ), 25.88 (CH ₃ ), 25.54 (CH ₂ ), 25.14 (CH ₂ ), 19.56 (CH ₃ ), 17.81 (CH ₃ ). dec-9-enoatefrans-3,7-dimethylocto-2, 6-dien-1 -yl( D6 :

D6

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.87 - 5.73 (m, 1 H), 5.38 - 5.28 (m, 1 H), 5.13 - 5.04 (m, 1 H), 5.03 - 4.86 (m, 2H), 4.59 (d, J = 7.1 Hz, 2H), 2.33 - 2.25 (m, 2H), 2.15 - 1 .99 (m, 6H), 1 .69 (dd, J = 7.9, 0.8 Hz, 6H), 1 .66 - 1 .54 (m, 5H), 1 .42 - 1 .24 (m, 8H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.05 (CO), 142.27 (C), 139.27 (CH), 131 .97 (C), 123.89 (CH), 1 18.52 (CH _), 1 14.32 (CH ₂ ), 61 .33 (CH ₂ ), 39.68 (CH ₂ ), 34.52 (CH ₂ ), 33.92 (CH ₂ ), 29.25 (CH ₂ ), 29.23 (CH ₂ ), 29.07 (CH ₂ ), 28.99 (CH ₂ ), 26.44 (CH ₂ ), 25.84 (CH ₃ ), 25.13 (CH ₂ ), 17.84 (CH ₃ ), 16.62 (CH ₃ ).

g) dec-9-enoate c/ ^' s-3,7-dimethylocto-2, 6-dien-1 -yl

D7

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.87 - 5.73 (m, 1 H), 5.38 - 5.28 (m, 1 H), 5.13 - 5.04 (m, 1 H), 5.03 - 4.86 (m, 2H), 4.56 (dd, J = 7.3, 0.8 Hz, 2H), 2.33 - 2.25 (m, 2H), 2.15 - 1 .99 (m, 6H), 1 .76 (d, J = 1 .3 Hz, 3H), 1 .70 - 1 .57 (m, 8H), 1 .42 - 1 .24 (m, 8H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174,03 (CO), 142,65 (C), 139,28 (CH) 132,30 (C), 123,72 (CH) 1 19,39 (CH), 1 14,32 (CH ₂ ), 61 ,05 (CH ₂ ), 34,53 (CH ₂ ), 33,91 (CH ₂ ), 32,31 (CH ₂ ), 29,25 (CH ₂ ), 29,07 (CH ₂ ), 28,99 (CH ₂ ), 26,82 (CH ₂ ) 25,85 (CH ₃ ) 25,12 (CH ₂ ), 23,68(CH ₃ ), 17,81 (CH ₃ ).

h) oleyl dec-9-enoate (D8):

D8

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.87 - 5.72 (m, 1 H), 5.41 - 5.27 (m, 2H), 5.04 - 4.89 (m, 2H), 4.05 (t, J = 6.7 Hz, 2H), 2.28 (t, J = 7.5 Hz, 2H), 2.08 - 1 .97 (m, 6H), 1 .50 - 1 .16 (m, 30H), 0.88 (t, J = 6.5 Hz, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 169.87, 145.71 , 139.23, 139.07, 1 14.47, 1 14.34, 101 .82, 53.85, 33.89, 33.84, 29.45, 29.17, 29.03, 28.98, 28.97, 28.88, 28.87, 27.62, 26.43, 24.75. Oleic acid esters

a) dec-9-en-1-yl oleinate (D9):

D9

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.86 - 5.74 (m, 1H), 5.41 - -5.26 (m, 2H), 5.05 - 4.90 (m, 2H), 4.05 (t, J = 6.7 Hz, 2H), 2.28 (t, J = 7.5 Hz, 2H), 2.06 - 1.94 (m, 6H), 1.49 - 1.17 (m, 30H), 0.88 (t, J = 6.5 Hz, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.15, 139.30, 130.13, 129.89, 114.31, 64.53, 34.55, 33.94, 32.06, 29.92, 29.84, 29.68, 29.50, 29.48, 29.34, 29.33, 29.29, 29.26, 29.18, 29.03, 28.78, 27.37, 27.31, 26.06, 25.16, 22.84, 14.28.

b) octo-7-en-1-yl oleate (D10):

D10

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.89-5.71 (m, 1H), 5.43-5.27 (m, 2H), 5.10-4.86 (m, 2H), 4.05 (t, J= 6.7 Hz, 2H), 2.29 (t, J =7.5 Hz, 2H), 1.47-1.19 (m, 24H), 0.97-0.81 (m, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.14, 139.11, 130.14, 129.90, 114.46, 64.49, 34.55, 33.83, 32.06, 29.93, 29.85, 29.68, 29.48, 29.33, 29.30, 29.27, 28.92, 28.86, 28.75, 27.37, 27.32, 25.94, 25.17, 22.84, 14.28.

c) hex-5-en-1-yl oleate (D11):

D11

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.80 (ddt, J= 16.9, 10.2, 6.7 Hz, 1H), 5.42 - 5.27 (m, 2H), 5.09 - 4.90 (m, 2H), 4.07 (t, J = 6.6 Hz, 2H), 2.29 (t, J = 7.4 Hz, 2H), 2.14- 1.96 (m, 4H), 1.70 - 1.57 (m, 4H), 1.52 - 1.39 (m, 2H), 1.38 - 1.21 (m, 22H), 0.92 - 0.84 (m, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.12, 138.51, 130.14, 129.89, 114.95, 64.30, 34.53, 33.44, 32.06, 29.92, 29.85, 29.68, 29.48, 29.33, 29.29, 29.26, 28.23, 27.37, 27.32, 25.35, 25.16, 22.84, 14.28.

d) c/ ^' s-non-6-en-1-yl oleate (D12):

D12 ¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.45 - 5.24 (m, 4H), 4.05 (t, J = 6.7 Hz, 2H), 2.36 - 2.23 (m, 2H), 2.11 - 1.92 (m, 8H), 1.69 - 1.57 (m, 4H), 1.45 - 1.22 (m, 24H), 0.95 (t, J = 7.6 Hz, 3H), 0.90 - 0.86 (m, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.13, 132.01, 130.14, 129.90, 128.97, 64.48, 34.55, 32.06, 29.92, 29.85, 29.68, 29.50, 29.48, 29.34, 29.29, 29.27, 28.71, 27.37, 27.32, 27.08, 25.71, 25.17, 22.84, 20.67, 14.53, 14.28.

e) 3,7-dimethyl-octo-6-en-1 -yl oleate (D13):

D13

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.43 - 5.26 (m, 2H), 5.08 (t _septete , J = 7.1, 1.4 Hz, 1H), 4.16-4.03 (m, 2H), 2.28 (t, J = 7.6 Hz, 2H), 2.07 - 1.88 (m, 6H), 1.70 - 1.66 (m, 3H), 1.61 - 1.59 (m, 3H), 1.72 - 1.38 (m, 6H), 1.37-1.23 (m, 20H), 1.23-1.12 (m, 1H), 0.97-0.82 (m, 6H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.13, 131.47, 130.13, 129.89, 124.71, 62.92, 37.13, 35.62, 34.57, 32.06, 29.92, 29.85, 29.68, 29.63, 29.48, 29.33, 29.29, 29.27, 27.37, 27.32, 25.88, 25.54, 25.16, 22.84, 19.56, 17.80, 17.80, 14.28.

f) trans-3, 7-dimethylocto-2, 6-dien-1-yl oleate(D14 :

D14

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.40 - 5.26 (m, 3H), 5.12 - 5.05 (m, 1H), 4.59 (d, J= 7.1 Hz, 2H), 2.29 (t, J = 7.6 Hz, 2H), 2.14- 1.94 (m, 8H), 1.73 - 1.66 (m, 6H), 1.66 - 1.55 (m, 6H), 1.39 - 1.21 (m, 20H), 0.93-0.83 (m, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.06, 142.27, 131.96, 130.13, 129.90, 123.89, 118.52, 61.33, 39.68, 34.54, 32.06, 29.92, 29.85, 29.68, 29.48, 29.33, 29.28, 29.26, 27.37, 27.32, 26.44, 25.84, 25.16, 22.84, 17.84, 16.62, 14.28. g) c/ ^' s-3,7-dimethylocto-2, 6-dien-1-yl oleate(D15:

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.40-5.27 (m, 3H), 5.13-5.05 (m, 1H), 4.59-4.52 (m, 2H), 2.29 (t, J = 7.6 Hz, 2H), 2.16 - 1.94 (m, 8H), 1.76 (q, J = 1.1 Hz, 3H), 1.71 - 1.65 (m, 3H), 1.67 - 1.54 (m, 5H), 1 .38 - 1 .21 (m, 20H), 0.92 - 0.83 (m, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.05, 142.64, 132.30, 130.13, 129.90, 123.72, 1 19.39, 61 .05, 34.54, 32.31 , 32.06, 29.92, 29.84, 29.68, 29.48, 29.33, 29.29, 29.26, 27.36, 27.32, 26.81 , 25.85, 25.14, 23.68, 22.84, 17.82, 14.28.

h) oleyl oleate (D16):

D16

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.40 - 5.30 (m, 4H), 4.05 (t, J = 6.7 Hz, 2H), 2.29 (t, J = 7.6 Hz, 2H), 2.06 - 1 .96 (m, 8H), 1 .68 - 1 .56 (m, 4H), 1 .40 - 1 .20 (m, 42H), 0.88 (t, J = 6.8 Hz, 6H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.15, 130.14, 130.12, 129.93, 129.90, 124.73, 64.55, 34.55, 32.06, 29.92, 29.89, 29.85, 29.68, 29.58, 29.48, 29.39, 29.37, 29.33, 29.29, 29.27, 28.80, 27.37, 27.34, 27.32, 26.08, 25.17, 22.85, 14.28.

Esters of 9-decenoic acid following isomerization of double bonds

a) dec-8-en-1 -yl dec-8-enoate (D17):

D17

¹ H NMR (400 MHz, (CD ₃ ) ₂ CO): δ (ppm) = 5.48 - 5.32 (m, 4H), 4.02 (t, 2H, J = 6.7 Hz), 2.27 (t, 2H, J = 7.4 Hz), 2.01 - 1 .91 (m, 4H), 1 .71 - 1 .54 (m, 10H), 1 .38 - 1 .12 (m, 14H).

¹³ C NMR (100 MHz, (CD ₃ ) ₂ CO): δ (ppm) = 173.4 (CO), 132.1 (CH), 132.1 (CH), 125.2 (CH), 125.1 (CH), 64.4 (CH ₂ ), 34.5 (CH ₂ ), 33.2 (CH ₂ ), 33.1 (CH ₂ ), 30.2 (CH ₂ ), 30.1 (CH ₂ ), 29.8 (CH ₂ ), 29.7 (CH ₂ ), 29.6 (CH ₂ ), 29.5 (CH ₂ ), 29.4 (CH ₂ ), 26.6 (CH ₂ ), 25.6 (CH ₂ ), 18.0 (2*CH ₃ ).

b) c/ ^' s-non-6-en-1 -yl dec-8-enoate D18):

D18

¹ H NMR (400 MHz, (CD ₃ ) ₂ CO): δ (ppm) = 5.46 - 5.27 (m, 4H), 4.03 (t, 2H, J = 6.6 Hz), 2.27 (t, 2H, J = 7.4 Hz), 2.07 - 1 .94 (m, 6H), 1 .63 - 1 .56 (m, 7H), 1 .38 - 1 .30 (m, 10H), 0.93 (t, 3H, J = 7.6 Hz).

¹³ C NMR (100 MHz, (CD ₃ ) ₂ CO): δ (ppm) = 173.5 (CO), 132.3 (CH), 132.1 (CH), 129.6 (CH), 125.2 (CH), 64.4 (CH ₂ ), 34.6 (CH ₂ ), 33.2 (CH ₂ ), 30.1 (CH ₂ ), 30.0 (CH ₂ ), 29.6 (CH ₂ ), 29.5 (CH ₂ ), 29.3 (CH ₂ ), 27.5 (CH ₂ ), 26.2 (CH ₂ ), 25.6 (CH ₂ ), 21 .0 (CH ₂ ), 18.0 (CH ₃ ), 14.6 (CH ₃ ). c) octo-6-en-1 -yl dec-8-enoate (D19):

D19

¹ H NMR (400 MHz, (CD ₃ ) ₂ CO): δ (ppm) = 5.42 - 5.39 (m, 4H), 4.02 (t, 2H, J = 6.6 Hz), 2.26 (t, 2H, J = 7.4 Hz), 2.00 - 1 .93 (m, 4H), 1 .66 - 1 .54 (m, 10H), 1 .39 - 1 .29 (m, 10H).

¹³ C NMR (100 MHz, (CD ₃ ) ₂ CO): δ (ppm) = 173.5 (CO), 132.1 (CH), 132.0 (CH), 125.3 (CH), 125.2 (CH), 64.4 (CH ₂ ), 34.6 (CH ₂ ), 33.1 (CH ₂ ), 33.1 (CH ₂ ), 30.1 (CH ₂ ), 29.9 (CH ₂ ), 29.6 (CH ₂ ), 29.5 (CH ₂ ), 29.3 (CH ₂ ), 26.1 (CH ₂ ), 25.6 (CH ₂ ), 18.0 (2*CH ₃ ).

d) dec-9-en-1 -yl dec-8-enoate (D20):

D20

¹ H NMR (400 MHz, (CDCI ₃ ): δ (ppm) = 5.91 - 5.69 (m, 1 H), 5.54 - 5.30 (m, 2H), 5.08 - 4.86 (m, 2H), 4.05 (t, J = 6.7 Hz, 2H), 2.37 - 2.24 (m, 2H), 2.09 - 2.00 (m, 2H), 2.00 - 1 .91 (m, 2H), 1 .70 - 1 .53 (m, 8H), 1 .45 - 1 .21 (m, 13H).

¹³ C NMR(100 MHz, CDCI ₃ ): δ (ppm) = 174.14 (CO), 139.30 (CH), 131 .60 (CH), 124.85 (CH), 1 14.30 (CH ₂ ), 64.54 (CH ₂ ), 34.55 (CH ₂ ), 33.93 (CH ₂ ), 32.65 (CH ₂ ), 29.54 (CH ₂ ), 29.50 (CH ₂ ), 29.34 (CH ₂ ), 29.18 (CH ₂ ), 29.17 (CH ₂ ), 29.03 (CH ₂ ), 28.92 (CH ₂ ), 28.79 (CH ₂ ), 26.06 (CH ₂ ), 25.14 (CH ₂ ), 18.07 (CH ₂ ).

e) octo-7-en-1 -yl dec-8-enoate (D21 ):

D21

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.80 (ddt, J = 17.0, 10.2, 6.7 Hz, 1 H), 5.58 - 5.30 (m, 2H), 5.09 - 4.86 (m, 2H), 4.05 (t, J = 6.7 Hz, 2H), 2.28 (t, J = 7.5 Hz, 2H), 2.09 - 2.00 (m, 2H), 1 .99 - 1 .91 (m, 2H), 1 .70 - 1 .57 (m, 6H), 1 .46 - 1 .22 (m, 13H).

¹³ C NMR(100 MHz, CDCI ₃ ): δ (ppm) = 174.13 (CO), 139.10 (CH), 131 .59 (CH), 124.85 (CH), 1 14.45 (CH ₂ ), 64.48 (CH ₂ ), 34.54 (CH ₂ ), 33.82 (CH ₂ ), 32.64 (CH ₂ ), 29.53 (CH ₂ ), 29.17 (CH ₂ ), 28.91 (CH ₂ ), 28.85 (CH ₂ ), 28.75 (CH ₂ ), 25.94 (CH ₂ ), 25.13 (CH ₂ ), 18,07 (CH ₂ ).

f) octo-6-en-1 -yl dec-9-enoate (D22):

D22

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.80 (ddt, J = 16.9, 10.2, 6.7 Hz, 1 H), 5.48 - 5.33 (m, 2H), 5.13 - 4.84 (m, 2H), 4.05 (t, J = 6.7 Hz, 2H), 2.29 (t, J = 7.5 Hz, 2H), 2.12 - 1 .92 (m, 4H), 1 .71 - 1 .56 (m, 6H), 1 .46 - 1 .24 (m, 13H).

¹³ C NMR(100 MHz, CDCI ₃ ): δ (ppm) = 174.1 1 (CO), 139.26 (CH), 131 .32 (CH), 125.07 (CH), 1 14,33 (CH ₂ ), 64.48 (CH ₂ ), 34.54 (CH ₂ ), 33.91 (CH ₂ ), 32.56 (CH ₂ ), 29.31 (CH ₂ ), 29.25 (CH ₂ ), 29.24 (CH ₂ ), 29.08 (CH ₂ ), 28.99 (CH ₂ ), 28.67 (CH ₂ ), 25.58 (CH ₂ ), 25.14 (CH ₂ ), 18.07 (CH ₃ ).

g) hex-5-en-1 -yl undec-10-enoate (D23):

D23

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.80 (ddtd, J = 16.9, 10.1 , 6.7, 4.3 Hz, 2H), 5.07 - 4.86 (m, 4H), 4.06 (t, J = 6.6 Hz, 2H), 2.32 - 2.25 (m, 2H), 2.14 - 1 .95 (m, 4H), 1 .73 - 1 .54 (m, 4H), 1 .50 - 1 .41 (m, 2H), 1 .40 - 1 .25 (m, 10H).

¹³ C NMR (100 MHz, CDCI ₃ ): δ (ppm) = 174.13 (CO), 139.33 (CH), 138.51 (CH), 1 14.94 (CH ₂ ), 1 14.28 (CH ₂ ), 64.29 (CH ₂ ), 34.52 (CH ₂ ), 33.94 (CH ₂ ), 33.44 (CH ₂ ), 29.44 (CH ₂ ), 29.35 (CH ₂ ), 29.28 (CH ₂ ), 29.20 (CH ₂ ), 29.03 (CH ₂ ), 28.22 (CH ₂ ), 25.35 (CH ₂ ), 25.14 (CH ₂ ).

Example II

An alternative esterification reaction yielding dienes used in the metathesis cvclization RCM (PRF = porous phenolsulfonic acid-formaldehyde resin catalyst).

R, R' = H or C ₈ H ₁₇

n = 4 or 7

Carboxylic acid (1 eq.), alcohol (1 eq.) and a PRF (porous phenolsulfonic acid formaldehyde resin) catalyst (10 mg/1 mmol acid) were placed in a single-necked round flask with a stirring element, prepared according to the procedure known from literature [M. Minakawa, H. Baek, Y. M. A. Yamada, J. W. Han, Y. Uozumi, Org. Lett, 2013, 15, 5798-5801 ]). The reaction flask was then sealed with a glass stopper and placed in an oil bath at a temperature of 90°C for 14 hours. Afterwards, the reaction mixture was cooled to room temperature and diluted with n-heptane approx. tenfold. After filtering off the catalyst, the mixture was concentrated under reduced pressure and the crude product was purified by column chromatography using silica gel and 1 % EtOAc/n-heptane mixture (v/v) as eluent.

a) Oleyl oleate (D16):

D16 Obtained according to the general procedure using: oleic acid (0.72 g, 2.6 mmol), oleic alcohol (0.68 g, 2.6 mmol) and PSF (26 mg).92% yield (1.15 g).

¹ H NMR (400 MHz, CDCI ₃ ) δ (ppm) = 5.41 - 5.24 (m, 4H), 4.05 (t, J = 6.7 Hz, 2H), 2.29 (t, J = 7.5 Hz, 2H), 2.09 - 1.90(m, 8H), 1.73 - 1.49 (m, 4H), 1.39 - 1.20 (m, 42H), 0.88 (t, J= 6.8 Hz, 6H) ppm

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.14, 130.13, 130.11, 129.92, 129.89, 64.54, 34.55, 32.06, 29.92, 29.88, 29.85, 29.68, 29.58, 29.48, 29.39, 29.37, 29.33, 29.29, 29.27, 28.80, 27.37, 27.34, 27.32, 26.08, 25.17, 22.84, 14.28 ppm.

b) Hept-6-en-1-yl oleate (D24):

D24

Obtained according to the general procedure using: oleic acid (1.26 g, 4.4 mmol), hept-6-en-1-ol (0.50 g, 4.4 mmol).59% yield (0.99 g).

¹ H NMR (400 MHz, CDCI ₃ ) δ (ppm) = 5.80 (ddt, J= 16.9, 10.2, 6.7 Hz, 1H), 5.43-5.25 (m, 2H), 5.06- 4.87 (m, 2H), 4.06 (t, J = 6.7 Hz, 2H), 2.35 - 2.21 (m, 2H), 2.11 - 1.96 (m, 6H), 1.71 - 1.54 (m, 4H), 1.48 - 1.19 (m, 24H), 0.88 (t, J= 6.9 Hz, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ) δ (ppm) = 174.12, 138.86, 130.13, 129.89, 114.62, 64.42, 34.54, 33.76, 32.06, 29.92, 29.84, 29.68, 29.48, 29.33, 29.29, 29.26, 28.65, 28.63, 27.37, 27.32, 25.56, 25.16, 22.84, 14.28.

c) Dec-9-enoate c/s-non-6-en-1-yl (D4):

D4

The reaction time was 20 hours, otherwise the conditions were as in the general procedure. Quantity of reagents: dec-9-enoic acid (1.19 g, 7.0 mmol), c/s-non-6-en-1-ol (1.00 g, 7.0 mmol), PSF (70 mg).85% yield (1.74g).

¹ H NMR (400 MHz, CDCI ₃ ) δ (ppm) = 5.80 (ddtd, J= 16.9, 10.2, 6.7, 1,8 Hz, 2H), 5.05 - 4.86 (m, 4H), 4.05 (t, J= 6.7 Hz, 2H), 2.28 (t, J =7.5 Hz, 2H), 2.14-1.97 (m, 4H), 1.68 - 1.53 (m, 4H), 1.49 -1.22 (m, 12H).

¹³ C NMR (101 MHz, CDCI ₃ ) δ (ppm) = 174.10, 139.24, 138.84, 114.61, 114.32, 77.48, 77.16, 77.16, 76.84, 64.42, 34.51 , 33.90, 33.75, 33.74, 29.24, 29.23, 29.06, 28.98, 28.63, 28.62, 25.55, 25.13.

d) Hept-6-en-1-yl dec-9-enoate (D25):

D25 The reaction time was 66 hours, otherwise the conditions were as in the general procedure. Quantities of reagents: dec-9-enoic acid (1 .49 g, 8.8 mmol), hept-6-en-1 -ol (1 .00 g, 8.8 mmol), PSF (90 mg). 57% yield (1 .33 g).

¹ H NMR (400 MHz, CDCI ₃ ) δ (ppm) = 5.80 (ddt, J = 17.0, 1 0.2, 6.7 Hz, 1 H), 5.45 - 5.24 (m, 2H), 5.05 - 4.85 (m, 2H), 4.05 (t, J = 6.7 Hz, 2H), 2.28 (t, J = 7.6 Hz, 2H), 2.1 1 - 1 .95 (m, 6H), 1 .67 - 1 .54 (m, 4H), 1 .48 - 1 .22 (m, 12H), 0.95 (t, J = 7.5 Hz, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ) δ (ppm) = 174.1 1 , 139.25, 131 .99, 128.96, 1 14.32, 77.48, 77.16, 76.84, 64.47, 34.52, 33.91 , 29.48, 29.25, 29.24, 29.07, 28.98, 28.70, 27.07, 25.70, 25.14, 20.66, 14.52.

Example III

Description of the etheral diene synthesis, (9Z)-1 -(((6Z)-non-6-en-1 -yl)oxy)oktadeca-9-en (D26):

Under an inert gas atmosphere, alcohol A7 (1 eq.) was dissolved in anhydrous N,N-dimethylformamide. Sodium hydride (1 .2 eq.) was added in 4 portions and stirred at room temperature for 30 minutes, then the temperature was increased to 50°C and the stirring continued for another 30 minutes. One portion of sodium iodide was then added. Finally, oleyl bromide was added dropwise and the temperature was increased to 90°C. The reaction was continued under argon atmosphere for 12 hours. The crude mixture was washed with water (3 x 1 0 mL) and brine (1 x 10 mL) and dried over sodium sulfate (Na ₂ S0 ₄ ). The product was purified by column chromatography with 2% EtOAc/n-hexane (v/v). The target compound D26 was obtained at a 53% yield.

(9ZH -(((6Z)-non-6-en-1 -yl)oxy)oktadeca-9-en (D26):

D26

¹ H NMR (400 MHz, CDCI ₃ ) δ (ppm) = 5.43 - 5.28 (m, 4H), 3.39 (dt, J = 6.8, 0.9 Hz, 4H), 2.08 - 1 .94 (m, 8H), 1 .62 - 1 .50 (m, 4H), 1 .42 - 1 .1 9 (m, 26H), 0.95 (t, J = 7.5 Hz, 3H), 0.91 - 0.85 (m, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ) δ (ppm) = 131 .80, 130.07, 130.00, 129.25, 71 .13, 71 .04, 32.06, 29.93, 29.91 , 29.84, 29.78, 29.68, 29.66, 29.65, 29.48, 29.42, 27.36, 27.20, 26.35, 26.00, 22.85, 20.66, 14.55, 14.29. Example IV

General procedure for the RCM macrocvclization reaction in toluene at atmospheric pressure in the presence of an inert gas. Preparation of one compound M11 from four different dienes D1 , D8, D9 and

D16.

M1 1

Suitable diene Dx (1 eq.) and tetrafluorobenzoquinone (4 mol%) were dissolved in anhydrous toluene (concentration of 1 .5 mM) in a dried flask under inetrt gas atmosphere. Precatalyst (Cat. 1 , 2 mol%) was dissolved in dry toluene in a Schlenk flask (concentration of 1 mg/1 ml_) and added during the reaction at intervals of 1 5 minutes (20 portions of the catalyst). The reaction was conducted at atmospheric pressure under inert gas atmosphere (argon). The reaction was conducted at 50°C for 5 hours. The progress of the reaction was monitored using thin layer chromatography (TLC). Once the reaction was over, the catalyst was deactivated by the addition of SnatchCat solution [CAS: 51 641 -96-4] and stirred for 30 minutes. The solvent was evaporated, and the product was purified by column chromatography with 20% toluene/ n- hexane (v/v).

RCM Reactions of ester dienes, derivatives of oleic and 9-decenoic acid in toluene.

The purpose of the example is to demonstrate the possibility of synthesis of macrocyclic lactones from biomass: oleic and 9-decenoic acids. In addition, there occurs a non-terminal double bond C=C - ester derivatives with one non-terminal double bond are closed in RCM reactions, achieving higher yields of the expected products. Preparation of one type of a macrocyclic compound (M1 1 ) from four different dienes (Dx) - for details, refer to Fig. 2

Reaction conditions:

^• Solvent: anhydrous toluene [PhMe]

^• Reaction time: 5 hours

^• Temperature: 50°C

^• Additives: tetrafluorobenzoquinone (4 mol%)

^• Precatalyst [Ru]: Cat. 1 (2% mol)

^• Substrate concentration: 0.0015 mol/dm ³ [C = 1 .5 mM]

Table 1 . Results of the preparation reaction of 1 9-membered M11 macrocycle.

The graphical presentation of the experiments is shown in Fig. 2 Example V

Preparation of 16- and 17-membered macrocvcles in the RCM reaction in toluene, atmospheric pressure, inert gas atmosphere.

This example uses the same reaction conditions as in example III for a wider spectrum of dienes (Dx). The cumulative results are presented in Table 2 below. The graphical presentation of the experiments is included in Fig. 3.

Table 2. Results of the preparation reaction of 17-membered and 1 6-membered macrocycles.

Example VI

General method for the RCM reactions of dienes with C=C bonds substituted with short alkyl groups

Cyclization of RCM dienes was performed in accordance with the general procedure described in example III, shortened RCM reaction conditions:

• Solvent: anhydrous toluene [PhMe];

• Reaction time: 5 hours; • Temperature: 50°C;

• Substrate concentration: 0.0015 mol/dm ³ [C = 1 .5 mM];

^• Additives: tetrafluorobenzoquinone (4 mol%);

• Catalyst [Ru]: Cat. 1 (2% mol)

Table 3. Cyclization of dienes with CH ₃ substituents at the C=C double bond in toluene

Example VII

General method for the RCM reactions of dienes with C=C bonds substituted with short alkyl groups only in the acid portion

Cyclization of RCM dienes was performed in accordance with the general procedure described in example III, shortened RCM reaction conditions:

• Solvent: anhydrous toluene [PhMe];

^• Reaction time: 5 hours;

• Temperature: 50°C;

• Substrate concentration: 0.0015 mol/dm ³ [C = 1 .5 mM];

^• Additives: tetrafluorobenzoquinone (4 mol%);

• Catalyst [Ru]: Cat. 1 (2% mol)

Table 4. Cyclization of dienes with short substituents at the C=C double bond in the carboxy portion in toluene. Example VIII

General method for the RCM reactions of dienes with C=C bonds substituted with short alkyl groups only in the alcohol portion

Table 5. Cyclization of diene D22 to macrocycle M3 in toluene.

Example IX

General procedure for the RCM macrocyclization reaction in ethyl acetate, atmospheric pressure in the presence of an inert gas.

Suitable ester (1 eq.) and tetrafluorobenzoquinone (4 mol%) were dissolved in anhydrous ethyl acetate (concentration of 12 to 100 mM) in a dried flask under atmosphere of inert gas. Precatalyst (Cat. 1 , 2 mol% [20000 ppm] to 0.05 mol% [500 ppm]) was dissolved in dry ethyl acetate in a Schlenk flask (concentration of 1 mg/1 ml_) and added during the reaction at intervals of 15 minutes. The reaction was conducted at 77 °C for 5 to 24 hours. The progress of the reaction was monitored using thin layer chromatography (TLC). Once the reaction was over, the catalyst was deactivated by the addition of SnatchCat solution and stirred for 30 minutes. The solvent was evaporated, and the product was purified by column chromatography with 20% toluene/n-hexane (v/v).

The purpose of the example is to demonstrate the possibility of macrocyclization in ethyl acetate [ Green Chem., 2014, 16, 1 125-1 130]. First, the results of the paper were reproduced with the same concentration (C = 5 mM -> for examples in toluene C = 1 .5 mM), and then model reactions were tested at a higher concentration range.

Reaction conditions:

• Solvent: anhydrous ethyl acetate [EtOAc];

^• Reaction time: 5 hours to 24 hours (detailed in Table 6);

• Temperature: 77°C;

^• Substrate concentration: 12 hours to 100 hours (detailed in Table 6);

^• Additives: tetrafluorobenzoquinone;

^• Catal st [Ru]: Cat. 1 ;

D12 Table 6. RCM macrocyclization reactions of c/ ^' s-non-6-en-1 -yl oleate (D12).

( ^a ) complex mixture of products

( ^b ) reaction conducted for 5 hours without no quinone addition

Example X

List of macrocvclic products obtained in the RCM reaction

a) (9-E, Z)-butadec-9-en-14-olide (M1 ):

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.52 - 5.30 (m, 2H), 4.1 6 - 4.07 (m, 2H), 2.40 - 2.26 (m, 2H), 2.10 - 1 .97 (m, 4H), 1 .77 - 1 .54 (m, 4H), 1 .52 - 1 .19 (m, 10H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.24 (CO), 174.06 (CO), 131 .58(CH), 130.81 (CH), 130.79 (CH), 129.36 (CH), 63.98 (CH ₂ ), 63.92 (CH ₂ ), 34.69 (CH ₂ ), 34.52 (CH ₂ ), 31 .86 (CH ₂ ), 31 .39 (CH ₂ ), 28.62 (CH ₂ ), 28.45 (CH ₂ ), 28.12 (CH ₂ ), 27.95 (CH ₂ ), 27.94 (CH ₂ ), 27.82 (CH ₂ ), 27.64 (CH ₂ ), 27.45 (CH ₂ ), 27.36 (CH ₂ ), 27.20 (CH ₂ ), 27.10 (CH ₂ ), 26.46 (CH ₂ ), 25.62 (CH ₂ ), 25.18 (CH ₂ ), 25.00 (CH ₂ ).

b) (8-E. Z)-butadec-8-en-14-olide (M2):

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.38 - 5.19 (m, 2H), 4.20 - 4.04 (m, 2H), 2.38 - 2.27 (m, 2H), 2.12 - 1 .96 (m, 4H), 1 .72 - 1 .57 (m, 4H), 1 .50 - 1 .18 (m, 10).

¹³ C NMR (100 MHz, CDCI ₃ ): δ (ppm) = 174.12 (CO), 131 .40 (CH), 131 .06 (CH), 63.44 (CH ₂ ), 33.96 (CH ₂ ), 31 .98 (CH ₂ ), 31 .76 (CH ₂ ), 28.55 (CH ₂ ) 28.47 (CH ₂ ) 28.35 (CH ₂ ), 27.86 (CH ₂ ), 27.13 (CH ₂ ), 25.16 (CH ₂ ), 24.95 (CH ₂ ), 23.94 (CH ₂ ). c) (9-E, Z)-pentadec-9-en-15-olide (M3):

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.41 - 5.23 (m, 2H), 4.12 - 4.03 (m, 2H), 2.38 - 2.27 (m, 2H), 2.14 - 1 .98 (m, 4H), 1 .69 - 1 .54 (m, 4H), 1 .42 - 1 .21 (m, 12H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.10 (CO), 174.07 (CO), 131 .43(CH), 130.90 (CH), 130.38 (CH), 130.08 (CH), 64.67 (CH ₂ ), 64.58 (CH ₂ ), 34.88 (CH ₂ ), 32.43 (CH ₂ ), 31 .61 (CH ₂ ), 29.27 (CH ₂ ), 29.1 7 (CH ₂ ), 29.09 (CH ₂ ), 28.83 (CH ₂ ), 28.63 (CH ₂ ), 28.41 (CH ₂ ), 28.36 (CH ₂ ), 28.24 (CH ₂ ), 27.87 (CH ₂ ), 27.84 (CH ₂ ), 27.59 (CH ₂ ), 27.39 (CH ₂ ), 27.08 (CH ₂ ), 26.53 (CH ₂ ), 26.37 (CH ₂ ), 25.65 (CH ₂ ),25.10 (CH ₂ ), 24.68 (CH ₂ ).

d) (8-E, Z)-pentadec-8-en-15-olide (M4):

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.49 - 5.22 (m, 2H), 4.1 9 - 4.04 (m, 2H), 2.36 - 2.28 (m, 2H), 2.09 - 1 .96 (m, 4H), 1 .73 - 1 .56 (m, 4H), 1 .49 - 1 .21 (m, 12H).

¹³ C NMR (100 MHz, CDCI ₃ ): δ (ppm) = 174.20 (CO), 130.93 (CH), 130.87 (CH), 130.24 (CH), 130.14 (CH), 64.45 (CH ₂ ), 63.90 (CH ₂ ), 34.97 (CH ₂ ), 34.67 (CH ₂ ), 31 .84 (CH ₂ ), 31 .54 (CH ₂ ), 29.55 (CH ₂ ), 29.45 (CH ₂ ), 28.99 (CH ₂ ), 28.60(CH ₂ ), 28.45 (CH ₂ ), 28.27 (CH ₂ ), 28.19 (CH ₂ ), 28.07 (CH ₂ ), 27.82 (CH ₂ ), 27.67 (CH ₂ ), 27.38 (CH ₂ ), 26.63 (CH ₂ ), 26.47 (CH ₂ ), 26.24 (CH ₂ ), 26.03 (CH ₂ ), 25.39 (CH ₂ ), 25.24 (CH ₂ ).

e) (9-E, Z)-13-metylopentadec-9-en-15-olide (M5):

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.41 - 5.27 (m, 2H), 4.24 - 4.06 (m, 2H), 2.44 - 2.21 (m, 2H), 2.19 - 1 .92 (m, 4H), 1 .76 - 1 .56 (m, 1 1 H), 0.94 - 0.79 (m, 3H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.05 (CO), 174.02 (CO), 131 .04 (CH), 130.62 (CH), 130.53 (CH), 129.76 (CH), 62.20 (CH ₂ ), 61 .84 (CH ₂ ), 36.59 (CH ₂ ), 36.45 (CH ₂ ), 36.41 (CH ₂ ), 35.92 (CH ₂ ), 35.20 (CH ₂ ), 34.70 (CH ₂ ), 31 .26 (CH ₂ ), 29.48 (CH ₂ ), 29.01 (CH), 28.74 (CH ₂ ), 28.36 (CH ₂ ), 28.33 (CH ₂ ), 28.14 (CH ₂ ), 27.57 (CH ₂ ), 27.54 (CH ₂ ), 27.10 (CH ₂ ), 26.79 (CH ₂ ), 26.40 (CH ₂ ), 26.37 (CH), 25.51 (CH ₂ ), 25.08 (CH ₂ ), 24.70 (CH ₂ ), 19.46 (CH ₃ ), 17.20 (CH ₃ ). f)

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.48 - 5.25 (m, 3H), 4.64 - 4.48 (m, 2H), 2.39 - 2.32 (m, 2H), 2.26 - 2.10 (m, 4H), 2.02 - 1 .92 (m, 2H), 1 .84 - 1 .58 (m, 5H), 1 .37 - 1 .24 (m, 8H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.38 (CO), 1 74.27 (CO), 145.72 (C), 141 .41 (C), 131 .14 (CH), 130.58 (CH), 129.40 (CH), 129.08 (CH), 120.02 (CH), 1 18.28 (CH), 60.94 (CH ₂ ), 60.79 (CH ₂ ), 34.27 (CH ₂ ), 33.83 (CH ₂ ), 32.27 (CH ₂ ), 31 .04 (CH ₂ ), 30.98 (CH ₂ ), 29.34 (CH ₂ ), 27.65 (CH ₂ ), 27.33 (CH ₂ ), 27.30 (CH ₂ ), 27.23 (CH ₂ ), 27.21 (CH ₂ ), 26.87 (CH ₂ ), 26.65 (CH ₂ ), 26.57 (CH ₂ ), 26.13 (CH ₂ ), 25.79 (CH ₂ ), 24.92 (CH ₂ ), 24.50 (CH ₂ ), 24.26 (CH ₃ ), 22.55 (CH ₃ ).

g) (9-E, Z;13-a-13-metylopentadec-9,13-dien-1 5-olide (M7):

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.47 - 5.20 (m, 3H), 4.56 (m, 2H), 2.39 - 2.29 (m, 2H), 2.24 - 2.08 (m, 4H), 2.05 - 1 .91 (m, 2H), 1 .75 - 1 .53 (m, 5H), 1 .36 - 1 .25 (m, 8H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 173.96 (CO), 1 73.90 (CO), 142.34 (C), 140.62 (C), 130.93 (CH), 130.13 (CH), 130.08 (CH), 129.52 (CH), 1 1 9.93 (CH), 1 18.67 (CH), 61 .27 (CH ₂ ), 61 .18 (CH ₂ ), 39.33 (CH ₂ ), 39.00 (CH ₂ ), 34.99 (CH ₂ ), 34.37 (CH ₂ ), 31 .45 (CH ₂ ), 29.05 (CH ₂ ), 28.29 (CH ₂ ), 27.91 (CH ₂ ), 27.84 (CH ₂ ), 27.73 (CH ₂ ), 27.68 (CH ₂ ), 27.58 (CH ₂ ), 27.10 (CH ₂ ), 27.05 (CH ₂ ), 26.92 (CH ₂ ), 26.29 (CH ₂ ), 24.84 (CH ₂ ), 24.30 (CH ₂ ), 17.22 (CH ₃ ), 15.53 (CH ₃ ).

h) (10-E. Z)-pentadec-10-en-15-olide (M12):

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.45 - 5.24 (m, 2H), 4.1 7 - 4.09 (m, 2H), 2.38 - 2.28 (m, 2H), 2.12 - 1 .96 (m, 4H), 1 .70 - 1 .54 (m, 4H), 1 .47 - 1 .14 (m, 12H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.10 (CO), 131 .97 (CH), 130.48 (CH), 130.26 (CH), 129.73 (CH), 64.26 (CH ₂ ), 64.1 1 (CH ₂ ), 34.91 (CH ₂ ), 34.03 (CH ₂ ), 32.18 (CH ₂ ), 32.14 (CH ₂ ), 29.30 (CH ₂ ), 28.55 (CH ₂ ), 28.48 (CH ₂ ), 28.43(CH ₂ ), 28.36 (CH ₂ ), 28.32 (CH ₂ ), 28.15 (CH ₂ ), 28.09 (CH ₂ ), 27.77 (CH ₂ ), 27.35 (CH ₂ ), 27.34 (CH ₂ ), 27.26 (CH ₂ ), 26.75 (CH ₂ ), 26.70 (CH ₂ ), 26.62 (CH ₂ ), 25.62 (CH ₂ ), 25.40 ), 25.31 (CH ₂ ). (8-E, Z)-hexadec-8-en-16-olide (M8),

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.44 - 5.23 (m, 2H), 4.1 8 - 4.03 (m, 2H), 2.36 - 2.26 (m, 2H), 2.08 - 1 .94 (m, 4H), 1 .70 - 1 .53 (m, 4H), 1 .46 - 1 .21 (m, 14H).

¹³ C NMR (100 MHz, CDCI ₃ ): δ (ppm) = 174.28 (CO), 173.98 (CO), 131 .44 (CH), 130.83 (CH), 130.33 (CH), 130.22 (CH), 64.47 (CH ₂ ), 64.40 (CH ₂ ), 34.72 (CH ₂ ), 33.45 (CH ₂ ), 31 .49 (CH ₂ ), 31 .36 (CH ₂ ), 29.03 (CH ₂ ), 28.99 (CH ₂ ), 28.86 (CH ₂ ), 28.85(CH ₂ ), 28.81 (CH ₂ ), 28.33 (CH ₂ ), 27.91 (CH ₂ ), 27.77 (CH ₂ ), 27.58 (CH ₂ ), 27.51 (CH ₂ ), 26.89 (CH ₂ ), 26.35 (CH ₂ ), 26.32 (CH ₂ ), 26.20 (CH ₂ ), 25.92 (CH ₂ ), 25.74 (CH ₂ ), 25.16 ), 24.66 (CH ₂ ).

j) (9-E, Z)-hexadec-9-en-16-olide (M9):

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.43 - 5.27 (m, 2H), 4.20 - 4.02 (m, 2H), 2.38 - 2.25 (m, 2H), 2.03 (m, 4H), 1 .61 (m, 4H), 1 .45 - 1 .20 (m, 14H)

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.21 (CO), 174.07 (CO), 131 .32 (CH), 130.73 (CH), 130.47 (CH), 130.23 (CH), 64.51 (CH ₂ ), 64.49 (CH ₂ ), 35.05 (CH ₂ ), 34.88 (CH ₂ ), 31 .92 (CH ₂ ), 31 .55 (CH ₂ ), 29.77 (CH ₂ ), 29.35 (CH ₂ ), 29.02 (CH ₂ ), 28.77(CH ₂ ), 28.75 (CH ₂ ), 28.71 (CH ₂ ), 28.63 (CH ₂ ), 28.29 (CH ₂ ), 28.10 (CH ₂ ), 28.06 (CH ₂ ), 27.99 (CH ₂ ), 27.88 (CH ₂ ), 27.08 (CH ₂ ), 26.91 (CH ₂ ), 26.63 (CH ₂ ), 26.08 (CH ₂ ), 25.94 ), 25.32 (CH ₂ ), 25.17 (CH ₂ ).

k) (8-E. Z)-heptadec-8-en-17-olide (M10):

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.53 - 5.16 (m, 2H), 4.15 - 4.05 (m, 2H), 2.31 (td, J = 7.0, 5.3 Hz, 2H), 2.12 - 1 .91 (m, 4H), 1 .72 - 1 .54 (m, 4H), 1 .47 - 1 .15 (m, 16H).

¹³ C NMR (100 MHz, CDCI ₃ ): δ (ppm) = 173.55 (CO), 130.77 (CH), 130.74 (CH), 129.87 (CH), 129.86 (CH), 64.40 (CH ₂ ), 63.99 (CH ₂ ), 34.57 (CH ₂ ), 34.48 (CH ₂ ), 31 .85 (CH ₂ ), 31 .86 (CH ₂ ), 29.53 (CH ₂ ), 29.14 (CH ₂ ), 28.94 (CH ₂ ), 28.96 (CH ₂ ), 28.81 (CH ₂ ), 28.78 (CH ₂ ), 28.65 (CH ₂ ), 28.60 (CH ₂ ), 28.54 (CH ₂ ), 28.35 (CH ₂ ), 28.22 (CH ₂ ), 27.86 (CH ₂ ), 27.54 (CH ₂ ), 27.32 (CH ₂ ), 26.97 (CH ₂ ), 26.46 (CH ₂ ), 26.01 (CH ₂ ), 25.80 (CH ₂ ), 25.09 (CH ₂ ), 25.00 (CH ₂ ).

I) (9-E, Z)-octadec-9-en-18-olide (M11 ):

¹ H NMR (400 MHz, CDCI ₃ ) : δ (ppm) = 5.38 - 5.24 (m, 2H), 4.13 - 4.07 (m, 2H), 2.30 (t, J = 6.9 Hz, 2H), 2.10 - 1 .96 (m, 4H), 1 .69 - 1 .56 (m, 4H), 1 .40 - 1 .1 7 (m, 18H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 174.34 (CO), 174.26 (CO), 130.96 (CH), 130.95 (CH), 130.43 (CH), 130.30 (CH), 64.74 (CH ₂ ), 64.42 (CH ₂ ), 35.16 (CH ₂ ), 35.10 (CH ₂ ), 32.30 (CH ₂ ), 29.81 (CH ₂ ), 29.70 (CH ₂ ), 29.54 (CH ₂ ), 29.47 (CH ₂ ), 29.40 (CH ₂ ), 29.31 (CH ₂ ), 29.30 (CH ₂ ), 29.27 (CH ₂ ), 29.24 (CH ₂ ), 29.1 1 (CH ₂ ), 28.98 (CH ₂ ), 28.97 (CH ₂ ), 28.95 (CH ₂ ), 28.25 (CH ₂ ), 28.03 (CH ₂ ), 27.92 (CH ₂ ), 27.26 (CH ₂ ), 26.47 (CH ₂ ), 26.32 (CH ₂ ), 25.48 (CH ₂ ), 25.47 (CH ₂ ).

m) (10-E, Z)-oxacvclohexadec-10-en (M12):

¹ H NMR (400 MHz, CDCI ₃ ): δ (ppm) = 5.38 - 5.25 (m, 2H), 4.46 - 4.36 (m, 4H), 2.15 - 1 .95 (m, 4H), 1 .60 - 1 .48 (m, 4H), 1 .46 - 1 .36 (m, 6H), 1 .35 - 1 .24 (m, 8H).

¹³ C NMR (101 MHz, CDCI ₃ ): δ (ppm) = 131 .22 (CH), 130.93 (CH), 130.15 (CH), 130.03 (CH), 70.42 (CH ₂ 0), 70.08 (CH ₂ 0), 69.45 (CH ₂ 0), 68.53 (CH ₂ 0), 32.74 (CH ₂ ), 32.18 (CH ₂ ), 30.35 (CH ₂ ), 30.14 (CH ₂ ), 29.15 (CH ₂ ), 29.04(CH ₂ ), 28.87 (CH ₂ ), 28.72 (CH ₂ ), 28.48 (CH ₂ ), 28.27 (CH ₂ ), 27.99 (CH ₂ ), 27.72 (CH ₂ ), 27.66 (CH ₂ ), 27.63 (CH ₂ ), 26.86 (CH ₂ ), 26.81 (CH ₂ ), 26.62 (CH ₂ ), 26.22 (CH ₂ ), 24.41 ), 23.99 (CH ₂ ).

Example XI

RCM macrocvclization reaction of oct-7-en-1 -yl oleate (D10) under conditions of reduced pressure and elevated temperature

(544 mM, 0,64 mol/kg)

Oct-7-en-1 -yl oleate (D10, 0.5 g; 1 .28 mmol) in the presence of tetrafluorobenzoquinone (8 mol%) was subjected to RCM metathesis reaction with ruthenium catalyst Cat. 5 (4 mol%) in paraffin oil (CAS: 8012- 95-1 , Sigma-Aldrich) at reduced pressure (of the order of 1 -10 ³ mbar). The reaction was conducted for 4 hours at a temperature of 150°C. The resulting products, which distilled from the reaction mixture, were collected in a collector cooled with dry ice. The distillate was analysed by GCMS. The product was obtained with an effective yield of 12% and a purity of 12%, while the ratio of E and Z isomers of the compound M9 was 1 .58.

Conclusion : conducting a RCM reaction with simultaneous distillation of the product is possible, the reaction requires optimisation of the conditions.

Example XII

Metathesis macrocvclization of diene D12 under conditions of high substrate concentration and reduced pressure, using paraffin oil as a diluent

(212 m , 0,25 mol/kg)

Paraffin oil (2 g, CAS: 8012-95-1 , Sigma-Aldrich) and c/s-non-6-en-1 -yl oleate (D12, 203 mg ; 0.5 mmol) were placed in a single-necked, 1 0ml_ round flask equipped with a magnetic stirring element. A catalyst was then added (X% mol, X - a numerical value representing the catalyst feed, see Table 9). Immediately afterwards, the reaction flask was connected to a system with a collector connected to a diffusion pump. After evacuating the reaction system , the reaction flask was immersed in a heating bath at a predetermined temperature. Reaction mixture was stirred for the next 8 hours, while maintaining the lowest possible pressure (of the order of 1 0 ^"6 mbar). During the reaction , products were collected in the collector attached to the reaction flask. After 8 hours, the connection of the reaction system to the diffusion flask was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the collector with hexane (20 mL), and then purified by chromatography using n-hexane and ethyl acetate. In the case of the reaction using 0.1 mol% or less of the catalyst, the ruthenium complex was introduced into the flask as a solution in dry and deoxygenated methylene chloride, after which the solvent was evaporated and the other ingredients were added.

Study of the metathetic process of cyclisation of c/ ^' s-non-6-en-1 -yl oleate (D12) was started by the optimization of the process temperature. The optimisation results are presented in Table 7. The experiments conducted showed that the minimum temperature at which the reaction is efficient is 1 10°C. The next step involved determining the catalytic activity of the available ruthenium complexes. Results of the catalytic activity of selected ruthenium complexes are summarized in Table 8. The following showed the greatest activity: Cat. 4, Cat. 5, Cat. 14 and Cat. 15. A series of experiments was then conducted to determine the minimum amount of ruthenium complex to ensure good reaction yield. The results of this part of studies are summarised in Table 9. Table 7. Test results to determine the minimum temperature of the process ensuring its good yield.

(a) Determined by gas chromatography (Purity = (signal intensity of E and Z isomers)/(signal intensity of all products) 100%).

(b) Reaction conducted at a pressure ~ ranging from 1 -10 ⁵ mbar to 5-10 ^"4 mbar.

Table 8. Test results of the catalytic activity of selected ruthenium complexes used in the amount of 0.5 mol%.

( ^a ) Determined by gas chromatography (Purity = (signal intensity of E and Z isomers)/(signal intensity of all products)100%).

Table 9. Results of catalytic tests of the most active ruthenium complexes to determine the lowest effective amount of the catalyst.

( ^a ) Determined by gas chromatography (Purity = (signal intensity of E and Z isomers)/(signal intensity of all products)100%).

( ^b ) The substrate and paraffin were filtered through Al ₂ 0 ₃ . Example XIII

Metathesis macrocvclization of D12 diene under reduced pressure in various high -boiling diluents.

(212 mM, 0,25 mol/kg)

The same reaction conditions were used as in example X using various high-boiling diluents ((i) paraffin oil [CAS: 8012-95-1 ; manufacturer: Sigma-Aldrich]; (ii) paraffin wax /solid paraffin [CAS: 8002-74-2; manufacturer: Aldrich]; (iii) polyethylene [CAS: 9002-88-4; manufacturer Aldrich]; (iv) ionic liquid [1 -butyl-2,3-dimethylimidazolium hexafluorophosphate; CAS: 22761 7-70-1 ; manufacturer: Aldrich]). The cumulative results are presented in Table 10 below.

Table 10. Results of experiments for selecting the optimal diluent.

Conditions: c/s-non-6-en-1 -vl oleate (D12, 0.203 g ; 1 .28 mmol); Cat. 5 (0.5 mol%); diluent (2 g); temperature = 1 10°C; pressure of the order of 1 -10 ^"6 mbar; reaction time = 8 hours.

( ^a ) Determined by GC (Purity = (signal intensity of E and Z isomers)/(signal intensity of all products) 100%).

( ^b ) 1 -butyl-2,3-dimethylimidazolium hexafluorophosphate;

Example XIV

Metathesis macrocvclization reactions yielding M3 using dienes with C=C bonds with various substituents as substrates.

General procedure of metathesis cyclization:

Paraffin oil (2 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for ring metathesis reaction (0.5 mmol; molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10ml_ round flask equipped with a magnetic stirring element. Next, a catalyst Cat. 5 was added 5 (2.5 μητιοΙ, 0.5 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to a diffusion pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a predetermined temperature. This was stirred for the next 8 hours, while maintaining the lowest possible pressure (lowest value obtained: 4-10 ^"6 mbar). During the reaction, products were collected in the collector attached to the reaction flask. After 8 hours, the connection of the reaction system to the diffusion pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the collector with hexane (20 mL), and then the solvents were evaporated under reduced pressure and purified by chromatography using n-hexane and ethyl acetate. Table 19. Metathesis cyclization reactions illustrating the effect of substituting C=C bonds in a substrate molecule

(212 mM, 0,25 mol/kg)

a) ll products) 100%).

Conclusion: The metathesis macrocyclization reaction is effective both for substrates with terminal C=C bonds and for substrates with C=C bonds substituted with alkyl groups.

Example XV

Demonstration of the RCM reaction course of a diolefin substrate through the stage of cross metathesis products between molecules of said compound (oligomers/polvmers)

Description of experiment 1:

Paraffin oil (2 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral Al ₂ 0 ₃ gel) and D25 compound (133.0 mg; 0.5 mmol, C = 6,2% w/w, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10ml_ round flask equipped with a magnetic stirring element. Next, a catalyst Cat. 5 was added (1 .8 g; 2.5 μητιοΙ, 0.5 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to a diffusion pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a temperature of 1 10 °C. After 15 minutes, the valve connecting the reaction system with the diffusion pump was closed and the system was opened in the air. A sample was taken from the reaction mixture, which upon analysis showed complete conversion of the D25 substrate and the presence of a small amount of oligomers and polymeric substances formed by acyclic metathesis of the D25 diene with a small amount of the M3 product. The resulting oligomers and polymeric substances were isolated using column chromatography, and then subjected to MALDI-TOF MS analysis, which showed the presence of compounds with a mass of more than 1000 Da.

D25 P ~ 4x10 ^"6 mbar,

C=6.2% wt

(212 mM, 0,25 mol/kg)

Diagram 1. An experiment illustrating the early stage of the RCM reaction yielding a macrocyclic product See Figure 7a for the illustration of the result of MALDI-TOF MS spectrometry analysis.

See Figure 8a for the illustration of the result of thin layer chromatography analysis (eluent: n- hexane/ethyl acetate = 1 00/5; v/v). Depicted from the left: D25 substrate standard, reaction mixture, M3 product standard, all co-deposited substances. The analysis illustrates the complete conversion of the substrate within a short time from the start of the reaction, with the main products being oligomers and polymeric substances.

Description of experiment 2:

Paraffin oil (2 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral Al ₂ 0 ₃ gel) and compound D12 (203.0 mg; 0.5 mmol; C = 9.2% w/w, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10ml_ round flask equipped with a magnetic stirring element. Next, a catalyst Cat. 5 was added (1 .8 mg; 2.5 μηιοΙ; 0.5 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to a diffusion pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a temperature of 1 10°C. After 20 minutes, the valve connecting the reaction system with the diffusion pump was closed and the system was opened in the air. A sample was taken from the reaction mixture, which upon analysis showed complete conversion of the D12 substrate and the presence of a small amount of oligomers and polymeric substances formed by acyclic metathesis of the D12 diene. The resulting oligomers and polymeric substances were isolated using column chromatography, and then subjected to MALDI-TOF MS analysis, which showed the presence of compounds with a mass of more than 1 000 Da.

(212 mM, 0,25 mol/kg)

Diagram 2. An experiment illustrating the early stage of the RCM reaction yielding a macrocyclic product

See Figure 7b for the illustration of the result of MALDI-TOF MS spectrometry analysis.

See Figure 8b for the illustration of the result of thin layer chromatography analysis (eluent: n- hexane/ethyl acetate = 1 00/5; v/v). Depicted from the left: D12 substrate standard, reaction mixture, M3 product standard, all co-deposited substances. The analysis illustrates the complete conversion of the substrate within a short time from the start of the reaction, with the main products being oligomers and polymeric substances.

Conclusion: While example XIV illustrates that D12 and D25 are efficiently converted into macrocyclic M3 after 8 hours, example XIV shows that these substrates under the conditions used (the same catalyst in the same amount, the same diluent and substrate concentration, the same temperature and pressure) are fully converted to form oligomers and polymeric substances within a short time from the start of the reaction. This means that oligomers and polymeric substances are the transitional stage of the course yielding the macrocyclic product. Example XVI

Demonstration of the applicability of the method in relation to substrates with various structure

The experiments presented below were conducted according to the procedure presented in Example XIV.

(212 mM, 0,25 mol/kg)

Diagram 3. Metathesis cyclization of 3,7-dimethyl-oct-6-en-1 -yl oleate (yield = 40%, purity = 87%, E/Z =

4.1 9)

(212 mM, 0,25 mol/kg)

Diagram 4. Metathesis cyclization of oct-7-en-1 -yl oleate (yield = 43%, purity = 80%, E/Z = 2.1 0)

(212 mM, 0,25 mol/kg)

Diagram 5. Metathesis cyclization of oleyl oleate (yield = 23%, purity

(212 mM, 0,25 mol/kg)

Schemat 6. Metathesis cyclization of (9-Z)-1 -(((6-Z)-non-6-en-1 -yl)oxy)octadeca-9-ene (yield = 28%, purity = 90%, E/Z = 3.1 1 )

(212 mM, 0,25 mol/kg)

Diagram 7. Metathesis cyclization of nona-1 , 8-dien-5-on (yield = 64%) Et0 ₂ C C0 ₂ Et

P ~ 8x10 ^"3 mbar,

C=8.9% wt

(346 mM, 0,41 mol/kg)

Diagram 8. Metathesis cyclization of diethyl diallylmalonate (yield = 85%)

^ n ^ Cat. 4 (0,5% mol)

paraffin oil, ► /

'—_° _x J '

90 ^' ° ^' C, 2 h \

P ~ 1000 mbar

_ C≡23.1% w _

(1 ,94 M, 3,0 mol/kg)

Diagram 9. Metathesis cyclization of diallyl ether (yield = 24%)

Conclusions: the examples above confirm that the method for the preparation of unsaturated cyclic compounds of the invention is useful for using it for substrates with various structure and ring sizes.

Example XVII (complementing example XVI)

Demonstration of the applicability of the method in relation to substrates with various structure

General procedure of metathesis cyclization:

Paraffin oil (2 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for the ring metathesis reaction (0.5 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10ml_ round flask equipped with a magnetic stirring element. Next, catalyst Cat. 5 was added. Immediately afterwards, the reaction flask was connected to a system with a collector connected to a diffusion pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a temperature determined as 1 10°C. This was stirred for the next 8 hours, while maintaining the lowest possible pressure. The vacuum level was read from the vacuum meter connected directly to the diffusion pump (the vacuum was of the order of 10 ^~6 ). During the reaction, products were collected in the collector attached to the reaction flask. After 8 hours, the connection of the reaction system to the diffusion pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the collector with hexane (20 mL), and then the solvents were evaporated under reduced pressure and purified by chromatography using n-hexane and ethyl acetate.

D13

Diagram 10. Metathesis cyclization of 3,7-dimethyl-oct-6-en-1 -yl oleate.

For 1 mol% Cat. 5: yield = 51 %, purity = 91 %, E/Z proportion = 4.3

For 2 mol% Cat. 5: yield = 56%, purity = 92%, E/Z proportion = 4.3

M9

Diagram 11. Metathesis cyclization of 7-oct-1 -enyl oleate.

For 1 mol% Cat. 5: yield = 75%, purity = 57%, E/Z proportion = 2.1

For 2 mol% Cat. 5: yield = 79%, purity = 55%, E/Z proportion = 2.2

M11

Diagram 12. Metathesis cyclization of oleyl oleate.

For 2 mol% Cat. 5: yield = 55%, purity = 76%, E/Z proportion = 3.3

D26 0,25 mol/kg

M12

Diagram 13. Metathesis cyclization of (9Z)-1 -(((6Z)-non-6-en-1 -ylo)oxy)octadec-9-ene.

For 1 %mol Cat. 5: yield = 93%, purity = 97%, E/Z proportion = 4.9

Example XVIII (complementing example XIII)

Metathesis macrocvclization of D12 diene under reduced pressure in various hiqh-boilinq diluents.

General procedure of metathesis cyclization using PAO as diluent

PAO (2 g, filtered through a neutral Al ₂ 0 ₃ gel) and c/s-non-6-en-1 -yl oleate (0.5 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10-mL round flask equipped with a magnetic stirring element. Next, catalyst Cat. 5 was added. Immediately afterwards, the reaction flask was connected to a system with a collector connected to a diffusion pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a predetermined temperature. This was stirred for the next 8 hours, while maintaining the lowest possible pressure. The vacuum level was read from the vacuum meter connected directly to the diffusion pump (the vacuum was of the order of 10 ^"6 ). During the reaction, products were collected in the collector attached to the reaction flask. After 8 hours, the connection of the reaction system to the diffusion pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the collector with hexane (20 mL), and then the solvents were evaporated under reduced pressure and purified by chromatography using n-hexane and ethyl acetate.

Table 12. Results of experiments for selecting the optimal diluent (complementing table 10).

Conditions: c/s-non-6-en-1 -yl oleate (D12, 0.203 g ; 1 .28 mmol); Cat. 5 (0.5 mol%); diluent (2 g); temperature = 1 10°C; pressure measured at the pump of the order of x ^* 10 ^~6 mbar; reaction time = 8 hours.

( ^a ) Determined by GC (Purity = (signal intensity of E and Z isomers)/(signal intensity of all products) 100%).

Information from specification sheets of PAQ4 and PAQ6 used:

PAQ4, SpectraSvnTM 4 Polvalphaolefin, ExxonMobil Chemical

Composition (CAS-No. / EINECS-No. : Various): Branched Alkanes

Kinematic Viscosity, cSt @ 212°F, 100°C 4.1

Kinematic Viscosity, cSt @ 104°F, 40°C 19.0

Kinematic Viscosity, cSt @ -40°F, -40°C 2.900

Viscosity Index 126

Pour Point, °F, °C -87 (-66)

Flash Point (COC), °F, °C 428 (220)

Fire Point (COC), °F, °C493 (256)

Volatility, Noack, wt% 14.0

Specific Gravity, 60 60°F, 15.6 15.6°C 0.820

Total Acid Number <0.05

Odor No Foreign Odor Appearance Clear and Bright

Color, Pt-Co <0.5

PAQ6, Synfluid® PAO 6 cSt, Cheyron Phillips Chemical Company LP

Composition (CAS-No. / EINECS-No. : 68037-01 -4): 1 -Decene Homopolymer Hydrogenated 100%

Kinematic Viscosity, cSt @ 212°F, 100°C 5.9

Kinematic Viscosity, cSt @ 104°F, 40°C 30.5

Kinematic Viscosity, cSt @ -40°F, -40°C 7.712

Viscosity Index 137

Pour Point, °F, °C -78 (-61 )

Flash Point (COC), °F, °C 473 (245)

Fire Point (COC), °F, °C 529 (276)

Volatility, Noack, wt% 6.6

Specific Gravity, 60 60°F, 15.6 15.6°C 0.8278

Density, lb/gal 6.893

Total Acid Number <0.03

Bromine Index <200

Odor No Foreign Odor

Appearance Clear and Bright

Color, Pt-Co 0

Example XIX (complementing example XII to table 8)

Diagram 14. Metathesis cyclization of c/ ^' s-non-6-en-1 -yl oleate using Umicore M51™ complex

Table 13. Metathesis cyclization of c/ ^' s-non-6-en-1 -yl oleate using Umicore M51™ complex (Fig. 9)

Item Catalyst quantity [% mol] Yield M3 (%) Purity M3 (%) ^a Ratio of E/Z ^a isomers

1 1 51 23 3.4

2 0.5 33 29 3.6 Example XX

Metathesis macrocvclization of diene D12 under conditions of high substrate concentration and reduced pressure (Reactions using rotary oil pump)

General procedure of metathesis cyclization using rotary oil pump

Paraffin oil (2 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral Al ₂ 0 ₃ gel) or PA06 (filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for the ring metathesis reaction (concentration per weight and molar concentration are given for particular reactions in respective diagrams) were placed in a single- necked, 10ml_ round flask equipped with a magnetic stirring element. Next, a catalyst Cat. 5 or Cat. 4 was added. Immediately afterwards, the reaction flask was connected to a system with a collector connected to an oil pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a predetermined temperature. During the reaction, products were collected in the collector attached to the reaction flask. The nominal pressure of the pump (read from the vacuum gauge) was 1 ^* 10 ^~3 , real pressure in the apparatus (read on the MacLeod gauge) was 1 ^* 10 ^~2 .

After 6 hours, the connection of the reaction system to the oil pump was closed, the heating bath was removed, the stirring was stopped and the system was filled with inert gas (argon). The next day, a fresh portion of the catalyst was added and the reaction was continued for another 6 hours. Following an appropriate number of cycles, the crude product was eluted from the collector with n-hexane (20 mL), and then the solvents were evaporated under reduced pressure and purified by chromatography using n- hexane and ethyl acetate.

Diagram 15. Reaction of c/ ^' s-non-6-en-1 -yl oleate conducted 4x 6h.

Yield = 92%, purity = 93%, E/Z ratio = 3.7

Diagram 16. Reaction of c/ ^' s-non-6-en-1 -yl oleate conducted 2x 6h.

Yield = 92%, purity = 96%, E/Z ratio = 3.5

D12 1 ,23 mol/kg

M3

Diagram 17. Reaction of c/s-non-6-en-1 -yl oleate conducted 2x 6h in 3g scale. Yield = 78%, purity = 87%, E/Z ratio

Example XXI

Metathesis cvclization of civetone

M13

Diagram 18. Macrocyclization of civetone

Yield = 69%, purity = 86%, E/Z ratio = 3.0

Example XXII

Macrocyclization of cvclohept-4-en-1 -one

Diagram 19. Macrocyclization of cyclohept-4-en-1 -one.

Table 14. Results for macrocyclization of cyclohept-4-en-1 -one for various procedures.

Procedure 1 .

Paraffin oil (2.72 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for the ring metathesis reaction D29 (0.68 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 1 0ml_ round flask equipped with a magnetic stirring element. Next, a catalyst Cat. 5 was added (0.01 mmol, 1 .0 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to a membrane vacuum pumpmembrane vacuum pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a temperature determined as 90°C. This was stirred for the next 6 hours, while maintaining the lowest possible pressure of 7-8 mbar indicated by the vacuum meter of the membrane vacuum pump. During the reaction, products were collected in the collector attached to the reaction flask. After 6 hours, the connection of the reaction system to the membrane pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the collector with diethyl ether (20 mL), then evaporated on a rotary evaporator at a pressure of 300 mbar at room temperature. 34 mg of the product was obtained with a purity of 99%, equivalent to a 45% yield. (Table 2, example 1 ) Procedure no. 2.

Paraffin oil (4 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for the ring metathesis reaction D29 (1 .0 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10ml_ round flask equipped with a magnetic stirring element. In parallel, a stopcock (014) was prepared connected to a cold trap. Next, a catalyst Cat. 5 was added (0.01 mol, 1 ,0 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to a membrane vacuum pump. After evacuating the reaction system, the cold trap was immersed in liquid nitrogen, and the reaction flask - in a heating bath at a temperature determined as 90°C. This was stirred for the next 24 hours, while maintaining the lowest possible pressure of 7-8 mbar indicated by the vacuum meter of the membrane vacuum pump. During the reaction, products were collected in the collector attached to the reaction flask. After 24 hours, the connection of the reaction system to the membrane vacuum pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the cold trap with diethyl ether (20 mL), then evaporated on a rotary evaporator at a pressure of 300 mbar at room temperature. 80 mg of the product was obtained with a purity of 81 %, equivalent to a 59% yield. (Table 2, example 2)

Procedure no. 3.

Paraffin oil (4 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral AI203 gel) and a substrate for the ring metathesis reaction D29 (0.5 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10ml_ round flask equipped with a magnetic stirring element. In parallel, a stopcock (014) was prepared connected to a cold trap monted backwards. Next, a catalyst Cat. 5 was added (0.01 mol, 1 ,0 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to a membrane vacuum pump. After evacuating the reaction system, the cold trap was immersed in liquid nitrogen, and the reaction flask - in a heating bath at a temperature determined as 90°C. This was stirred for the next 24 hours, while maintaining the lowest possible pressure of 7-8 mbar indicated by the vacuum meter of the membrane vacuum pump. During the reaction, products were collected in the collector attached to the reaction flask. After 24 hours, the connection of the reaction system to the membrane vacuum pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the cold trap with diethyl ether (20 mL), then evaporated on a rotary evaporator at a pressure of 300 mbar at room temperature. 99 mg of the product was obtained with a purity of 90%, equivalent to a 81 % yield. (Table 2, example 3)

Procedure no. 4.

A polyalphaolefin - PA06 (4 g, filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for ring metathesis reaction D29 (1 .0 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10-mL round flask equipped with a magnetic stirring element. In parallel, a stopcock (014) was prepared connected to a cold trap mounted backwards. Next, a catalyst Cat. 5 was added (0.01 mol, 1 ,0 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to a membrane vacuum pump. After evacuating the reaction system, the cold trap was immersed in liquid nitrogen, and the reaction flask - in a heating bath at a temperature determined as 90°C. This was stirred for the next 24 hours, while maintaining the lowest possible pressure of 7-8 mbar indicated by the vacuum meter of the membrane vacuum pump. During the reaction, products were collected in the collector attached to the reaction flask. After 24 hours, the connection of the reaction system to the membrane vacuum pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the cold trap with diethyl ether (20 ml_), then evaporated on a rotary evaporator at a pressure of 300 mbar at room temperature. 87 mg of the product was obtained with a purity of 99%, equivalent to a 79% yield. (Table 2, example 4)

Example XXIII

Macrocvclization of oxacvcloocto-4-en-2-one

D30

Diagram 20. Macrocyclization of oxacycloocto-4-en-2-one.

Table 1 5. Results of macrocyclization of oxacycloocto-4-en-2-one.

Procedure 1 .

Paraffin oil (3 g, CAS: 8012-95-1 , Sigma-Aldrich ; filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for the ring metathesis reaction D30 (0.75 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 1 0ml_ round flask equipped with a magnetic stirring element. In parallel, a stopcock (014) was prepared connected to a double cold trap. Next, a catalyst Cat. 5 was added (7.5 pmol, 1 ,0 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to a rotary oil pump. After evacuating the reaction system , the cold trap was immersed in liquid nitrogen, and the reaction flask - in a heating bath at a temperature determined as 55°C. This was stirred for the next 8 hours, while maintaining the lowest possible pressure of 1 x1 0 ^~3 mbar indicated by the vacuum meter of the rotary oil pump. During the reaction, products were collected in the collector attached to the reaction flask. After 8 hours, the connection of the reaction system to the oil pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the cold trap with diethyl ether (20 ml_), then evaporated on a rotary evaporator at a pressure of 300 mbar at room temperature. 67.7 mg of the product was obtained with a purity of 20%, equivalent to a 1 4% yield. (Table 1 5, example 1 ) Example XXIV

Macrocvclization of cvclohexadecene.

M16

D31

Diagram 21. Macrocyclization of cyclohexadecene

Table 16. Results for macrocyclization of cyclohexadecene for various procedures.

Procedure 1 .

A polyalphaolefin - PA06 (2 g, filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for ring metathesis reaction D31 (0.5 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10-mL round flask equipped with a magnetic stirring element. In parallel, a stopcock (014) was prepared connected to a cold trap mounted backwards. Next, a catalyst Cat. 4 was added (5 pmol, 1 ,0 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to an oil pump. After evacuating the reaction system, the cold trap was immersed in liquid nitrogen, and the reaction flask - in a heating bath at a temperature determined as 90°C. This was stirred for the next 24 hours, while maintaining the lowest possible pressure of 1 x10 ^~3 mbar indicated by the vacuum meter of the rotary oil pump. During the reaction, products were collected in the collector attached to the reaction flask. After 24 hours, the connection of the reaction system to the oil pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the cold trap with diethyl ether (20 mL), then evaporated on a rotary evaporator at a pressure of 20 mbar at 37°C (water bath temperature). 124.7 mg of the product was obtained with a purity of 20%, equivalent to a 22% yield. (Table 16, example 4)

Procedure 2.

Paraffin oil (2 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for the ring metathesis reaction D31 (0.5 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10ml_ round flask equipped with a magnetic stirring element. In parallel, a stopcock (014) was prepared connected to a cold trap mounted backwards. Next, a catalyst Cat. 4 was added (5 pmol, 1 ,0 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to an oil pump. After evacuating the reaction system, the cold trap was immersed in liquid nitrogen, and the reaction flask - in a heating bath at a temperature determined as 90°C. This was stirred for the next 24 hours, while maintaining the lowest possible pressure of 1 x10 ^~3 mbar indicated by the vacuum meter of the rotary oil pump. During the reaction, products were collected in the collector attached to the reaction flask. After 24 hours, the connection of the reaction system to the oil pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the cold trap with diethyl ether (20 mL), then evaporated on a rotary evaporator at a pressure of 20 mbar at 37°C (water bath temperature). 102 mg of the product was obtained with a purity of 17%, equivalent to a 15% yield. (Table 1 6, example 3)

Procedure 3.

Paraffin oil (2 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral AI203 gel) and a substrate for the ring metathesis reaction D31 (0.5 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10ml_ round flask equipped with a magnetic stirring element. In parallel, a stopcock (014) was prepared connected to a cold trap mounted backwards. Next, a catalyst Cat. 5 was added (5 μηιοΙ, 1 ,0 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to an oil pump. After evacuating the reaction system, the cold trap was immersed in liquid nitrogen, and the reaction flask - in a heating bath at a temperature determined as 90°C. This was stirred for the next 24 hours, while maintaining the lowest possible pressure of 1 x10 ^~3 mbar indicated by the vacuum meter of the rotary oil pump. During the reaction, products were collected in the collector attached to the reaction flask. After 24 hours, the connection of the reaction system to the oil pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the cold trap with diethyl ether (20 mL), then evaporated on a rotary evaporator at a pressure of 20 mbar at 37°C (water bath temperature). 98.8 mg of the product was obtained with a purity of 16%, equivalent to a 14% yield. (Table 1 6, example 2)

Procedure 4.

Paraffin oil (4 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for the ring metathesis reaction D31 (1 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10ml_ round flask equipped with a magnetic stirring element. Next, a catalyst Cat. 5 was added (1 mmol, 1 .0 mol%). Immediately afterwards, the reaction flask was connected to a system with a collector connected to a membrane vacuum pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a temperature determined as 90°C. This was stirred for the next 8 hours, while maintaining the lowest possible pressure of 7-8 mbar indicated by the vacuum meter of the membrane vacuum pump. During the reaction, products were collected in the collector attached to the reaction flask. After 8 hours, the connection of the reaction system to the membrane vacuum pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the collector with diethyl ether (20 mL), then evaporated on a rotary evaporator at a pressure of 300 mbar at room temperature. 21 1 mg of the product was obtained with a purity of 1 6%, equivalent to a 16% yield. (Table 1 6, example 1 )

Example XXV

Metathesis cvclization of 7-oct-1 -enyl oleate using paraffin oil as a diluent with a temperature gradient of 40-> 1 10°C

General procedure of metathesis cyclization:

Paraffin oil (2 g, CAS: 8012-95-1 , Sigma-Aldrich; filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for the ring metathesis reaction (0.5 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) were placed in a single-necked, 10ml_ round flask equipped with a magnetic stirring element. Next, catalyst Cat. 4 was added. Immediately afterwards, the reaction flask was connected to a system with a collector connected to a diffusion pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a temperature determined as 40°C. The temperature was gradually increased to 1 10°C over 30 minutes. The stirring at the determined temperature of 1 10°C was continued for the next 7 hours and 30 minutes while maintaining the lowest pressure possible. The vacuum level was read from the vacuum meter connected directly to the diffusion pump (the vacuum was of the order of 10 ^~6 ). During the reaction, products were collected in the collector attached to the reaction flask. After 8 hours, the connection of the reaction system to the diffusion pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the collector with hexane (20 mL), and then the solvents were evaporated under reduced pressure and purified by chromatography using n-hexane and ethyl acetate.

Diagram 22. Metathesis cyclization of 7-oct-1 -enyl oleate.

Yield = 78%, purity = 87%, E/Z ratio = 2.1

Example XXVI

Metathesis cyclization of 7-oct-1 -enyl oleate using PAO 6 as a diluent with a temperature gradient of 40-> 1 10°C

General procedure of metathesis cyclization:

PAO 6 (2 g, filtered through a neutral Al ₂ 0 ₃ gel) and a substrate for the ring metathesis reaction (0.5 mmol, molar concentration in the reaction mixture = 0.25 mol/kg) we placed in a single-necked, 10-mL round flask equipped with a magnetic stirring element. Next, catalyst Cat. 4 was added. Immediately afterwards, the reaction flask was connected to a system with a collector connected to a diffusion pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a temperature determined as 40°C. The temperature was gradually increased to 1 10°C over 30 minutes. The stirring at the determined temperature of 1 10°C was continued for the next 7 hours and 30 minutes while maintaining the lowest pressure possible. The vacuum level was read from the vacuum meter connected directly to the diffusion pump (the vacuum was of the order of 10 ^~6 ). During the reaction, products were collected in the collector attached to the reaction flask. After 8 hours, the connection of the reaction system to the diffusion pump was closed, the heating bath was removed, the stirring was stopped and the reaction system was opened so that air could access it. The crude product was eluted from the collector with hexane (20 mL), and then the solvents were evaporated under reduced pressure and purified by chromatography using n-hexane and ethyl acetate.

M9

Diagram 23. Metathesis cyclization of 7-oct-1 -enyl oleate.

Yield = 86%, purity = 94%, E/Z ratio = 2.1

Example XXVII

Metathesis cyclization of 3-but-1 -enyl oleate using paraffin oil as a diluent and a diffusion pump

The reaction was conducted in accordance with the procedure and conditions of example XIII (i)

D32 0,25 mol/kg

M17

Diagram 24. Metathesis cyclization of 3-but-1 -enyl oleate.

Yield = 43%, purity = 93%, E/Z ratio = 2.4

Example XXVIII

Metathesis cyclization of 3-but-1 -enyl oleate using paraffin oil as a diluent and a rotary oil pump.

The reaction was conducted in accordance with the procedure of example XX using paraffin oil as diluent

M17

Diagram 25. Metathesis cyclization of 3-but-1 -enyl oleate.

Yield = 25%, purity = 67%, E/Z ratio = 2.5

Example XXIX

Metathesis cyclization of 3-but-1 -enyl oleate using PAO 6 as a diluent and a rotary oil pump.

The reaction was conducted in accordance with the procedure of example XX using PAO 6 as diluent.

M17

Diagram 26. Metathesis cyclization of 3-but-1 -enyl oleate.

Yield = 25%, purity = 95%, E/Z ratio = 2.8 Experimental part:

1 1 -docosan

1 -dodecene (1 eq.) and tetrafluorobenzoquinone (0.5 mol%) were placed in a 250 mL single-necked round flask and then heated to 80°C. Catalyst

cat. 13 (500 ppm) was dissolved in 1 mL of methylene chloride and added to the flask. The reaction mixture was heated for 30 minutes, after which it was cooled to room temperature and SnatchCat solution was added. After 30 minutes, the contents of the flask were diluted with n-hexane and filtered through Si0 ₂ , eluting with pure n-hexane. The filtrate was evaporated and then dried using rotary oil pump A colourless oil was obtained that solidified at room temperature. 97% yield.

¹ H NMR (400 MHz, CDCI ₃ ) 5.45 - 5.29 (m, 2H), 2.08 - 1 .87 (m, 4H), 1 .41 - 1 .15 (m, 32H), 0.95 - 0.80 (m, 6H); ¹³ C NMR (400 MHz, CDCI ₃ ) 130.51 , 130.05, 32.78, 32.09, 29.94, 29.82, 29.80, 29.73, 29.70, 29.52, 29.48, 29.33, 27.36, 22.86, 14.30.

4-pentadecanoic acid (K6)

q.) and 1 1 -docosan (5 eq.) were dissolved in methylene chloride in a single-necked round flask under the atmosphere of argon. Tetrafluorobenzoquinone (5.5 mol%) was then added, and the reaction mixture was heated to 40°C. Catalyst cat. 18 (2 mol%) was added in ten portions every 30 minutes. After 5 hours, the mixture was cooled to room temperature and SnatchCat solution was added. The product was purified by chromatography using 20% EtOAc in n-hexane. An orange solid was obtained. 92% yield.

¹ H NMR (400 MHz, CDCI ₃ ) δ 5.53 - 5.29 (m, 2H), 2.45 - 2.28 (m, 4H), 2.07 - 1 .93 (m, 2H), 1 .39 - 1 .21 (m, 17H), 0.92 - 0.84 (m, 3H); ¹³ C NMR (101 MHz, CDCI ₃ ) δ 132.36, 132.08, 127.60, 127.01 , 34.12, 32.65, 32.07, 29.80, 29.78, 29.71 , 29.66, 29.57, 29.50, 29.46, 29.29, 27.74, 27.37, 22.85, 22.66, 14.28.

methyl 3-oxo-2-((Z)-hexadec-7-en-1 -yl)-(Z)-1 1 -eikosate (D27)

TiCI ₄ (1 .5 eq.) dissolved in 4 mL of dry toluene was added dropwise under an inert gas atmosphere to a mixture of methyl oleate (1 .0 eq.) and NBu ₃ (18 eq.) in 16 mL of dry toluene at 0 to

5°C. The temperature was maintained for one hour after the dropwise addition was over, and then 20 mL of water was added and washed twice with diethyl ether. The combined ether layers were dried over Na ₂ S0 ₄ . The product was purified by chromatography using 2.5% Et ₂ 0 in n-hexane. A yellow oil was obtained. 93% yield.

¹ H NMR (400 MHz, CDCI ₃ ) δ 5.40 - 5.27 (m, 4H), 3.71 (s, 3H), 3.43 (t, J = 7.4 Hz, 1 H), 2.61 - 2.39 (m, 2H), 2.07 - 1 .95 (m, 8H), 1 .90 - 1 .74 (m, 2H), 1 .64 - 1 .50 (m, 2H), 1 .40 - 1 .17 (m, 40H), 0.93 - 0.83 (m, 6H); ¹³ C NMR (101 MHz, CDCI ₃ ) δ 205.63, 170.58, 130.19, 130.14, 129.87, 129.79, 59.16, 52.43, 42.02, 32.06, 29.91 , 29.85, 29.77, 29.68, 29.48, 29.44, 29.42, 29.26, 29.16, 29.12, 28.43, 27.63, 27.37, 27.32, 27.27, 23.59, 22.84, 14.28. (9Z,26Z)-pentatriakonta-9,26-dien-18-on (D28)

1 equivalent of diene D27 was dissolved in the mixture of THF-MeOH

5% NaOH solution. The reaction mixture was heated for 5 hours at a temperature of 70°C. It was then cooled to 0°C and H ₂ S0 ₄ was added until the reaction was slightly acidic. After evaporation of the solvents, the mixture was washed twice with diethyl ether. The combined ether layers were dried over Na ₂ S0 ₄ . The product was purified by chromatography using 2% EtOAc in n-hexane. A yellow oil was obtained. 92% yield.

¹ H NMR (400 MHz, CDCI ₃ ) δ 5.40 - 5.28 (m, 4H), 2.37 (t, J = 7.6 Hz, 4H), 2.05 - 1 .95 (m, 8H), 1 .62 - 1 .49 (m, 4H), 1 .40 - 1 .19 (m, 40H), 0.93 - 0.83 (m, 6H); ¹³ C NMR (101 MHz, CDCI ₃ ) δ 21 1 .81 , 130.12, 129.89, 42.96, 32.06, 29.92, 29.85, 29.68, 29.48, 29.40, 29.27, 27.36, 27.31 , 24.02, 22.84, 14.28.

eikosa-1 ,8-dien-5-one (D29)

A suitable carboxylic acid K61 (1 eq.) was dissolved in anhydrous methylene chloride under an inert gas

atmosphere. A few drops of A/,/V-dimethylformamide were added, and then oxalyl chloride (1 .2 eq.) was added dropwise at room temperature. Gas emission and change of colour to yellow were observed. After an hour, substrate conversion was checked using ¹ H NMR. Methylene chloride and unreacted oxalyl chloride were evaporated using a membrane vacuum pump. 25 mL of THF was added to the resulting oil, after which the evaporation of the solvent was repeated. The resulting acid chloride was then placed in a 500 mL three-necked round flask, dissolved in 270 mL THF. After cooling the mixture to -78°C, Fe(acac) ₃ (5 mol%) was added in one portion. After dissolving the catalyst, a homoallyl magnesium bromide solution (0.77 M in THF, 17 mL) was added dropwise to the mixture and allowed to rest while stirring for 30 minutes, after which 20 mL of saturated ammonium chloride solution was added and allowed to rest while stirring until it reached room temperature. After evaporation of the solvents, the mixture was washed four times with methyl tert-butyl ether. The combined ether layers were dried over MgS0 ₄ . The product was purified by chromatography using 10% EtOAc in n-hexane. A white solid was obtained. 83% yield.

¹ H NMR (400 MHz, CDCI ₃ ) δ 5.87 - 5.73 (m, 1 H), 5.39 (dd, J = 7.2, 5.7 Hz, 2H), 5.20 - 4.92 (m, 2H), 2.56 - 2.40 (m, 4H), 2.38 - 2.1 9 (m, 4H), 2.07 - 1 .89 (m, 2H), 1 .43 - 1 .19 (m, 18H), 0.93 - 0.81 (m, 3H); ¹³ C NMR (1 01 MHz, CDCI ₃ ) δ 209.93, 137.33, 131.80, 131 .46, 128.35, 127.80, 1 1 5.34, 1 15.31 , 42.91 , 42.04, 32.66, 32.06, 29.80, 29.78, 29.70, 29.66, 29.62, 29.49, 29.47, 29.31 , 27.90, 27.87, 27.34, 26.97, 22.84, 21 .80, 14.27.

Obtained by the following:

General method for the preparation of diene esters (Dx), substrates for the RCM reaction

but-3-en-1 - l pentadeca-4-enoate (D30)

7.0, 1 0.2, 6.7 2H), 4.13 (td, 07 - 1 .91 (m, 2H), 1 .38 - 1 .19 (m, 16H), 0.92 - 0.84 (m, 3H); ^{1 J} C NMR (101 MHz, CDCI ₃ ) δ 173.39, 134.21 , 132.03, 131 .72, 127.99, 127.42, 1 17.32, 1 17.30, 63.53, 63.48, 34.54, 33.25, 32.67, 32.07, 29.79, 29.71 , 29.67, 29.61 , 29.50, 29.47, 29.30, 28.10, 27.36, 22.98, 22.85, 14.28.

hexadeceno-1 ,16-diol

100 mL of THF and 7 equivalents of lithium aluminium hydride were placed in a 250 mL single-necked round flask and then cooled to a temperature of 0°C.

The whole was stirred and then 1 equivalent of hexadecandioic acid was added portionwise. The reaction mixture was heated to room temperature and then heated at THF reflux for 4 hours. Afterwards, the reaction mixture was cooled to 0°C and diluted with diethyl ether to a volume of 200 mL. Next, the following solutions were added dropwise: 9.8 mL water, 9.8 mL of a 15% solution of NaOH (aq), 29.4 mL water. The mixture was allowed to heat to room temperature and was stirred for 15 minutes. Next, MgS0 ₄ was added and the mixture was allowed to rest while stirring for another 15 followed by methylene chloride. The resulting filtrate was evaporated and then dried to yield 7.27 grams of diol. 81 % yield.

¹ H NMR (400 MHz, CD ₃ OD) δ 3.52 (t, J = 6.6 Hz, 4H), 3.31 - 3.29 (m, 4H), 1 .39 - 1 .25 (m, 24H); ¹³ C NMR (101 MHz, CD ₃ OD) δ 61 .58, 32.25, 29.36, 29.35, 29.32, 29.20, 25.53.

Octacose-6,22-dien (D31 )

The diol (1 eq.) and 100 mL acetonitrile were placed in a 200 mL beaker with a stirring element. The mixture was re-heated to a temperature of 50°C, after which copper complex [Cu(MeCN) ₄ ]PF ₆ (10 mol%), TEMPO (10 mol%) 2,2'-bipyridyl (10 mol%) and 1 -methylimidazole (20 mol%) were added one by one. The reaction was conducted for 4 hours until the substrate disappeared. Afterwards, the whole was evaporated and dissolved in methylene chloride, and SnachCat solution was then added. After stirring, the solution was filtered (through Si0 ₂ ), washing it with methylene chloride, and then the solution was evaporated.

Hexyl triphenylphosphine bromide (2.1 eq.) was dissolved in 120 mL tetrahydrofuran under the atymosphere of argon in a 250 mL single-necked round flask. 2.5M solution of n-butyllithium in hexane (2.1 eq) was added dropwise to the resulting mixture, and allowed to rest while stirring for 30 minutes. The resulting solution was cooled to 0°C, and the previously obtained aldehyde in a solution of tetrahydrofuran (1 eq.) was slowly added dropwise. The reaction mixture was heated to room temperature and then stirring was continued for another 2 hours at room temperature. 50 mL of saturated ammonium chloride solution was then added. The mixture was washed four times with methylene chloride. The combined ether layers were dried over MgS0 ₄ . The product was purified by chromatography using n- hexane. A colourless oil was obtained. 75% yield.

¹ H NMR (400 MHz, CDCI ₃ ) 5.46 - 5.27 (m, 4H), 2.10 - 1 .90 (m, 8H), 1 .44 - 1 .16 (m, 36H), 0.97 - 0.80 (m, 6H); ¹³ C NMR (101 MHz, CDCI ₃ ) δ 130.05, 130.04, 31 .69, 29.93, 29.85, 29.82, 29.73, 29.62, 29.48, 27.36, 27.33, 22.75, 14.25. But-3-en-1 -yl oleate (D32)

Oleic acid K3 (1 eq.) and 3-buten-1 -ol A10 (1 .5 eq.) were dissolved in toluene (20 mL), after which two drops of sulfuric acid were added. The

Dean-Stark apparatus was then mounted and the mixture was heated for 3 hours under reflux. After cooling to room temperature, the reaction mixture was transferred to a separator, washed with saturated sodium bicarbonate solution (1 x 5 mL) and brine (1 x 5 mL). The organic fraction was concentrated on a rotary evaporator. The crude product was purified by column chromatography with 2% EtOAc/n-hexane (v/v). A colourless oil was obtained with a 87% yield.

¹ H NMR (400 MHz, CDCI ₃ ) δ 5.78 (ddt, J = 16.9, 10.2, 6.7 Hz, 1 H), 5.39 - 5.28 (m, 2H), 5.15 - 5.02 (m, 2H), 4.12 (t, J = 6.8 Hz, 2H), 2.42 - 2.34 (m, 2H), 2.29 (t, J = 7.5 Hz, 2H), 2.05 - 1 .96 (m, 4H), 1 .67 - 1 .56 (m, 2H), 1 .38 - 1 .20 (m, 20H), 0.94 - 0.83 (m, 3H). ; ¹³ C NMR (1 01 MHz, CDCI ₃ ) δ 13C NMR (101 MHz, cdcl3) δ 174.0, 134.2, 130.1 , 129.9, 1 17.3, 63.4, 34.5, 33.3, 32.1 , 29.9, 29.8, 29.7, 29.5, 29.3, 29.3, 27.4, 27.3, 25.1 , 22.8, 14.3.

cycloheptadec-9-en-1 -on (M13)

Ή NMR (400 MHz, CDCI ₃ ) δ 5.38 - 5.23 (m, 2H), 2.37 (dt, J = 9.4, 6.8 Hz, 4H), 1 .98 (ddt, J = 8.2, 3.9, 2.4 Hz, 4H), 1 .69 - 1 .51 (m, 4H), 1 .43 - 1 .13 (m, 16H); ¹³ C NMR (100 MHz, CDCI ₃ ) δ 213.31 , 212.68, 131 .07, 130.25, 42.59, 42.56, 32.06, 29.14, 28.93,

28.89, 28.72, 28.47, 28.33, 28.24, 27.52, 26.80, 24.13, 23.98.

cyclohept-4-en-1 -on (M14)

1 H NMR (400 MHz, CDCI ₃ ) δ 5.78 (t, J = 2.9 Hz, 2H), 2.71 - 2.60 (m, 4H), 2.43 - 2.28 (m, 4H); ¹³ C NMR (1 00 MHz, CDCI ₃ ) δ 213.8, 129.6, 42.6, 24.2.

(9-E/Z)-dodec-9-en-12-olid (M17)

Ή NMR (400 MHz, CDCI ₃ ) δ 5.60 - 5.25 (m, 2H), 4.24 - 4.08 (m, 2H), 2.45 - 2.23 (m, 4H), 2.13 - 1 .94 (m, 2H), 1 .72 - 1 .57 (m, 2H), 1 .53 - 1 .10 (m, 8H). ; ¹³ C NMR (101 MHz, CDCI3) δ ¹³ C NMR (1 01 MHz, cdcl3) δ 174.8, 174.1 , 134.8, 134.8, 132.3, 127.2, 126.5, 64.3, 63.0, 35.5, 34.0, 32.7, 32.7, 32.1 , 29.8, 27.6, 27.5, 27.4, 27.4, 27.4, 27.4, 27.3,

27.0, 26.1 , 26.0, 24.7, 24.3, 23.6. Example XXX (complementing example XII to table 8)

D12 0,25 mol/kg

M3

Diagram 27. Metathesis cyclization of c/ ^' s-non-6-en-1 -yl oleate using Bertrand complex Yield = 42%, purity = 24%, E/Z ratio = 2.9

Example XXXI (complementing example XII to table 8)

D12 0,25 mol/kg

M3

Diagram 28. Metathesis cyclization of c/s-non-6-en-1 -yl oleate using a complex of cat. 19.

Yield = 29%, purity = 38%, E/Z ratio = 2.8

Example XXXI

Metathesis cvclization of 3-but-1 -enyl oleate using PAO 6 as a diluent with a temperature gradient of 40-> 1 10°C and a diffusion pump

The reaction was conducted in accordance with the procedure and conditions of example XXVI

D32 0,25 mol/kg

M17

Diagram 29. Metathesis cyclization of 3-but-1 -enyl oleate.

Yield = 73%, purity = 96%, E/Z ratio = 3.6 Example XXXII

Metathesis cvclization of c/ ^' s-non-6-en-1 -yl oleate using PAO 6 as a diluent and a diffusion pump in a weight concentration of 90% w/w.

PA06 (60 mg) and c/ ^' s-non-6-en-1 -yl oleate (D12, 61 0 mg ; 1 .5 mmol) were placed in a single-necked, 1 0ml_ round flask equipped with a magnetic stirring element. Next, catalyst cat. 4 was added in the amount of 1 %mol. Immediately afterwards, the reaction flask was connected to a system with a collector connected to a diffusion pump. After evacuating the reaction system, the reaction flask was immersed in a heating bath at a temperature determined as 1 10°C. This was stirred for the next 8 hours, while maintaining the lowest possible pressure (of the order of 1 -1 0 ⁶ mbar). During the reaction, products were collected in the collector attached to the reaction flask. After 8 hours, the connection of the reaction system to the diffusion flask was closed, the heating bath was removed, the stirring was stopped and th e reaction system was opened so that air could access it. The crude product was eluted from the collector with hexane (20 mL), and then purified by chromatography using n-hexane and ethyl acetate.

Diagram 29. Metathesis cyclization of cis-non-6-en-1 -yl oleate at a concentration of 90% w/w. Yield = 34%, purity = 83%, E/Z ratio = 2.7