Title:
純粋な鏡像的シクロペンタンおよびシクロペンテンβ-アミノ酸の新規な高度に鏡像選択的製造方法
Document Type and Number:
Japanese Patent JP4020425
Kind Code:
B2
Abstract:
Prepn. of enantiomerically pure cyclopentane- or cyclopentene- beta -aminoacids of formula (I) comprises:(a) converting a meso-cyclopentane- or cyclopentene dicarboxylic anhydride of formula (II) into an enantiomerically pure monoester of formula (IVa) via enantiomerically pure salt of formula (IV), by asymmetric alcoholysis with an alcohol of formula (III) in a solvent in presence of an equimolar amt. of a chiral amine base in pure enantiomer form;(b) activating the free carboxy function then reacting with liq. ammonia to give the enantiomerically pure amide of formula (V);(c) cleaving the ester residue R<15> in an inert solvent in presence of a nucleophilic auxiliary, by enzymatic methods or in presence of a palladium catalyst to give the acid or salt of formula (VI);(d) carrying out Hoffmann rearrangement with alkali(ne earth) metal hypochlorite in aq. alkali(ne earth) metal hydroxide soln.;(e) blocking the free amino gp. in soln. using a conventional amino-protecting gp., isolating the protected cpds. and cleaving the protecting gp. to give the pure enantiomer of (I). A,L = H;D, E = H, halo, OH or 1-8C alkyl,etc.; or D+E = =CR<6>R<7>, =N-OH, =O or =S; or A+D or E+L = additional bond;R<6>, R<7> = H, halo, 1-8C alkyl, 1-8C alkoxy,etc.; R<2> = H, amino-protecting gp., 1-8C alkyl (opt. substd. by 1 or 2 of OH, CHO up to 6C acyl, phenyl and benzoyl, where phenyl and benzoyl are themselves opt. substd. by 1 or 2 of halo, NO2, CN and 1-6C alkyl),etc.;R<3> =H or 1-8C alkyl (opt. substd. by phenyl); or R<2>+R<3> = =CHR<14>;R<14> = H or 1-8C alkyl (opt. substd. by halo, OH,etc.;T = O, S or NH; R<1> = H, 1-8C alkyl (opt. substd. by 1-3 of OH, halo,etc.), phenyl (opt. substd. by 1-3 of OH, halo, NO2,etc.);or if T = e.g. NH, R<15> = 2-5C alkyl or 2-5C alkenyl (opt. substd. by CN, SiMe3, Ph or CCl3);V = chiral amine base;X = H, alkali metal or alkaline earth metal. Enantiomerically pure cpds. (IV), (IVa) and (V) are new.
Inventors:
Mitsutendorf, Joachim
Arolto, Hermann
Huay, Peter
Matsuke, Michael
Milli Tour, Hans-Christian
Morse, Claus-Helmut
Arolto, Hermann
Huay, Peter
Matsuke, Michael
Milli Tour, Hans-Christian
Morse, Claus-Helmut
Application Number:
JP51881895A
Publication Date:
December 12, 2007
Filing Date:
January 09, 1995
Export Citation:
Assignee:
Bayer Actien Gezershyaft
International Classes:
C07C61/35; C07C67/08; C07D307/93; C07C69/608; C07C69/74; C07C69/753; C07C69/757; C07C227/32; C07C229/28; C07C229/48; C07C231/02; C07C231/18; C07C233/58; C07C255/14; C07C271/24; C07D453/04; C07F7/08; C07C233/00; C07D453/00
Domestic Patent References:
| JP6056751A |
Other References:
The Journal of Organic Chemistry, Vol.54,No.21,1989, P5115-5122
Tetrahedron:Asymmetry, Vol.4,No.5,1993, P1047-1050
Chemical and Pharmaceutical Bulletin, Vol.35,No.6,1987,P2266-2271
Angewandte Chemie, Vol.23,No.1,1984, P67-68
Acta Chem.Scand., Vol.46,No.11,1992, P1127-1129
Tetrahedron:Asymmetry, Vol.4,No.5,1993, P1047-1050
Chemical and Pharmaceutical Bulletin, Vol.35,No.6,1987,P2266-2271
Angewandte Chemie, Vol.23,No.1,1984, P67-68
Acta Chem.Scand., Vol.46,No.11,1992, P1127-1129
Attorney, Agent or Firm:
Heikichi Odashima