Title:
LARGE STERIC HINDERANCE PALLADIUM-NITROGEN-HETEROCYCLIC CARBENE COMPLEX, PREPARATION METHOD FOR SAME, APPLICATIONS OF SAME, AND SYNTHESIS METHOD FOR SONIDEGIB BASED ON SAME
Document Type and Number:
WIPO Patent Application WO/2022/078306
Kind Code:
A1
Abstract:
The present invention relates to the technical field of organic synthesis and chemical catalysis. Disclosed are a large steric hinderance palladium-nitrogen-heterocyclic carbene complex, a preparation method for same, applications of same in efficiently catalyzing a C-N coupling reaction in room temperature conditions, and a synthesis method for sonidegib based on same. The structure of the large steric hinderance palladium-nitrogen-heterocyclic carbene complex of the present invention has diphenylimidazole as the main ligand skeleton and a functionalized allyl as an ancillary ligand, with the introduction of the functionalized allyl to serve as an ancillary ligand beside the metal center of a catalyst, provides significantly increased catalytic activity and stability, is applicable in efficiently catalyzing the C-N coupling reaction, specifically, efficiently catalyzing the C-N coupling reaction at room temperature conditions, and attains a yield of up to 99%. Also provided in the present invention is a method for synthesizing in three steps at room temperature with an aryl/aliphatic amine and an aryl chloride as reactants and catalyzed by a palladium catalytic system. The synthesis method of the present invention has few steps and attains a total yield of up to 74.5%.
Inventors:
QIU LIQIN (CN)
OUYANG JIASHENG (CN)
OUYANG JIASHENG (CN)
Application Number:
PCT/CN2021/123160
Publication Date:
April 21, 2022
Filing Date:
October 12, 2021
Export Citation:
Assignee:
UNIV SUN YAT SEN (CN)
International Classes:
C07F15/00; B01J31/22; C07C209/10; C07C211/48; C07C211/54; C07D213/74; C07D295/023; C07D295/033; C07D401/12; C07D405/12; C07D405/14; C07D409/12; C07D413/04; C07D417/12; C07D471/04
Foreign References:
| CN112209972A | 2021-01-12 | |||
| CN109293649A | 2019-02-01 |
Other References:
OUYANG JIA-SHENG, LIU SIQI, PAN BENDU, ZHANG YAQI, LIANG HAO, CHEN BIN, HE XIAOBO, CHAN WESLEY TING KWOK, CHAN ALBERT S. C., SUN T: "A Bulky and Electron-Rich N -Heterocyclic Carbene–Palladium Complex (SIPr) Ph 2 Pd(cin)Cl: Highly Efficient and Versatile for the Buchwald–Hartwig Amination of (Hetero)aryl Chlorides with (Hetero)aryl Amines at Room Temperature", ACS CATALYSIS, AMERICAN CHEMICAL SOCIETY, US, vol. 11, no. 15, 6 August 2021 (2021-08-06), US , pages 9252 - 9261, XP055921142, ISSN: 2155-5435, DOI: 10.1021/acscatal.1c01929
XU LIANG, SHI YIAN: "Chiral N -Heterocyclic Carbene−Pd(0)-Catalyzed Asymmetric Diamination of Conjugated Dienes and Triene", THE JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, vol. 73, no. 2, 1 January 2008 (2008-01-01), pages 749 - 751, XP055921143, ISSN: 0022-3263, DOI: 10.1021/jo702167u
SUSANNE M. PODHAJSKY; YASUMASA IWAI; AMANDA COOK-SNEATHEN; MATTHEW S. SIGMAN;: "Asymmetric palladium-catalyzed hydroarylation of styrenes and dienes", TETRAHEDRON, ELSEVIER SIENCE PUBLISHERS, AMSTERDAM, NL, vol. 67, no. 24, 11 February 2011 (2011-02-11), AMSTERDAM, NL , pages 4435 - 4441, XP028216330, ISSN: 0040-4020, DOI: 10.1016/j.tet.2011.02.027
LUAN XINJUN, WU LINGLIN, DRINKEL EMMA, MARIZ RONALDO, GATTI MICHELE, DORTA RETO: "Highly Chemo- and Enantioselective Synthesis of 3-Allyl-3-aryl Oxindoles via the Direct Palladium-Catalyzed α-Arylation of Amides", ORGANIC LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 12, no. 9, 7 May 2010 (2010-05-07), US , pages 1912 - 1915, XP055921145, ISSN: 1523-7060, DOI: 10.1021/ol1003093
XU LIANG, SHI YIAN: "Chiral N -Heterocyclic Carbene−Pd(0)-Catalyzed Asymmetric Diamination of Conjugated Dienes and Triene", THE JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, vol. 73, no. 2, 1 January 2008 (2008-01-01), pages 749 - 751, XP055921143, ISSN: 0022-3263, DOI: 10.1021/jo702167u
SUSANNE M. PODHAJSKY; YASUMASA IWAI; AMANDA COOK-SNEATHEN; MATTHEW S. SIGMAN;: "Asymmetric palladium-catalyzed hydroarylation of styrenes and dienes", TETRAHEDRON, ELSEVIER SIENCE PUBLISHERS, AMSTERDAM, NL, vol. 67, no. 24, 11 February 2011 (2011-02-11), AMSTERDAM, NL , pages 4435 - 4441, XP028216330, ISSN: 0040-4020, DOI: 10.1016/j.tet.2011.02.027
LUAN XINJUN, WU LINGLIN, DRINKEL EMMA, MARIZ RONALDO, GATTI MICHELE, DORTA RETO: "Highly Chemo- and Enantioselective Synthesis of 3-Allyl-3-aryl Oxindoles via the Direct Palladium-Catalyzed α-Arylation of Amides", ORGANIC LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 12, no. 9, 7 May 2010 (2010-05-07), US , pages 1912 - 1915, XP055921145, ISSN: 1523-7060, DOI: 10.1021/ol1003093
Attorney, Agent or Firm:
GUANGZHOU JUNCT INTELLECTUAL PROPERTY AGENCY FIRM (GENERAL PARTNERSHIP) (CN)
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