Title:
PREPARATION METHOD FOR TETRA-SUBSTITUTED ALLENOIC ACID COMPOUND BASED ON PALLADIUM CATALYTIC SYSTEM
Document Type and Number:
WIPO Patent Application WO/2022/166870
Kind Code:
A1
Abstract:
Disclosed in the present invention is a preparation method for a tetra-substituted allenoic acid compound based on a palladium catalytic system, that is, an optically active allenoic acid compound having axial chirality is directly constructed in one step by reacting tertiary propargyl alcohol, carbon monoxide and water in an organic solvent under the action of a palladium catalyst, a chiral bisphosphine ligand, an organic phosphoric acid, and an organic additive, and the theoretical yield can reach 100%. The method of the present invention is simple to operate, the raw materials and reagents are easy to obtain, the reaction conditions are mild, the substrate universality is wide, the functional group compatibility is good, the reaction has high enantioselectivity (77%-96% ee), and the reaction is well compatible with complex natural products or substrates of a drug molecular skeleton. The optically active allenoic acid compound obtained by the present invention can be used as an important intermediate for constructing a γ-butyrolactone compound containing a tetra-substituted chiral quaternary carbon center, tetra-substituted allenol, tetra-substituted allenal, tetra-substituted allenyl ketone, tetra-substituted allenamide and other compounds.
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Inventors:
MA SHENGMING (CN)
ZHENG WEIFENG (CN)
QIAN HUI (CN)
ZHENG WEIFENG (CN)
QIAN HUI (CN)
Application Number:
PCT/CN2022/074914
Publication Date:
August 11, 2022
Filing Date:
January 29, 2022
Export Citation:
Assignee:
UNIV FUDAN (CN)
International Classes:
C07C51/14; C07C51/12; C07C57/42; C07C253/30; C07C255/41; C07D333/24
Foreign References:
| CN111302928A | 2020-06-19 | |||
| CN108976123A | 2018-12-11 | |||
| CN104109174A | 2014-10-22 |
Other References:
ZHENG WEI-FENG, ZHANG WANLI, HUANG CHAOFAN, WU PENGLIN, QIAN HUI, WANG LEI, GUO YIN-LONG, MA SHENGMING: "Tetrasubstituted allenes via the palladium-catalysed kinetic resolution of propargylic alcohols using a supporting ligand", NATURE CATALYSIS, vol. 2, no. 11, 1 November 2019 (2019-11-01), pages 997 - 1005, XP055947159, DOI: 10.1038/s41929-019-0346-z
WANG JIE, ZHANG WANLI, WU PENGLIN, HUANG CHAOFAN, ZHENG YANGGUANGYAN, ZHENG WEI-FENG, QIAN HUI, MA SHENGMING: "Chiral tertiary propargylic alcohols via Pd-catalyzed carboxylative kinetic resolution", ORGANIC CHEMISTRY FRONTIERS, vol. 7, no. 23, 24 November 2020 (2020-11-24), pages 3907 - 3911, XP055947175, DOI: 10.1039/D0QO01106A
SOWMIANARAYANAN RAMASWAMY ET AL: "Enantiomerically selective pig liver esterase-catalysed hydrolyses of racemic allenic esters", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, no. 20, 1 January 1986 (1986-01-01), Royal Society of Chemistry, GB, pages 1545 - 1546, XP055712060, ISSN: 0022-4936, DOI: 10.1039/c39860001545
WANG JIE, ZHANG WANLI, WU PENGLIN, HUANG CHAOFAN, ZHENG YANGGUANGYAN, ZHENG WEI-FENG, QIAN HUI, MA SHENGMING: "Chiral tertiary propargylic alcohols via Pd-catalyzed carboxylative kinetic resolution", ORGANIC CHEMISTRY FRONTIERS, vol. 7, no. 23, 24 November 2020 (2020-11-24), pages 3907 - 3911, XP055947175, DOI: 10.1039/D0QO01106A
SOWMIANARAYANAN RAMASWAMY ET AL: "Enantiomerically selective pig liver esterase-catalysed hydrolyses of racemic allenic esters", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, no. 20, 1 January 1986 (1986-01-01), Royal Society of Chemistry, GB, pages 1545 - 1546, XP055712060, ISSN: 0022-4936, DOI: 10.1039/c39860001545
Attorney, Agent or Firm:
MSJLAW OFFICE (CN)
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