Enantioselective Synthesis of Pyridines with All-Carbon Quaternary Carbon Centers via Cobalt-Catalyzed Desymmetric [2+2+2] Cycloaddition

被引：52

作者：

Li, Ke ^{[1
]}

Wei, Linsheng ^{[1
]}

Sun, Minghe ^{[1
]}

Li, Bing ^{[1
]}

Liu, Min ^{[1
]}

Li, Changkun ^{[1
]}

机构：

[1] Shanghai Jiao Tong Univ, Frontiers Sci Ctr Transformat Mol, Sch Chem & Chem Engn, Shanghai Key Lab Mol Engn Chiral Drugs, 800 Dongchuan Rd, Shanghai 200240, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2021年 / 60卷 / 37期

关键词：

cobalt; desymmetrization; pyridine synthesis; quaternary carbon; regioselectivity; ONE-STEP SYNTHESIS; AXIALLY CHIRAL BIARYLS; ASYMMETRIC HYDROGENATION; LIGANDS; NITRILES; CONSTRUCTION; COBALTACYCLOPENTADIENE; ALPHA; OMEGA-DIYNES; DERIVATIVES; ACETYLENES;

D O I：

10.1002/anie.202105452

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A Co-catalyzed enantioselective desymmetric [2+2+2] cycloaddition for synthesis of pyridines with all-carbon quaternary carbon centers has been developed. The regio- and enantioselectivities are controlled by the inherent nature of terminal alkynes and the substituents on the bisoxazolinephosphine ligands. Pyridines with 5-substitutents could be obtained with >20:1 regioselectivity and up to 94 % ee when terminal alkyl, alkenyl or silyl alkynes and DTBM/Ph-based NPN* ligand L6 were used. Terminal aryl alkynes and Ph/Bn-based ligand L4 leads to formation of pyridines with 6-substitutents in up to 99 % ee.

引用

页码：20204 / 20209

页数：6

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