Development of Highly Enantio- and Z-Selective Grubbs Catalysts via Controllable C-H Bond Activation

Li, Shaofeng1,2; Feng, Shijie1,2; Zhou, Yali1,2; Liu, Chao1,2; Chen, Bo1,2; Xing, Xiangyou1,2

2023-10-06

10.1021/jacs.3c08420

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Impact Factor & Quartile

0002-7863

1520-5126

Asymmetric olefin metathesis is a powerful strategy for stereocontrolled synthesis that allows the formation of chiral elements in conjunction with carbon-carbon double bonds. Here, we report a new series of cyclometalated stereogenic-at-Ru catalysts that enable highly efficient asymmetric ring opening/cross-metathesis (AROCM) and asymmetric ring-closing metathesis (ARCM) reactions. Single enantiomers of these catalysts with either right-handed or left-handed configurations at the Ru center can be easily accessed via highly stereoselective C-H bond activation-based cyclometalation. Right-handed chiral Ru catalysts enabled the Z- and enantioselective AROCM of a wide range of norbornenes and terminal alkenes, generating densely functionalized cyclopentanes with excellent stereo- and enantioselectivities (99:1 Z/E, up to 99% ee). Left-handed chiral Ru catalysts enabled the facile ARCM of sterically unhindered, all-terminal prochiral trienes, which had not been achieved by previous Ru catalysts, providing simple cyclic ethers and amides with tertiary or quaternary carbon stereocenters with excellent enantioselectivities (up to 99% ee).

SCI

English

NI Journal Papers

First ; Corresponding

Shenzhen YOUWEI Tech Group[2020B121201002] ; Guangdong Provincial Key Laboratory of Catalysis[2021A1515010329] ; Guangdong Basic and Applied Basic Research Foundation[JCYJ20220530114611025]

Chemistry

Chemistry, Multidisciplinary

WOS:001082691600001

AMER CHEMICAL SOC

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China

Li, Shaofeng,Feng, Shijie,Zhou, Yali,et al. Development of Highly Enantio- and Z-Selective Grubbs Catalysts via Controllable C-H Bond Activation[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023,145(41).

Li, Shaofeng,Feng, Shijie,Zhou, Yali,Liu, Chao,Chen, Bo,&Xing, Xiangyou.(2023).Development of Highly Enantio- and Z-Selective Grubbs Catalysts via Controllable C-H Bond Activation.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,145(41).

Li, Shaofeng,et al."Development of Highly Enantio- and Z-Selective Grubbs Catalysts via Controllable C-H Bond Activation".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145.41(2023).