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Updated: Jul 14, 2025
Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
Development of Highly Enantio- and Z-Selective Grubbs Catalysts via Controllable C-H Bond Activation
Shaofeng Li1, Shijie Feng1, Yali Zhou1
1Shenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, China.
Abstract:
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).
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