Aryl-to-Vinyl 1,4-Nickel Migration/Reductive Cross-Coupling Reaction for the Stereoselective Synthesis of Multisubstituted Olefins |
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| Authors: | Cui-Tian Wang Peng-Yu Liang Ming Li Bin Wang Yu-Zhao Wang Xue-Song Li Wan-Xu Wei Xue-Ya Gou Ya-Nan Ding Zhe Zhang Yu-Ke Li Xue-Yuan Liu Prof. Yong-Min Liang |
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| Affiliation: | 1. State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000 P. R. China;2. College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu, 730070 P. R. China;3. Department of Chemistry and Centre for Scientific Modeling and Computation, Chinese University of Hong Kong, Hong Kong, China |
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| Abstract: | The aryl-to-vinyl nickel 1,4-migration (1,4-Ni migration) reaction has been reported for the first time. The generated alkenyl Ni species undergo a reductive coupling reaction with unactivated brominated alkanes affording a series of trisubstituted olefins. This tandem reaction exhibits mild conditions, a broad substrate scope, high regioselectivity, and excellent Z/E stereoselectivity. A series of controlled experiments have shown that the critical 1,4-Ni migration process is reversible. In addition, the alkenyl nickel intermediates obtained after migration are highly Z/E stereoselective and do not undergo Z/E isomerization. The obtained trace isomerization products are caused by the instability of the product. |
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| Keywords: | 1,4-Nickel Migration C−H Activation Multisubstituted Olefins Reductive Cross-Coupling Z/E Stereoselective |
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