Catalytic Diastereo- and Enantioselective Cyclopropanation of gem-Dihaloalkanes and Terminal Olefins |
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| Authors: | Hou-Lu Liu Xinyu Wang Ke Gao Zhaobin Wang |
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| Institution: | 1. Department of Chemistry, Zhejiang University, Hangzhou, 310058 China
Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science, Westlake University, Hangzhou, 310024 China;2. Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science, Westlake University, Hangzhou, 310024 China |
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| Abstract: | Chiral cyclopropane derivatives are essential in synthetic chemistry and drug discovery. Their synthesis commonly relies on asymmetric cyclopropanation of diazo compounds, potentially explosive and needing stabilizing substituents. Thus, asymmetric catalytic transformations of non-stabilized carbenes or carbenoids remain a formidable challenge. Herein, we report the unprecedented chromium-catalyzed asymmetric cyclopropanation of readily available gem-dihaloalkanes and terminal olefins. Distinct from previous approaches, gem-dihaloalkanes serve as suitable precursors for non-stabilized carbenes or carbenoids, furnishing various functionalized chiral cyclopropanes. Mechanistic studies, including radical trapping, non-linear effect, and UV/Vis spectroscopy, provide insights into the catalytic process, featuring radical-polar crossover. |
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| Keywords: | Asymmetric Cyclopropanation Chromium Catalysis gem-Dihaloalkane Non-Stabilized Carbene Terminal Olefin |
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