Enantioselective Synthesis of Cyclopropanes Via CuH-Catalyzed Intramolecular Hydroalkylation
ACS catalysis(2024)
摘要
A Cu-catalyzed cyclopropanation of gamma-bromocrotonate derivatives via a hydrocupration-alkylation sequence is described. This hydroalkylation process is of good generality and allows access to chiral cyclopropanes bearing aryl, heteroaryl, N-indole, alkenyl, and alkyl substituents, all with complete trans-diastereoselectivity, enantioselectivities up to >99:1 er, and good to high yields. An experimental and computational mechanistic analysis was undertaken, which provided a full understanding of the factors affecting the reaction's diastereo- and enantioselectivity. More specifically, it was found that the Cu-catalyst drives both the conjugate hydride addition and alkylation steps and that the reaction enantioselectivity is governed by distortion effects of the metal coordination sphere at the diastereomeric TSs.
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关键词
CuH-catalysis,enantioselective catalysis,hydrocupration,olefinhydroalkylation,cyclopropanes
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