A Cu-catalyzed regio- and enantioselective hydroallylation of 1-trifluoromethylalkenes with hydrosilanes and allylic chlorides has been developed. An in situ generated CuH species undergoes the hydrocupration regio- and enantioselectively to form a chiral α-CF₃ alkylcopper intermediate, which then leads to the optically active hydroallylated product. The key to success is the use of not only an appropriate chiral bisphosphine ligand but also 18-crown-6 to suppress the otherwise predominant β-F elimination from the α-CF₃ alkylcopper intermediate. The asymmetric Cu catalysis successfully constructs the nonbenzylic and nonallylic CF₃-substituted C_sp³ chiral center, which is difficult to operate by other means.

中文翻译：

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铜催化的 1-三氟甲基烯烃的区域选择性和对映选择性水解：冠醚的影响

已开发出 Cu 催化的 1-三氟甲基烯烃与氢硅烷和烯丙基氯的区域选择性和对映选择性氢化烯丙基化。一个原位生成CUH物种经历hydrocupration区域选择性和对映选择性地形成手性α-CF ₃烷基铜中间体，其然后导致光学活性hydroallylated产物。成功的关键是不仅要使用合适的手性双膦配体，还要使用 18-crown-6 来抑制 α-CF ₃烷基铜中间体的主要 β-F 消除。不对称Cu催化成功构建了非苄基和非烯丙基CF ₃取代的C _{sp ³} 手性中心，其他方式难以操作。