An operationally convenient cobalt‐catalyzed one‐pot one‐step hydrosilylation/hydroboration reaction of arylidenecyclopropanes is developed to access racemic 1,4‐borylsilylalkanes. In addition, the corresponding asymmetric reaction is developed with a chiral copper catalyst to prepare 1,4‐borylsilylalkanes with high enantioselectivity by a one‐pot two‐step procedure. Mechanistic studies reveal that this difunctionalization process begins with metal‐hydride‐catalyzed ring‐opening hydrosilylation of arylidenecyclopropanes to generate homoallylsilane intermediates, followed by regio‐ or enantioselective metal‐hydride‐catalyzed hydroboration of homoallylsilanes to produce skipped borylsilylalkanes. Selective transformations of C–B and Si–H bonds in skipped borylsilylalkane products are also demonstrated.

中文翻译：

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芳基环丙烷的一锅法钴或铜催化的不对称开环氢硅烷氢化/硼氢化


开发了一种操作方便的钴催化单锅法一步法芳基环丙烷加氢甲硅烷化/硼氢化反应，用于获得外消旋 1,4-硼基硅烷烃。此外，使用手性铜催化剂开发相应的不对称反应，通过一锅两步程序制备具有高对映选择性的 1,4-硼基硅烷烃。机理研究表明，这种二功能化过程始于芳基环丙烷的金属氢化物催化的开环氢硅烷化反应，生成高烯丙基硅烷中间体，然后是区域或对映选择性金属氢化物催化的同烯丙基硅烷氢硼化反应，以产生跳跃的硼酰基硅烷烃。还证明了跳跃的硼基硅烷基烷烃产物中 C-B 和 Si-H 键的选择性转变。