Transition metal (TM)-catalysed directed hydroboration of aliphatic internal olefins which facilitates the construction of complex alkylboronates is an essential synthetic methodology. Here, an efficient method for the borylation of cyclopropanes involving TM-catalysed directed C–C activation has been developed. Upon exposure to neutral Rh(I)-catalyst systems, N-Piv-substituted cyclopropylamines (CPAs) undergo proximal-selective hydroboration with HBpin to provide valuable γ-amino boronates in one step which are otherwise difficult to synthesize by known methods. The enantioenriched substrates can deliver chiral products without erosion of the enantioselectivities. Versatile synthetic utility of the obtained γ-amino boronates is also demonstrated. Experimental and computational mechanistic studies showed the preferred pathway and the origin of this selectivity. This study will enable the further use of CPAs as valuable building blocks for the tunable generation of C–heteroatom or C–C bonds through selective C–C bond activation.

中文翻译：

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铑催化环丙烷的选择性C-C键活化和硼化

过渡金属（TM）催化的脂肪族内烯烃的定向硼氢化有利于复杂烷基硼酸酯的构建，是一种重要的合成方法。在这里，开发了一种有效的环丙烷硼基化方法，涉及 TM 催化的定向 C-C 活化。暴露于中性 Rh( I )-催化剂体系后，N -Piv-取代的环丙胺 (CPA) 与 HBpin 发生近端选择性硼氢化反应，一步即可提供有价值的 γ-氨基硼酸盐，否则很难通过已知方法合成。对映体富集的底物可以提供手性产物而不损害对映体选择性。还证明了所获得的γ-氨基硼酸酯的多功能合成用途。实验和计算机制研究表明了首选途径和这种选择性的起源。这项研究将进一步利用 CPA 作为有价值的构建模块，通过选择性 C-C 键激活来可调生成 C-杂原子或 C-C 键。