Bioisosteric replacement has emerged as a clear strategy for drug-structure optimization. Naphthalene is the core element of many chiral pharmaceuticals and drug candidates. However, as a promising isostere of naphthalene, the chiral version of 1,2-benzazaborine has rarely been explored due to the lack of efficient synthetic methods. Here we describe a copper-catalysed enantioselective hydroboration of alkenes with 1,2-benzazaborines. The method provides a general platform for the atom-economic and efficient construction of diverse chiral 1,2-benzazaborine compounds (more than 60 examples) that bear a 2-carbon-stereogenic centre or allene skeleton in high yields and excellent enantioselectivities. Three 1,2-benzazaborine analogues of bioactive chiral naphthalene-containing molecules have been prepared, and a series of transformations around chiral 1,2-benzazaborines have also been developed. Notably, the hydroboration process of this study reveals that the identity of 1,2-benzazaborine plays an essential role in the rate-determining step and catalyst resting state.

生物等排替代已成为药物结构优化的明确策略。萘是许多手性药物和候选药物的核心元素。然而，作为一种有前途的萘电子等排体，由于缺乏有效的合成方法，1,2-苯并硼啉的手性版本很少被探索。在这里，我们描述了铜催化的烯烃与 1,2-苯并氮硼烷的对映选择性硼氢化反应。该方法为原子经济且高效地构建具有 2-碳立体中心或丙二烯骨架的多种手性 1,2-苯并氮杂硼化合物（超过 60 个实例）提供了一个通用平台，具有高产率和优异的对映选择性。已经制备了三种具有生物活性的手性含萘分子的1,2-苯并硼烷类似物，并且还开发了一系列围绕手性1,2-苯并氮硼烷的转化。值得注意的是，本研究的硼氢化过程表明，1,2-苯并氮杂硼啉的特性在速率决定步骤和催化剂静止状态中起着至关重要的作用。