A general, efficient, highly enantio‐ and chemoselective N‐heterocyclic carbene (NHC)/Ni‐catalyzed addition of readily available and stable arylboronic esters to ketones is reported. This protocol provides unexpectedly fast access (usually 10 min) to various chiral tertiary alcohols with exceptionally broad substrate scope and excellent functional group tolerance (76 examples, up to 98 % ee). This process is orthogonal to other known Ni‐mediated Suzuki–Miyaura couplings, as it tolerates aryl chlorides, fluorides, ethers, esters, amides, nitriles, and alkyl chlorides. The reaction is applied to late‐stage modifications of various densely functionalized medicinally relevant molecules. Preliminary mechanistic studies suggest that a rare enantioselective η²‐coordinating activation of ketone carbonyls is involved. This cross‐coupling‐like mechanism is expected to enable other challenging transformations of ketones.

中文翻译：

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镍/ N-杂环碳烯催化可实现有机硼酸酯对酮的快速对映和化学选择性芳香化

据报道，一般高效，高度对映和化学选择性的N-杂环卡宾（NHC）/ Ni催化将易于获得的稳定的芳基硼酸酯加到酮中。该协议可提供出乎意料的快速访问权限（通常为10分钟），这些手性叔醇具有特别宽的底物范围和出色的官能团耐受性（76个示例，最高98％ee）。此过程与其他已知的Ni介导的Suzuki-Miyaura偶联正交，因为它可以耐受芳基氯，氟化物，醚，酯，酰胺，腈和烷基氯。该反应适用于各种紧密功能化的医学相关分子的后期修饰。初步机理研究表明，一种罕见的对映选择性η ²涉及酮羰基的配位活化。这种类似交叉耦合的机制有望实现酮类的其他挑战性转化。