Nickel-Catalyzed Enantioconvergent and Diastereoselective Allenylation of Alkyl Electrophiles: Simultaneous Control of Central and Axial Chirality.
Nickel-Catalyzed Enantioconvergent and Diastereoselective Allenylation of Alkyl Electrophiles: Simultaneous Control of Central and Axial Chirality.
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DOI：
10.1021/jacs.4c00593
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发表时间：
2024-03
影响因子：
15
通讯作者：
Asik Hossain;Robert L Anderson;Claudia S Zhang;Peng Chen;Gregory C Fu
中科院分区：
文献类型：
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作者：
Asik Hossain;Robert L Anderson;Claudia S Zhang;Peng Chen;Gregory C Fu
近年来，在同时控制邻位立体化学的方法的开发方面已经描述了显著的进展，其中两个立体化学元素都是中心手性;相比之下，控制中心手性和轴向手性的方法相对较少。本文报道了手性镍催化剂实现了外消旋仲烷基亲电试剂与前手性1，3-烯炔（在氢硅烷存在下）的对映体会聚和非对映体选择性偶联，生成具有相邻立体中心的手性四取代丙二烯。在该过程中形成碳-碳键和碳-氢键，其提供良好的立体选择性并且与一系列官能团相容。
In recent years, remarkable progress has been described in the development of methods that simultaneously control vicinal stereochemistry, wherein both stereochemical elements are central chirality; in contrast, methods that control central and axial chirality are comparatively rare. Herein we report that a chiral nickel catalyst achieves the enantioconvergent and diastereoselective coupling of racemic secondary alkyl electrophiles with prochiral 1,3-enynes (in the presence of a hydrosilane) to generate chiral tetrasubstituted allenes that bear an adjacent stereogenic center. A carbon-carbon and a carbon-hydrogen bond are formed in this process, which provides good stereoselectivity and is compatible with an array of functional groups.