Enantio- and E -Selective Copper-Catalyzed Three-Component Hydrofunctionalization of Internal Allenes Bearing Methylidenecyclobutanes with Diborons and Ketones

作者：Yujie Dong, Nianci Zhang, Rongjin Ning, Fazhou Yang, Jinbao Wang, Jun Liu, Hongchao Guo, Cheng Zhang · 发表于：Organic Letters · 年份：2025 · DOI：10.1021/acs.orglett.5c01718 · 被引用次数：4 · 研究领域：Organoboron and organosilicon chemistry、Catalytic Cross-Coupling Reactions、Catalytic C–H Functionalization Methods

Internal allenes are challenging substrates in copper-catalyzed borylative difunctionalization. When internal allenes featuring a methylidenecyclobutane motif were employed, a copper-catalyzed hydrofunctionalization reaction using diborons and ketones as reaction partners in the presence of a chiral monophosphorus ligand was developed, affording a series of unsaturated chiral tertiary alcohols preserving the methylidenecyclobutane motif in high regio- and stereoselectivities. Control experiments suggest that the reaction involves a boronation-deboronation process, and a plausible mechanism has been proposed.