Pd-Catalyzed Asymmetric Allenylation of Secondary Phosphine Oxides with Enyne-Type Propargylic Carbamates for the Construction of Chiral Allenyl Phosphine Oxides

作者：Yujie Dong, Nianci Zhang, Fazhou Yang, Jinbao Wang, Bo Wang, Jun Liu, Bing Zheng, Cheng Zhang, Leijie Zhou, Hongchao Guo · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.5c05571 · 被引用次数：4 · 研究领域：Asymmetric Hydrogenation and Catalysis、Catalytic Alkyne Reactions、Asymmetric Synthesis and Catalysis

Chiral allenyl phosphine oxides represent a significant kind of synthetic target with promising potential for various applications. However, explorations toward their asymmetric synthesis remain scarce, primarily due to the competitive coordination of phosphine oxides with metal catalysts. Herein, we report a Pd-catalyzed enantioselective allenylation of secondary phosphine oxide for the efficient construction of a variety of chiral allenyl phosphine oxides. The success of this reaction arises from the enhanced (bidentate form) coordination of a newly designed, fungicide-inspired enyne-type propargylic carbamate with a chiral Pd complex. This protocol features high yields and enantioselectivities, scalability, and versatile derivatization. Mechanistic studies confirmed the exclusion of a kinetic resolution pathway.