Phosphine-Catalyzed Stereoselective Ring-Opening Addition of Cyclopropenones with Nucleophiles

作者：Lulu Yang, Xin He, Jiao Jiao, Yuhai Tang, Jing Li, Yang Li, Ruixia Gao, Yong Wu, Silong Xu · 发表于：The Journal of Organic Chemistry · 年份：2023 · DOI：10.1021/acs.joc.3c00603 · 被引用次数：24 · 研究领域：Cyclopropane Reaction Mechanisms、Synthetic Organic Chemistry Methods、Click Chemistry and Applications

A phosphine-catalyzed ring-opening addition reaction of cyclopropenones with a variety of nucleophiles (NuH), including oxygen-, nitrogen-, sulfur-, and carbon-based ones, has been investigated, which produces potentially useful α,β-unsaturated carbonyl derivatives in high yields (up to 99%), high regioselectivity, and exclusive E -selectivity. The reaction proceeds in high efficiency under very mild conditions using only 1 mol % PPh 3 as the catalyst at room temperature. The method is also amenable for the synthesis of deuterated alkenes when deuterated nucleophiles (NuD) are employed. The mechanism is investigated by experiments and DFT calculations, which suggests an α-ketenyl phosphorus ylide as a key intermediate in the catalytic cycle that captures the nucleophiles in a stereoselective manner.