Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan.
J Am Chem Soc. 2021 Nov 10;143(44):18394-18399. doi: 10.1021/jacs.1c10042. Epub 2021 Nov 1.
We report herein on the phosphine-catalyzed hydrovinylation reaction by three-component coupling of acyl fluorides, silyl enol ethers, and alkynoates. The key to the success of the reaction is the formal transmetalation between pentacoordinate P(V) species (i.e., fluorophosphorane) and a silyl enol ether, which allows for C-C bond formation between the polarity-mismatched sites. The bond formation that cannot be attained even by transition metal catalysis is accomplished by a P(III)/P(V) manifold.
我们在此报告了通过酰氟、硅基烯醇醚和炔酸酯的三组分偶联反应实现的膦催化氢甲酰化反应。反应成功的关键在于五配位 P(V)物种（即氟膦烷）和硅基烯醇醚之间的形式转金属化，这使得极性不匹配的位点之间能够形成 C-C 键。即使通过过渡金属催化也无法实现的键形成，通过 P(III)/P(V) 多相反应得以完成。
