Development of a more efficient catalyst for the redox-neutral organocatalytic mitsunobu reaction by DFT-guided catalyst design  

作　　者：Dingguo Song Changjun Zhang Yuqi Cheng Linlin Chen Jie Lin Changdi Zheng Ting Liu Yuxin Ding Fei Ling Weihui Zhong 

机构地区：[1]College of Pharmaceutical Sciences,Zhejiang University of Technology,Hangzhou 310014,China

出　　处：《Green Synthesis and Catalysis》2024年第4期290-296,共7页绿色合成与催化（英文）

基　　金：financially supported by the National Natural Science Foundation of China(Nos.22078298,21978271 and 22178315);Natural Science Foundation of Zhejiang Province(No.LY21B020007);China Postdoctoral Science Foundation(No.2022M712824);Key Research and Development Program of Zhejiang Province(No.2023C03117).

摘　　要：The study of a Mitsunobu reaction is an important topic.Denton and co-workers first reported a novel(2-hydroxybenzyl)diphenylphosphine oxide for realizing the catalytic Mitsunobu reaction via a five-membered phosphonium species.However,it is still worth investigating how to improve catalysts with higher efficiency.Guided by computational and experimental studies,we designed a new type of biphenyl-based phosphine oxide that would form a six-membered phosphonium species as a key intermediate to trigger the catalytic Mitsunobu reaction with a lower barrier of the rate-determining step(30.3 kcal/mol).DFT calculations revealed that only trans dehydration was participated in our catalytic progress and a strongπ-πinteraction and small spatial constraint of TS-V were crucial for high behavior.This readily accessible,highly stable,easily recyclable and efficient catalyst would boost the catalytic Mitsunobu reaction.

关 键 词：Phosphine oxide Mitsunobu reaction Late-sFtage diversification Drug discovery process 

分 类 号：O64[理学—物理化学]