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 phosphoni...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.展开更多
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)+1 种基金China Postdoctoral Science Foundation(No.2022M712824)Key Research and Development Program of Zhejiang Province(No.2023C03117).
文摘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.
