P(NMe_(2))_(3)介导1,2-二羰基化合物与α,β-不饱和酮的[1+4]环化反应及多取代2,3-二氢呋喃的合成  

Synthesis of Polysubstituted 2,3-Dihydrofurans via P(NMe_(2))_(3)-Mediated[1+4]Annulation of 1,2-Dicarbonyl Compounds withα,β-Unsaturated Ketones

作　　者：薛飞雪 曾建伟 严泰山 韩杰 贺峥杰[1,2] Xue Feixue;Zeng Jianwei;Yan Taishan;Han Jie;He Zhengjie(State Key Laboratory of Elemento-Organic Chemistry,College of Chemistry,Nankai University,Tianjin 300071;Collaborative Innovation Center of Chemical Science and Engineering(Tianjin),Tianjin 300071)

机构地区：[1]南开大学化学学院元素有机化学国家重点实验室,天津300071 [2]天津化学化工协同创新中心,天津300071

出　　处：《有机化学》2022年第11期3805-3815,共11页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21472096,22171143)资助项目。

摘　　要：在P(NMe_(2))_(3)作用下,1,2-二羰基化合物与α,β-不饱和酮顺利发生分子间[1+4]环化反应,生成带有全碳季碳中心的多取代2,3-二氢呋喃类化合物,从而以较高的收率及较宽的底物范围提供了合成该类化合物的新方法.在某些情况下,[1+2]环化反应竞争发生生成多取代的环丙烷化合物.借助密度泛函理论(DFT)计算手段,讨论了反应机理及有关[1+2]环化反应与[1+4]环化反应的化学选择性.A[1+4]annulation of 1,2-dicarbonyl compounds withα,β-unsaturated ketones has been readily realized under the mediation of P(NMe_(2))_(3),producing polysubstituted 2,3-dihydrofurans bearing a quaternary carbon center in fair to good yields with a broad substrate scope.This reaction accordingly constitutes a new synthetic method for such compounds.In some cases,a[1+2]annulation reaction competitively occurs,delivering polysubstituted cyclopropanes.With the aid of density functional theory(DFT)calculation,a plausible mechanism for the[1+4]annulation and the chemoselectivity between[1+2]and[1+4]annulations has been discussed.

关 键 词：[1+4]环化反应 1 2-二羰基化合物 [1+2]环化反应 2 3-二氢呋喃 Kukhtin-Remirez加合物 

分 类 号：O626.11[理学—有机化学]