Diazo Esters as Dienophiles in Intramolecular (4+2) Cycloadditions: Computational Explorations of Mechanism

被引：53

作者：

Duan, Abing ^{[1
,2
,3
]}

Yu, Peiyuan ^{[3
]}

Liu, Fang ^{[3
]}

Qiu, Huang

Gu, Feng Long ^{[1
,2
]}

Doyle, Michael P. ^{[4
]}

Houk, K. N. ^{[3
]}

机构：

[1] South China Normal Univ, Minist Educ, Key Lab Theoret Chem Environm, Guangzhou 510006, Guangdong, Peoples R China

[2] South China Normal Univ, Sch Chem & Environm, Guangzhou 510006, Guangdong, Peoples R China

[3] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[4] Univ Texas San Antonio, Dept Chem, San Antonio, TX 78249 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 07期

基金：

美国国家科学基金会;

关键词：

DIELS-ALDER REACTIVITIES; 1,3-DIPOLAR CYCLOADDITIONS; DENSITY FUNCTIONALS; HARTREE-FOCK; DIENES; ORBITALS; KETENES; DESIGN; ACCESS;

D O I：

10.1021/jacs.6b12371

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The first experimental examples of Diels-Alder (DA) reactions of diazo compounds as heterodienophiles with dienes have been studied with density functional theory (DFT) using the M06-2X functional. For comparison, the reactivities of diazo esters as dienophiles or 1,3-dipoles with 1,3-dienes in intermolecular model systems have been analyzed by the distortion/interaction model. The 1,3-dipolar cycloaddition is strongly favored for the intermolecular system. The intramolecular example is unique because the tether strongly favors the (4 + 2) cycloaddition.

引用

页码：2766 / 2770

页数：5