Mechanism of triflimide-catalyzed [3,3]-sigmatropic rearrangements of N-allylhydrazones-predictions and experimental validation

被引：16

作者：

Gutierrez, Osvaldo ^{[2
]}

Strick, Benjamin F. ^{[1
]}

Thomson, Regan J. ^{[1
]}

Tantillo, Dean J. ^{[2
]}

机构：

[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA

[2] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

来源：

CHEMICAL SCIENCE | 2013年 / 4卷 / 10期

基金：

美国国家科学基金会;

关键词：

3,3 SIGMATROPIC REARRANGEMENT; COPE REARRANGEMENTS; BOND FORMATION; 1,5-HEXADIENE;

D O I：

10.1039/c3sc51564h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Computational analysis of the triflimide catalyzed [3,3]-sigmatropic rearrangement of N-allylhydrazones, using density functional theory calculations, is reported. Key mechanistic insight was obtained and predictions derived therefrom were confirmed experimentally through temperature dependence studies. The computational results have led to the development of electron deficient N-allylhydrazones capable of reacting under mild reaction conditions. Application of the rearrangement to form a new sp(3) stereogenic center is reported for the first time.

引用

页码：3997 / 4003

页数：7

共 32 条

[31] Experimental and Theoretical Investigations of the Formation of the Diazene PhS-N = C(H)N = NC(H) = NSPh from HCN2(SPh)3 by a Thiyl-Radical-Catalyzed Mechanism: Identification of the HC(NSPh)2* Radical and X-ray Structures of HCN2(SPh)3 and PhS-N = C(H)N = NC(H) = NSPh
Chivers, T.
McGarvey, B.
Parvez, M.
Vargas-Baca, I.
Inorganic Chemistry, 35 (13):
[32] Experimental and theoretical investigations of the formation of the diazene PhSN=C(H)N=NC(H)=NsPh from HCN2(SPh)(3) by a thiyl-radical-catalyzed mechanism: Identification of the HC(NSPh)2(center dot) radical and X-ray structures of HCN2(SPh)(3) and PhSN=C(H)N=NC(H)=NSPh
Chivers, T
McGarvey, B
Parvez, M
VargasBaca, I
Ziegler, T
INORGANIC CHEMISTRY, 1996, 35 (13) : 3839 - 3847

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