Highly Enantioselective Rh2(S-DOSP)4-Catalyzed Cyclopropenation of Alkynes with Styryldiazoacetates

被引：93

作者：

Briones, John F. ^{[1
]}

Hansen, Jorn ^{[1
]}

Hardcastle, Kenneth I. ^{[1
]}

Autschbach, Jochen ^{[2
]}

Davies, Huw M. L. ^{[1
]}

机构：

[1] Emory Univ, Dept Chem, Atlanta, GA 30322 USA

[2] SUNY Buffalo, Dept Chem, Buffalo, NY 14226 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 48期

基金：

美国国家科学基金会;

关键词：

DIRHODIUM(II); SELECTIVITY; DERIVATIVES; ENERGY;

D O I：

10.1021/ja106509b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Dirhodium tetrakis((S)-N-(dodecylbenzenesulfonyl)prolinate) (Rh-2(S-DOSP)(4)) is an effective catalyst for highly enantioselective cyclopropenation reactions between terminal alkynes and arylvinyldiazoacetates. The resulting vinylcyclopropenes can undergo rhodium-catalyzed regioselective rearrangement to cyclopentadienes. Computational studies indicate that the high enantioselectivity of the process is governed by the specific orientation of the alkyne during its approach to the carbenoid through a relatively late transition state. The specific orientation occurs due to the presence of a hydrogen bonding interaction between the alkyne hydrogen and a carboxylate ligand on the dirhodium catalyst.

引用

页码：17211 / 17215

页数：5

共 42 条

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