Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne-Aldehyde Coupling Reactions

被引：84

作者：

McCarren, P. R. ^{[2
]}

Liu, Peng ^{[2
]}

Cheong, Paul Ha-Yeon ^{[2
]}

Jamison, Timothy F. ^{[1
]}

Houk, K. N. ^{[2
]}

机构：

[1] MIT, Dept Chem, Cambridge, MA 02139 USA

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

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 19期

基金：

美国国家科学基金会;

关键词：

ALLYLIC ALCOHOLS; TETHERED ALKENES; CYCLIZATIONS; LIGAND; ANTI-1,2-DIOLS; INTERMEDIATE; 1,3-ENYNES;

D O I：

10.1021/ja900701g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of nickel-catalyzed reductive alkyne-aldehyde coupling reactions has been investigated using density functional theory. The preferred mechanism involves oxidative cyclization to form the nickeladihydrofuran intermediate followed by transmetalation and reductive elimination. The rate- and selectivity-determining oxidative cyclization transition state is analyzed in detail. The d -> Pi*(perpendicular to) back-donation stabilizes the transition state and leads to higher reactivity for alkynes than alkenes. Strong Lewis acids accelerate the couplings with both alkynes and alkenes by coordinating with the aldehyde oxygen in the transition state.

引用

页码：6654 / +

页数：3

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