均相金催化烯烃的氧化碳杂官能团化反应。

Homogeneous gold-catalyzed oxidative carboheterofunctionalization of alkenes.

机构信息

Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106, USA.

出版信息

J Am Chem Soc. 2010 Feb 10;132(5):1474-5. doi: 10.1021/ja909555d.

PMID:20050647

Abstract

Homogeneous carboamination, carboalkoxylation and carbolactonization of terminal alkenes are realized via oxidative gold catalysis, providing expedient access to various substituted N- or O-heterocycles. Deuterium-labeling studies established the anti nature of the alkene functionalization and the indispensible role of Au(I)/Au(III) catalysis. This study constitutes the first example of catalytically converting C(sp(3))-Au bonds into C(sp(3))--C(sp(2)) bonds in a cross-coupling manner and opens new opportunities to study gold alkene catalysis where alkylgold intermediates can be readily functionalized intermolecularly.

摘要

通过氧化金催化，实现了末端烯烃的均相碳氨化、碳烷氧基化和碳内酯化，为各种取代的 N-或 O-杂环化合物提供了便捷的合成途径。氘标记研究确立了烯烃官能化的反马氏规则性和 Au(I)/Au(III)催化的不可或缺性。该研究首次实现了以催化方式将 C(sp(3))-Au 键交叉偶联转化为 C(sp(3))--C(sp(2))键，为研究金烯催化反应提供了新的机会，其中烷基金中间体可易于进行分子间官能化。