炔丙醇作为β-氧碳烯前体的钌催化未活化烯烃的重排环丙烷化反应。

Propargyl alcohols as β-oxocarbenoid precursors for the ruthenium-catalyzed cyclopropanation of unactivated olefins by redox isomerization.

机构信息

Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.

出版信息

J Am Chem Soc. 2011 Apr 6;133(13):4766-9. doi: 10.1021/ja200971v. Epub 2011 Mar 14.

DOI:10.1021/ja200971v

Abstract

An atom-economical method for the direct synthesis of [3.1.0]- and [4.1.0]-bicyclic frameworks via Ru-catalyzed redox bicycloisomerization of enynols is reported. The presented results highlight the unique reactivity profile of propargyl alcohols, which function as β-oxocarbene precursors, in the presence of a ruthenium(II) complex. Furthermore, a rare case of a formal vinylic C-H insertion reaction is described.

摘要

报道了一种通过 Ru 催化的烯炔醇的氧化还原双环异构化反应来直接合成[3.1.0]-和[4.1.0]-双环骨架的原子经济性方法。所提出的结果突出了炔丙醇的独特反应性，它们在钌（II）配合物的存在下作为β-氧杂环丁烷前体发挥作用。此外，还描述了一个罕见的形式乙烯基 C-H 插入反应的例子。