钌催化2,2'-二乙炔基联苯的环异构化反应，涉及碳 - 碳三键的断裂

Ruthenium-Catalyzed Cycloisomerization of 2,2'-Diethynyl- biphenyls Involving Cleavage of a Carbon-Carbon Triple Bond.

作者信息

Matsuda Takanori, Kato Kotaro, Goya Tsuyoshi, Shimada Shingo, Murakami Masahiro

机构信息

Department of Applied Chemistry, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo, 162-8601, Japan.

Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto, 615-8510, Japan.

出版信息

Chemistry. 2016 Feb;22(6):1941-1943. doi: 10.1002/chem.201504937. Epub 2016 Jan 8.

DOI:10.1002/chem.201504937

PMID:26660656

Abstract

A ruthenium complex catalyzes a new cycloisomerization reaction of 2,2'-diethynylbiphenyls to form 9-ethynylphenanthrenes, thereby cleaving the carbon-carbon triple bond of the original ethynyl group. A metal-vinylidene complex is generated from one of the two ethynyl groups, and its carbon-carbon double bond undergoes a [2+2] cycloaddition with the other ethynyl group to form a cyclobutene. The phenanthrene skeleton is constructed by the subsequent electrocyclic ring opening of the cyclobutene moiety.

摘要

一种钌配合物催化2,2'-二乙炔基联苯发生新的环异构化反应，生成9-乙炔基菲，从而切断原始乙炔基的碳-碳三键。从两个乙炔基中的一个生成金属亚乙烯基配合物，其碳-碳双键与另一个乙炔基发生[2+2]环加成反应形成环丁烯。菲骨架是通过环丁烯部分随后的电环化开环构建的。