铑催化的1,6-烯炔与芳基硼酸通过β-氢消除/氢铑化序列的环化反应。

Rhodium-catalyzed cyclization reaction of 1,6-enynes with arylboronic acids through beta-hydride elimination/hydrorhodation sequence.

作者信息

Shimada Masahiko, Harumashi Tatsuro, Miura Tomoya, Murakami Masahiro

机构信息

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

出版信息

Chem Asian J. 2008 Jun 2;3(6):1035-40. doi: 10.1002/asia.200700407.

DOI:10.1002/asia.200700407

PMID:18454445

Abstract

Methoxy-substituted 1,6-enynes react with arylboronic acids in the presence of a rhodium(I) complex to give arylated cyclization products. This occurs by a multi-step mechanism consisting of rhodium/boron transmetalation, intermolecular carborhodation, intramolecular carborhodation, beta-hydride elimination, hydrorhodation, and beta-oxygen elimination. A shift of the position of a carbon-carbon double bond is observed, suggesting that the beta-hydride elimination/hydrorhodation process is repeatedly taking place.

摘要

甲氧基取代的1,6-烯炔在铑（I）配合物存在下与芳基硼酸反应，生成芳基化环化产物。这一过程通过多步机理发生，包括铑/硼转金属化、分子间碳铑化、分子内碳铑化、β-氢消除、氢铑化和β-氧消除。观察到碳-碳双键位置的移动，表明β-氢消除/氢铑化过程在反复进行。