由交叉共轭的α-烷氧羰基烯酮体系促进的多烯环化反应。关于在路易斯酸催化下假定的1,5-氢化物/1,3-烷基迁移的观察。

Polyene cyclization promoted by the cross-conjugated alpha-carbalkoxy enone system. Observation on a putative 1,5-hydride/1,3-alkyl shift under Lewis acid catalysis.

作者信息

Chou Ho-Hsuan, Wu Huang-Min, Wu Jen-Dar, Ly Tai Wei, Jan Ning-Wei, Shia Kak-Shan, Liu Hsing-Jang

机构信息

Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan 30013, ROC.

出版信息

Org Lett. 2008 Jan 3;10(1):121-3. doi: 10.1021/ol702631q. Epub 2007 Dec 4.

DOI:10.1021/ol702631q

PMID:18052186

Abstract

Polyene cyclization of compounds 3 and 4 under catalysis with AlCl3 and/or SnCl4 gave rise to complex bicyclic products 8 and 9, structures of which were highly unexpected, and X-ray analyses were invoked for unambiguously structural identification. Mechanistically, a tandem sigma-bond rearrangement process, including an unusual through-space 1,5-hydride or 1,3-alkyl shift as a key operation, is proposed.

摘要

在AlCl₃和/或SnCl₄催化下，化合物3和4的多烯环化反应生成了复杂的双环产物8和9，其结构非常出人意料，需借助X射线分析来明确结构鉴定。从机理上讲，提出了一个串联的σ键重排过程，其中包括一个不寻常的通过空间的1,5-氢化物或1,3-烷基迁移作为关键步骤。