将双环[2.2.1]庚 - 2,5 - 二烯（降冰片二烯）的[4 + 2 + 2]环加成物开环生成顺式稠合的双环[5.3.0]癸烷。

Opening the [4 + 2 + 2] cycloadducts of bicyclo[2.2.1]hepta-2,5-dienes (norbornadienes) to cis-fused bicyclo[5.3.0]decanes.

作者信息

Chen Y, Snyder J K

机构信息

Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215.

出版信息

J Org Chem. 2001 Oct 19;66(21):6943-57. doi: 10.1021/jo010269g.

DOI:10.1021/jo010269g

PMID:11597213

Abstract

Tetracyclo[5.4.0.0.(2,4)0(3,7)]undec-9-enes, prepared by the transition-metal-catalyzed [4 + 2 + 2] homo-Diels-Alder reactions of norbornadiene and 1,3-butadienes, can be opened using either acid-promoted or Zeise's dimer-mediated cyclopropane ring cleavage, ultimately leading to cis-fused bicyclo[5.3.0]decanes (perhydroazulenes). Stereoselective functionalization of the olefin unit in the tetracycloundecenes to an alcohol or diol prior to ring opening is tolerated by the Zeise's dimer (Pt(C(2)H(4))Cl(2)) catalyst to yield highly functionalized bicyclo[5.3.0]decanes, which form the core structure of numerous sesquiterpenes.

摘要

四环[5.4.0.0.(2,4)0(3,7)]十一碳-9-烯由降冰片二烯与1,3-丁二烯通过过渡金属催化的[4 + 2 + 2]同分子狄尔斯-阿尔德反应制备而成，可通过酸促进或蔡斯二聚体介导的环丙烷环裂解反应开环，最终生成顺式稠合的双环[5.3.0]癸烷（全氢薁）。在开环之前，蔡斯二聚体([Pt(C₂H₄)Cl₂]₂)催化剂能够耐受四环十一碳烯中烯烃单元向醇或二醇的立体选择性官能团化反应，从而生成高度官能团化的双环[5.3.0]癸烷，其构成了众多倍半萜的核心结构。