Studies on transannulation reactions across a nine-membered ring: the synthesis of natural product-like structures

Org Biomol Chem. 2011 Jul 21;9(14):5062-78. doi: 10.1039/c1ob05448a. Epub 2011 May 20.

Abstract

A series of diverse natural product-like structures have been synthesised by the use of a number of novel transannulation reactions across a cyclononene ring. Transannular cyclisations through oxygen functionality have generated a number of bicyclo[5.3.1]systems containing bridged cyclic ethers and bicyclo[5.2.2]lactones, as well as a tetrahydrofuran-containing bridged analogue of hexacyclinic acid. An unprecedented Brønsted acid mediated transannular cyclisation between proximal carbons generated bicyclo[4.3.0]nonanes which form the core of the pinguisane and austrodorane families of sesquiterpenoids. In all cases the key factor that determined the mode of reactivity was the conformation of the nine-membered ring and the distance between the reacting centres.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bridged Bicyclo Compounds / chemical synthesis*
  • Bridged Bicyclo Compounds / chemistry
  • Crystallography, X-Ray
  • Cyclization
  • Cycloparaffins / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Stereoisomerism

Substances

  • Bridged Bicyclo Compounds
  • Cycloparaffins