Allylsamarium Bromide-Mediated Cascade Cyclization of Homoallylic Esters. Synthesis of 2-(2-Hydroxyalkyl)cyclopropanols and 2-(2-Hydroxyethyl)bicyclo[2.1.1]hexan-1-ols

J Org Chem. 2015 Jan 2;80(1):52-61. doi: 10.1021/jo501797w. Epub 2014 Dec 15.

Abstract

In continuation of our previous study on the intramolecular reductive coupling of simple homoallylic esters promoted by allylSmBr/HMPA/H2O, which afforded a facile synthesis of 2-(2-hydroxyalkyl)cyclopropanols, here we report the reductive cascade cyclization of but-3-enyl but-3-enoates mediated by allylSmBr/HMPA/CuCl2·2H2O, in which the two C═C bonds were successively coupled to allow the construction of the structurally interesting bridged bicyclic tertiary alcohols. Thus, the 2-(2-hydroxyethyl)bicyclo[2.1.1]hexan-1-ols were prepared in moderate to good yields with excellent diastereoselectivity.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Allyl Compounds / chemistry*
  • Bridged Bicyclo Compounds / chemical synthesis*
  • Bridged Bicyclo Compounds / chemistry
  • Crystallography, X-Ray
  • Cyclization
  • Esters / chemistry*
  • Ethers, Cyclic / chemical synthesis*
  • Ethers, Cyclic / chemistry
  • Models, Molecular
  • Molecular Structure
  • Samarium / chemistry*

Substances

  • Allyl Compounds
  • Bridged Bicyclo Compounds
  • Esters
  • Ethers, Cyclic
  • cyclopropanol
  • Samarium