Enantioselective construction of all-carbon quaternary centers by branch-selective Pd-catalyzed allyl-allyl cross-coupling

J Am Chem Soc. 2011 Jun 29;133(25):9716-9. doi: 10.1021/ja2039248. Epub 2011 Jun 7.

Abstract

The Pd-catalyzed cross-coupling of racemic tertiary allylic carbonates and allylboronates is described. This reaction generates all-carbon quaternary centers in a highly regioselective and enantioselective fashion. The outcome of these reactions is consistent with a process that proceeds by way of 3,3'-reductive elimination of bis(η(1)-allyl)palladium intermediates. Strategies for distinguishing the product alkenes and application to the synthesis of (+)-α-cuparenone are also described.

Publication types

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

MeSH terms

  • Allyl Compounds / chemistry*
  • Catalysis
  • Dimerization
  • Palladium
  • Sesquiterpenes / chemical synthesis

Substances

  • Allyl Compounds
  • Sesquiterpenes
  • alpha-cuparenone
  • Palladium