Direct carbon-carbon bond formation via soft enolization: a biomimetic asymmetric Mannich reaction of phenylacetate thioesters

Org Lett. 2010 Aug 6;12(15):3376-9. doi: 10.1021/ol101152b.

Abstract

An asymmetric Mannich reaction of phenylacetate thioesters and sulfonylimines using cinchona alkaloid-based amino (thio)urea catalysts is reported that employs proximity-assisted soft enolization. This approach to enolization is based on the cooperative action of a carbonyl-activating hydrogen bonding (thio)urea moiety and an amine base contained within a single catalytic entity to facilitate intracomplex deprotonation. Significantly, this allows thioesters over a range of acidity to react efficiently, thereby opening the door to the development of a general mode of enolization-based organocatalysis of monocarboxylic acid derivatives.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amines / chemistry
  • Carbon / chemistry*
  • Catalysis
  • Cinchona Alkaloids / chemistry*
  • Combinatorial Chemistry Techniques
  • Esters
  • Molecular Structure
  • Phenylacetates / chemistry*
  • Sulfur Compounds / chemistry*

Substances

  • Amines
  • Cinchona Alkaloids
  • Esters
  • Phenylacetates
  • Sulfur Compounds
  • Carbon