The supersilyl group as a carboxylic acid protecting group: application to highly stereoselective aldol and Mannich reactions

Angew Chem Int Ed Engl. 2013 Jul 8;52(28):7198-202. doi: 10.1002/anie.201300102. Epub 2013 May 29.

Abstract

“Super Power”: The application of the "supersilyl” group as carboxylic acid protecting group has been investigated. The unique properties of the “supersilyl” group enabled it to outperform typical carboxyl protecting groups, conferring extraordinary protection upon the carboxyl functionality. “Supersilyl” esters were also utilized for the first time as stable carboxylic acid synthetic equivalents in highly stereoselective aldol and Mannich reactions. The value of this methodology has been further described by the easy photo-deprotection protocol and its applications in rapid synthesis of polyketide subunits.

Keywords: Mannich reaction; aldol reactions; carboxy groups; photodeprotection; protecting groups.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Aldehydes / chemistry*
  • Carboxylic Acids / chemistry*
  • Molecular Conformation
  • Peptides / chemical synthesis
  • Peptides / chemistry
  • Polyketides / chemical synthesis
  • Polyketides / chemistry
  • Silicon / chemistry*
  • Stereoisomerism

Substances

  • Aldehydes
  • Carboxylic Acids
  • Peptides
  • Polyketides
  • 3-hydroxybutanal
  • Silicon