An exceptionally mild catalytic thioester aldol reaction inspired by polyketide biosynthesis

J Am Chem Soc. 2003 Mar 12;125(10):2852-3. doi: 10.1021/ja029452x.


This report details our discovery of a new catalytic ester aldol reaction using malonic acid half thioesters (MAHTs) that directly affords beta-hydroxythioesters. The reaction is catalyzed by combination of a Cu(II) salt and an amine base, and it can be performed under exceptionally mild conditions (23 degrees C, open to the air, wet solvent). Methyl malonic acid half thioesters afforded syn aldol products with distereoselectivities greater than 6:1.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alcohols / chemical synthesis*
  • Aldehydes / chemistry*
  • Catalysis
  • Esters / chemistry
  • Ketones / chemical synthesis*
  • Ketones / chemistry*
  • Kinetics
  • Macrolides / chemistry
  • Macrolides / metabolism*
  • Sulfhydryl Compounds / chemistry


  • Alcohols
  • Aldehydes
  • Esters
  • Ketones
  • Macrolides
  • Sulfhydryl Compounds