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The Acyloin Condensation

  1. Jordan J. Bloomfield,
  2. Dennis C. Owsley,
  3. Janice M. Nelke

Published Online: 15 MAR 2011

DOI: 10.1002/0471264180.or023.02

Organic Reactions

Organic Reactions

How to Cite

Bloomfield, J. J., Owsley, D. C. and Nelke, J. M. 2011. The Acyloin Condensation. Organic Reactions. 23:2:259–404.

Author Information

  1. Monsanto Company, Corporate Research Department

Publication History

  1. Published Online: 15 MAR 2011

Abstract

The acyloin condensation usually involves the reductive dimerization of a carboxylic ester, although acid chlorides and the anhydrides have been used. The reducing agent is in an alkali metal and the product is an ene-diolate. Two gram-atoms of metal are required for each mole of ester with the concomitant formation of a mole of akoxide and one-half mole of the ene-diolate. Oxidation of acyloins to diketoes can be accomplished by a variety of reagents. Acyloins can be reduced to ketones by various modifications of the Clemmenson technique. Under mild conditions the ketone will dominate. This chapter presents a complete picture of both the linear and cyclic acyloin condensation with particular emphasis on developments since 1960. The discussion is closely limited to the acyloin condensation and its modifications.

Keywords:

  • condensation;
  • acyloin;
  • dicarboxylic acids;
  • monocarboxyl acids;
  • reduction;
  • oxalates;
  • malonates;
  • succinates;
  • glutarates;
  • adipates;
  • pimelates;
  • heterocyclic esters;
  • esters;
  • ketone;
  • semidiones;
  • experimental procedures