Tandem Pd(II)-catalyzed vinyl ether exchange-Claisen rearrangement as a facile approach to gamma,delta-unsaturated aldehydes

J Org Chem. 2007 May 25;72(11):4250-3. doi: 10.1021/jo062548f. Epub 2007 Apr 21.

Abstract

A sequential allyl vinyl ether formation-Claisen rearrangement process catalyzed by a palladium(II)-phenanthroline complex is reported. The effects of allylic alcohol structure, type of vinylating agent, and palladium catalysts are discussed. This method provides a convenient approach to gamma,delta-unsaturated aldehydes under mild conditions that avoid the use of toxic Hg(II) catalysts. The new methodology has been successfully demonstrated on the kilogram scale.

MeSH terms

  • Aldehydes / chemical synthesis*
  • Aldehydes / chemistry
  • Catalysis
  • Palladium / chemistry*
  • Phenanthrolines / chemistry*
  • Propanols / chemistry*
  • Stereoisomerism
  • Thermodynamics
  • Vinyl Compounds / chemistry*

Substances

  • Aldehydes
  • Phenanthrolines
  • Propanols
  • Vinyl Compounds
  • vinyl ether
  • allyl alcohol
  • Palladium