A new synthesis of β,γ-alkenyl carboxylic acids from α,β-alkenyl carboxylic acid chlorides and α,β-alkenyl aldehydes with one-carbon elongation

Abstract

Reaction of the lithium α-sulfinyl carbanion of chloromethyl phenyl sulfoxide with α,β-alkenyl carboxylic acid chlorides gave γ,δ-alkenyl α-chloro-β-keto sulfoxides in variable yields. The keto sulfoxides were also synthesized from α,β-alkenyl aldehydes in two steps in good overall yields: addition of the lithium α-sulfinyl carbanion of chloromethyl phenyl sulfoxide to α,β-alkenyl aldehydes followed by oxidation of the adducts with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone or Dess–Martin periodinane. These products were treated in sequence with potassium hydride, tert-butyllithium, and 5% aqueous sodium hydroxide, in one flask to give β,γ-alkenyl carboxylic acids with one-carbon elongation in good yields. The procedure offers a new method for synthesizing β,γ-alkenyl carboxylic acids from α,β-alkenyl carboxylic acid chlorides and α,β-alkenyl aldehydes with one-carbon elongation.