A novel tungsten-mediated carbonylation reaction via a tandem 1,3-metal sigmatropic shift through a σ-hex-2-en-4-yn-1-yl group

Abstract

Stirring of a THF solution of [W(η-C₅H₅)(CO)₃(σ-trans-CH₂CHCHCCMe)] with RXH (RXH = H₂O, MeOH, NH₂Buⁱ) over silica or Florisil gel leads to a new carbonylation reaction to give [W(η-C₅H₅)(CO)₂(η³-3-syn-RXCO-3-anti-Me-1-vinylallyl)] compounds in moderate yields, providing direct evidence for a tandem 1,3-metal shift across conjugated allyl and alkyne bonds.