Synthesis of .alpha.-substituted cyclobutanones and its application to the confirmation of the rearrangement of a bicyclo[2.2.1]heptane to a bicyclo[3.1.1]heptane derivative

Rearrangement of Allyl Homoallyl Ethers to γ,δ-Unsaturated Carbonyl Compounds Catalyzed by Iridium Complexes

“…The aliphatic Claisen rearrangement of allyl vinyl ethers has been adopted as a valuable synthetic tool for the synthesis of γ,δ-unsaturated carbonyl compounds, although the availability of the starting vinyl ethers is rather difficult the reaction of allyl formates with the Tebbe reagent, and the acid-catalyzed reaction of diallyl acetals, as well as the transition metal compound- or acid-catalyzed transvinylation between alkyl vinyl ethers and allylic alcohols . Diallyl ethers are reported to be converted into γ,δ-unsaturated aldehydes by heating in the presence of (Ph 3 P) 3 RuCl 2 6 or [(C 8 H 12 )Ir(PCH 3 Ph 2 ) 2 ]PF 6 , although these reactions must be carried out at higher temperature (>160 °C).…”

One-Pot Synthesis of γ,δ-Unsaturated Carbonyl Compounds from Allyl Alcohols and Vinyl or Isopropenyl Acetates Catalyzed by [IrCl(cod)]2

“…The Claisen rearrangement of allyl vinyl ethers is recognized as an attractive tool for the synthesis of olefins in a stereoselective manner as well as for the creation of asymmetrical carbon centers . Therefore, there have been several reports on the in situ generation of allyl vinyl ethers which are precursors for the Claisen rearrangement, e.g., acid-catalyzed decomposition of diallyl actates, vinylation of haloethers, Ru- and Ir-catalyzed rearrangement of diallyl ethers, organoaluminum-promoted allyl vinyl ethers, etc. The reaction of allyl alcohols with terminal alkynes catalyzed by Rh complexes is reported to lead to the Claisen rearrangement products .…”