Synthesis of Indenes by Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers

Abstract

The tandem gold(I)-catalyzed propargyl Claisen rearrangement/hydroarylation reaction of suitable propargyl vinyl ethers, followed by in situ reduction of the resulting carbonyl group, provides functionalized indenes in good to excellent yields. The reaction occurs at room temperature in dichloromethane in the presence of 3 mol % [IPrAuCl]/AgBF4 as the best catalytic system. Instead, cyclization of the allene intermediate either does not take place or is very slow with phosphine ligands. A variety of substituents and functional groups present on the substrate are tolerated. The effect of the aryl ring substituents and the results of a density functional theory computational study suggest that the final hydroarylation is the rate-determining step of this cascade process. Further in situ chain elongation, prior final work up of the tandem process, can be carried out by Wittig olefination of the aldehyde functionality, thus incrementing the diversity of the products obtained.