As a class of readily available and multifunctional building blocks, the chemistry of 4-alken-2-ynyl carbonates remains to be explored. Presented herein is a palladium-catalysed cascade transformative reaction between 4-alken-2-ynyl carbonates and ortho-functionalised activated alkenes. Achiral 1,1-bisalkyl-4-alken-2-ynyl carbonates undergo highly regioselective propargylic substitution with ortho-hydroxyphenyl-tethered activated alkenes, and an auto-tandem vinylogous addition, unusual central-carbon Tsuji-Trost alkylation, protonation and β-H elimination process is followed to furnish fused and spirocyclic frameworks with high structural complexity. Even kinetic transformations with racemic 1-monoalkylated 4-alken-2-ynyl carbonates can be accomplished in the assemblies with ortho-aminophenyl-tethered activated alkenes to afford the analogous alkaloid architectures. This palladium-catalysed auto-tandem protocol exhibits excellent chemo-, regio-, stereoselectivity and reaction efficacy, and substantial functionality compatibility is also observed.
This journal is © The Royal Society of Chemistry.