Highly catalyst-dependent cycloisomerisation of an O-tethered enyne derived from nerol

The cycloisomerisation of an O-tethered enyne derived from nerol has been studied using various catalytic systems such as PtCl2, AuCl3, {[AuCl(PPh3)]/AgPF6} and [Rh2Cl2(CO)4]. Whatever the catalyst used, formal Alder-ene 1,4-dienes were obtained as major products along with cyclopropane and 1,3-diene derivatives, indicating the crucial influence of the structure of the enyne substrate on the course of the reaction. Differences in terms of activity and selectivity nevertheless appeared when moving from Rh- or Pt-based catalysts to Au(I)-based catalysts: mechanistic pathways are proposed to explain these observations.

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► PtCl2, {[AuCl(PPh3)]/AgPF6} and [Rh2Cl2(CO)4] catalyse the cycloisomerisation of a nerol-derived O-tethered enyne.
► Formal Alder-ene 1,4-dienes are obtained as major products in the cycloisomerisation of a nerol-derived O-tethered enyne.
► Differences in terms of activity and selectivity appeared when moving from Rh- or Pt- to Au(I)-based catalysts.