An efficient and practical Rh­(III)-catalyzed redox-neutral [4 + 1] annulation of N-phenoxy amides with α,α-difluoromethylene alkynes has been realized to give direct access to the Z-configured monofluoroalkenyl dihydrobenzo­[d]­isoxazole framework with broad substrate compatibility and good functional group tolerance, which was further enhanced by the late-stage C–H modification of complex bioactive compounds. Subsequent density functional theory calculations revealed that the stereoselective β–F elimination involving an allene species played a decisive role in determining the reaction outcome and such Z-selectivity.

A unique Rh­(III)-catalyzed C–H activation/[3 + 2] annulation of N-phenoxyacetamides has been developed for the construction of dihydrobenzofurans via carbooxygenation of 1,3-dienes. This transformation features a redox-neutral process with specific chemoselectivity, good substrate/functional group compatibility, and profound synthetic potentials. A preliminary exploration to realize their asymmetric synthesis have been also successfully demonstrated, which further strengthens the practicality of this approach.

An efficient, mild and metal-free [3+2] annulation of N-phenoxy amides with gem-difluoroalkenes has been realized via base-mediated tandem [3,3]-sigmatropic rearrangement, which gives the direct access to 2-aminobenzofuran derivatives involving the...