Rh(III)-Catalyzed and synergistic dual directing group-enabled redox-neutral [3+3] annulation of N-phenoxyacetamides with α-allenols.

By virtue of α-allenols as innovative three-carbon annulation components, the Rh(III)-catalyzed redox-neutral C-H coupling of N-phenoxyacetamides with α-allenols has been realized for the assembly of 4-alkylidene chroman-2-ol frameworks via an unusual [3+3] annulation. This transformation features good functional group tolerance, specific regio-/chemoselectivity and potential synthetic utility. Mechanistic studies reveal that synergistic coordination modes between the dual directing groups (-ONHAc and -OH) and the rhodium metal center account for the observed exclusive selectivity.