TfOH-Catalyzed Phosphinylation of 2,3-Allenols into γ‑Ketophosphine Oxides

The first facile and efficient acid-catalyzed direct coupling of a wide range of unprotected 2,3-allenols with arylphosphine oxides was developed, offering a general, one-step approach for the synthesis of structurally diverse γ-ketophosphine oxides accompanied by concurrent CP/CO bond formation with remarkable functional group tolerance and complete atom-economy under metal- and additive-free conditions. Mechanistic studies showed that this transformation involved a rearrangement and a phospha-Michael reaction.