Ambiphilic Phosphinidene-Enabled Regioselective Ring-Opening of Epoxides

We disclose the use of phosphinidene as a single ambiphilic atom center that enables regioselective ring-opening of epoxides. A range of phosphinidene precursors and various epoxides are compatible with this transformation, affording the corresponding allyloxy phosphines. DFT calculations support a concerted mechanism in which the phosphinidene simultaneously interacts with both the oxygen atom and the β-hydrogen of the epoxides. This work offers a new strategy for small-molecule activation by low-coordinate main-group species.