Copper-Catalyzed P–H Insertions of α‑Imino Carbenes for the Preparation of 3‑Phosphinoylindoles

A highly efficient P–H insertion of α-imino copper carbene into H-phosphine oxides, leading to 3-phosphinoylindoles with a broad substrate diversity and good chemoselectivity, is established. This methodology provides a rapid and efficient approach for the C (sp2)–P bond formation via the P–H insertion strategy. The stereoselective P–H insertion of α-imino copper carbene represents a unique example of asymmetric P–H insertion, affording P-stereogenic 3-phosphinoylindoles with high stereoselectivities.