Pd(II)-Catalyzed Enantioselective Synthesis of P‑Stereogenic Phosphinamides via Desymmetric C–H Arylation

We present the enantioselective synthesis
of P-stereogenic phosphinamides
through Pd-catalyzed desymmetric ortho C–H arylation of diarylphosphinamides
with boronic esters. The method represents the first example of the
synthesis of P-stereogenic phosphorus compounds via the desymmetric
C–H functionalization strategy. The reaction proceeded efficiently
with a wide array of reaction partners to afford the P-stereogenic
phosphinamides in up to 74% yield and 98% ee. The efficiency was further
demonstrated by gram scale syntheses. Moreover, the flexible conversion
of the P-stereogenic phosphinamides into various types of P-stereogenic
phosphorus derivatives was also elaborated. Thus, the protocol provides
a novel tool for the efficient and versatile synthesis of P-stereogenic
compounds.