Stereoselective formation of P-N bonds via coupling of H-P species with amines and the addition of Grignard reagents to chiral <i>N</i>-phosphinoylimines

A series of P-stereogenic phosphinamides were effectively prepared in 65%–94% yield via coupling of H-P species with amines. Meanwhile, the synthesis of chiral N-phosphinoylimines were explored, which could react with Grignard reagents to afford multiple P,C-stereogenic phosphinamides with good yields and moderate diastereoselectivities.