Fig. 4. Substrate scope of enantioselective borylation of C-P bond.

Reaction conditions: 1 (0.10 mmol), B₂neop₂ (2.0 equiv), [Pd(Allyl)Cl]₂ (5 mol%), L5 (22 mol%), CuCl (0.75 equiv), Cs₂CO₃ (2.0 equiv), p-xylene (1.0 mL) for 12 h, then S₈ (5 equiv) or BH₃·SMe₂ (2 equiv, 10 M in Me₂S), unless otherwise stated. Isolated yields were reported. ee values of the major isomers are shown and determined by chiral HPLC analysis. dr values were determined by ¹H NMR analysis of the crude reaction mixtures; ^athe reaction was conducted at 35 °C for 36 h; ^b0.10 mmol scale.