Ligand-Controlled Regiodivergent Cyanoboration of Internal Allenes by Copper Catalysis

The first copper-catalyzed regiodivergent cyanoboration of internal allenes with B₂ pin₂ (bis(pinacolato)diboron) and NCTS (N-cyano-N-phenyl-p-toluenesulfonamide) derivatives is reported. The β,γ- and α,β-cyanoborylated products were synthesized with high regio- and stereo-selectivity. Computational studies revealed that nucleophilic addition of allylcopper or related intermediates on cyanation reagent is the regio- and stereo-determining step, while transmetalation with B₂ pin₂ is the rate-determining step. The nucleophilic addition step proceeds via inner-sphere mechanism in the Cu^I /P(o-tol)₃ and Cu^I /Xantphos (P(o-tol)₃ =tris(o-methylphenyl)phosphine, Xantphos=4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) catalytic systems and via outer-sphere mechanism in the Cu^II /Xantphos catalytic system, respectively.