Ligand-Controlled Regiodivergent Cyanoboration of Internal Allenes by Copper Catalysis.

The first copper-catalyzed regiodivergent cyanoboration of internal allenes with B 2 pin 2 (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 B 2 pin 2 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.