Nickel-Catalyzed Regiodivergent Cyanation of Allylic Alcohols: Scope, Mechanism, and Application to the Synthesis of 1,n-Dinitriles

Here, we report a regiodivergent cyanation of allylic alcohols under nickel catalysis. With a delicate control over the regioselectivity of allylic cyanation, more challenging branched products were successfully obtained. A variety of alkenyl nitriles and branched allylic nitriles can be synthesized. In addition, dinitriles can also be achieved from the corresponding allylic alcohols in good yields with high selectivity by a subsequent hydrocyanation process. The obtained dinitriles can easily undergo amidation or reduction or can be converted to heterocycles, piperidines, and multisubstituted pyridines. Density functional theory (DFT) calculations offered more information on the crucial role of ligands in tuning the regioselectivity and reactivity.

Automated summary

A regiodivergent cyanation of allylic alcohols under nickel catalysis was reported in this study, leading to the successful synthesis of challenging branched products. Dinitriles can also be obtained in good yields with high selectivity through subsequent hydrocyanation, which can be further functionalized into various compounds. Density functional theory (DFT) calculations provided insights into the role of ligands in tuning regioselectivity and reactivity.