The regioselectivity of hydrocyanation of a range of alkynols using nickel-based catalyst systems involving either triphenyl phosphite or α,α′-bis(diphenylphosphino)-o-xylene (phmep) has been investigated. The regioselectivity of the hydrocyanations involving the phosphine catalyst reflected dominant steric effects whereas results from the phosphite catalyst system showed some evidence for chelation control. Yields of nitriles from reactions based on the phosphite system were variable, whereas moderate to good yields of distilled products could be obtained consistently by using the phosphine -based system. An explanation for this variation in yield is proposed.
