C-N Bond Formation from Allylic Alcohols via Cooperative Nickel and Titanium Catalysis.

ABSTRACT

Amination of allylic alcohols is facilitated via cooperative catalysis. Catalytic Ti(O- i-Pr)4 is shown to dramatically increase the rate of nickel-catalyzed allylic amination, and mechanistic experiments confirm activation of the allylic alcohol by titanium. Aminations of primary and secondary allylic alcohols are demonstrated with a variety of amine nucleophiles. Diene-containing substrates also cyclize onto the nickel allyl intermediate prior to amination, generating carbocyclic amine products. This tandem process is only achieved under our cooperative catalytic system.