Palladium(II) 3-iminophosphine (3IP) complexes: Active precatalysts for the intermolecular hydroamination of 1,2-dienes (allenes) and 1,3-dienes with aliphatic amines under mild conditions

Abstract

The synthesis of alicyclic 3-iminophosphine ligands is extended to include a new framework incorporating a cyclohexenyl backbone with an N-aryl imino functionality ( 3IP Ar ). Accordingly, a series of palladium(II) complexes employing this new ligand have been synthesized and utilized in the intermolecular hydroamination of 3-methyl-1,2-butadiene (1,1-dimethylallene) and 2,3-dimethyl-1,3-butadiene with secondary amines. The complex [(3IP Ar)Pd(allyl)]OTf displays excellent catalytic activity in these reactions, selectively producing allylic amine products in high conversion under mild conditions, with an improved rate relative to that observed for our previously reported catalysts. Further, the reactivity trends for the (3IP)Pd triflate systems prove to be complimentary to other known late transition metal based catalytic systems.