Hydroformylation of Bisolefinic Amine Derivatives Catalyzed by Cobalt and Rhodium

Article abstract of DOI:10.1021/jo00335a022

Three bisolefinic carbamates and five N,N-diallyl N-substituted amines have been subjected to hydroformylation conditions under catalysis by HCo(CO)4, Co(CO)8 and (Ph3P)3Rh(H)CO in an attempt to prepare heterocyclic ketones.The products differ with amines and carbamates and with catalyst.Carbamate 3 and HCo(CO)4 gave 3-pyrrolidinone (4) in 45percent yield.The cobalt-catalyzed reaction of 8 and rhodium-catalyzed reaction of 3 and of 8 afforded products arising from hydroformylation at the terminal olefinic carbon.These mixtures usually included 2-pyrrolidinone; cobalt-catalyzed hydroformylation of chlorinated allylamines 10-12 provided N-benzyl-2-pyrrolidinone (14) and N,N-dibutylbenzylamine (16).Direct synthesis of potential intermediates including 18 has permitted the delineation of mechanistic rationale.