Direct amination of homoenolates catalyzed by N-Heterocyclic carbenes

N-Heterocyclic carbenes derived from N-mesityl-N-methyltriazolium salts are effective catalysts for generating homaenolate species from alpha,beta-unsaturated aldehydes. The unique intermediate adds to the electrophilic nitrogen of 1-acyl-2-aryidiazenes, and the resulting activated carbonyl unit undergoes an intramolecular acylation event. This formal [3+2] cycloaddition between alpha,beta-unsaturated aldehydes and acylaryldiazenes, catalyzed by an N-heterocyclic carbene, produces substituted pyrazolidinones in good yields. This new NHC-catalyzed reaction accommodates aromatic and alkyl (alpha,beta-unsaturated aldehydes and various aromatic diazenes. A chiral triazolium salt catalyzes the formation of the pyrazolidinone product in moderate yield and good enantioselectivity. The pyrazolidinones can undergo reductive N-N bond cleavage to give beta-amino acid derivatives.