Investigation of the Corey Bromolactamization with N-Functionalized Allylamines

N-Allylamines were employed for the diastereoselective synthesis of 8-bromo-substituted, cis-configured perhydroquinoxalines and β-bromoalcohols. The yield and constitution of the products depend considerably on the functionalization of the allylic N-atom. Herein the reaction of glycine-derived cyclohex-2-enamines under bromolactamization conditions (LiOtBu, NBS) is reported. Methyl carbamate led diastereoselectively to the cis-configured perhydroquinoxaline , whereas the amides and provided cis,trans-configured -bromoalcohols and . Based on high level theoretical calculations (DFT) factors controlling the cyclization of lithiated intermediates and the relative energies of possible products are discussed.