AN EFFICIENT APPROACH TO PYRROLES AND N-BRIDGEHEAD PYRROLES BY PROPARGYLATION CYCLOAMINATION OF 4-AMINO-1-AZABUTADIENE DERIVATIVES/

The thermal cycloamination of several propargyl-substituted 4-amino-1- azabutadienes 2 leading to 3-functionalized pyrroles 4-6 is described. Derivatives of pyrrolizidines 9 and indolizidines and azaazulenes 11- 13 are synthesized directly from cyclic imines 7 and 10, respectively, in a multistep process that involves metalation with LDA, addition of a nitrile, carbanion trapping with propargyl bromide, and cycloaminat ion. In all cases the more substituted imine nitrogen is involved in t he cyclization reaction; such an experimental finding is supported by theoretical calculations.