Allenyl Azide Cycloaddition Chemistry. Synthesis of Pyrrolidine-Containing Bicycles and Tricycles via the Possible Intermediacy of Azatrimethylenemethane Species

Thermolysis of 5-azidoallenes bearing a C(1) methyl group and either an aryl ring or an alkene on C(1) furnishes tricyclic (from the aryl substrates) or bicyclic (from the alkenyl substrates) pyrrolidine products following formal H-CN addition across an intermediate imine. High levels of diastereoselectivity are observed in all cases studied. This reaction cascade presumably passes through unobserved triazoline and azatrimethylenemethane diyl intermediates en route to product.