Allenyl azide cycloaddition chemistry: exploration of the scope and mechanism of cyclopentennelated dihydropyrrole synthesis through azatrimethylenemethane intermediates.
Detailed studies of the thermal conversion of 1-azidohepta-3,4,6-trienes into cyclopentennelated dihydropyrroles are presented. High levels of diastereoselectivity and regioselectivity are documented. A mechanistic proposal that accounts for all of the diverse results is developed through the use of density functional calculations. These calculations provide support for the intervention of unexpected mechanistic subtleties, such as the planarity of an azatrimethylenemethane diyl intermediate and an apparent Woodward-Hoffmann-type electrocyclization of a five-atom diyl array.
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA. ksf@chem.psu.edu
Ken S
KS
Feldman
Malliga R
MR
Iyer
Carlos
C
Silva López
Olalla
O
Nieto Faza
D001372:Aza Compounds / Q000737:chemistry*; D001386:Azides / Q000737:chemistry*; D020650:Combinatorial Chemistry Techniques; D003198:Computer Simulation; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D011758:Pyrroles / Q000737:chemistry*
D001372:Aza Compounds; D001386:Azides; D011758:Pyrroles; C531443:azatrimethylenemethane; D008697:Methane