Cyclization cascade of allenyl azides: a dual mechanism.
A density functional theory based computational approach to describing the mechanistic course of the allene azide cycloaddition cascade sequence has been developed. The results of these calculations permit characterization of key reactive intermediates (diradicals and/or indolidenes) and explain the different behaviors observed in the experimental studies between conjugated and nonconjugated species. Furthermore, computational analysis of certain intermediates offer insight into issues of regioselectivity and stereoselectivity in cases where different reaction channels are in competition, suggesting suitable substitutions to achieve a single regioisomer in the indole synthesis via azide-allene cyclization.
López
Carlos Silva
CS
Departamento de Quimica Organica, Universidade de Vigo, Lagoas Marcosende, 36200 Vigo, Galicia, Spain. silva@chem.umn.edu
Faza
Olalla Nieto
ON
Feldman
Ken S
KS
Iyer
Malliga R
MR
Ii
D Keith Hester
DK
D001386:Azides / Q000737:chemistry*; D003198:Computer Simulation; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure
D001386:Azides