Abstract
Collaborative work between experimentalists and computational chemists have demonstrated a stong synergy which allowed the rationalization of allenyl azide chemistry and permited the development of an efficient synthetic tool aimed at the preparation of several alkaloids. Saturated allenyl azides undergo a reaction cascade involving key diradical intermediates that follow the Curtin- Hammett model whereas unsaturated allenyl azides form indolidene intermediates that furnish the final indole products via electrocyclic ring closure events taking place out of the Curtin-Hammett regime. The regiochemistry of the reaction cascade with the latter substrates can be manipulated by Cu(I) addition to the reaction mixture.
Keywords: Allenyl azide, azatrimethylenemethane, indole, DFT, rationalization, Curtin-Hammett model, Indolidene intermediates, Curtin-Hammett regime, Diradical-mediated reactions, Trimethylenemethane (TMM) diyl, Triazoline intermediate, Regioslectivity, Anisotropy of the current induced density (ACID), Allenyl azide cyclization chemistry
Current Organic Chemistry
Title: Cyclization Cascade of Allenyl Azides: Synergy Between Theory and Experiment
Volume: 14 Issue: 15
Author(s): Olalla Nieto Faza, Ken S. Feldman and Carlos Silva Lopez
Affiliation:
Keywords: Allenyl azide, azatrimethylenemethane, indole, DFT, rationalization, Curtin-Hammett model, Indolidene intermediates, Curtin-Hammett regime, Diradical-mediated reactions, Trimethylenemethane (TMM) diyl, Triazoline intermediate, Regioslectivity, Anisotropy of the current induced density (ACID), Allenyl azide cyclization chemistry
Abstract: Collaborative work between experimentalists and computational chemists have demonstrated a stong synergy which allowed the rationalization of allenyl azide chemistry and permited the development of an efficient synthetic tool aimed at the preparation of several alkaloids. Saturated allenyl azides undergo a reaction cascade involving key diradical intermediates that follow the Curtin- Hammett model whereas unsaturated allenyl azides form indolidene intermediates that furnish the final indole products via electrocyclic ring closure events taking place out of the Curtin-Hammett regime. The regiochemistry of the reaction cascade with the latter substrates can be manipulated by Cu(I) addition to the reaction mixture.
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Cite this article as:
Nieto Faza Olalla, S. Feldman Ken and Silva Lopez Carlos, Cyclization Cascade of Allenyl Azides: Synergy Between Theory and Experiment, Current Organic Chemistry 2010; 14 (15) . https://dx.doi.org/10.2174/138527210793563305
DOI https://dx.doi.org/10.2174/138527210793563305 |
Print ISSN 1385-2728 |
Publisher Name Bentham Science Publisher |
Online ISSN 1875-5348 |
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