Cyclization cascade of allenyl azides: A dual mechanism

Carlos Silva López, Olalla Nieto Faza, Ken S. Feldman, Malliga R. Iyer, D. Keith Hester

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

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.

Original languageEnglish (US)
Pages (from-to)7638-7646
Number of pages9
JournalJournal of the American Chemical Society
Volume129
Issue number24
DOIs
StatePublished - Jun 20 2007

Fingerprint

Stereoselectivity
Regioselectivity
Azides
Cycloaddition
Cyclization
Density functional theory
Substitution reactions
Cycloaddition Reaction
propadiene
indole

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

López, C. S., Faza, O. N., Feldman, K. S., Iyer, M. R., & Hester, D. K. (2007). Cyclization cascade of allenyl azides: A dual mechanism. Journal of the American Chemical Society, 129(24), 7638-7646. https://doi.org/10.1021/ja070818l
López, Carlos Silva ; Faza, Olalla Nieto ; Feldman, Ken S. ; Iyer, Malliga R. ; Hester, D. Keith. / Cyclization cascade of allenyl azides : A dual mechanism. In: Journal of the American Chemical Society. 2007 ; Vol. 129, No. 24. pp. 7638-7646.
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López, CS, Faza, ON, Feldman, KS, Iyer, MR & Hester, DK 2007, 'Cyclization cascade of allenyl azides: A dual mechanism', Journal of the American Chemical Society, vol. 129, no. 24, pp. 7638-7646. https://doi.org/10.1021/ja070818l

Cyclization cascade of allenyl azides : A dual mechanism. / López, Carlos Silva; Faza, Olalla Nieto; Feldman, Ken S.; Iyer, Malliga R.; Hester, D. Keith.

In: Journal of the American Chemical Society, Vol. 129, No. 24, 20.06.2007, p. 7638-7646.

Research output: Contribution to journalArticle

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López CS, Faza ON, Feldman KS, Iyer MR, Hester DK. Cyclization cascade of allenyl azides: A dual mechanism. Journal of the American Chemical Society. 2007 Jun 20;129(24):7638-7646. https://doi.org/10.1021/ja070818l