A pseudopericyclic [3,5]-sigmatropic rearrangement of a coumarin trichloroacetimidate derivative

A pseudopericyclic [3,5]-sigmatropic rearrangement of a coumarin trichloroacetimidate derivative

Thermolysis of a coumarin trichloroacetimidate yields a single rearrangement product. The proposed mechanism is a pseudopericyclic allowed (Woodward-Hoffman forbidden) [3,5]-sigmatropic rearrangement to form the corresponding amide followed by a sigmatropic [1,5]-hydrogen migration. Transition state...

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Veröffentlicht in:Organic & biomolecular chemistry 2018, Vol.16 (6), p.874-879
Hauptverfasser: Rajale, Trideep, Sharma, Shikha, Unruh, Daniel K, Stroud, Daniel A, Birney, David M
Format: Artikel
Sprache:eng
Schlagworte:
Coumarin
Intermediates
Migration
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Zusammenfassung:Thermolysis of a coumarin trichloroacetimidate yields a single rearrangement product. The proposed mechanism is a pseudopericyclic allowed (Woodward-Hoffman forbidden) [3,5]-sigmatropic rearrangement to form the corresponding amide followed by a sigmatropic [1,5]-hydrogen migration. Transition state calculations at the B3LYP/6-31G(d,p) level support this mechanism and suggest the selectivity is influenced by the stability of the intermediates.
ISSN:1477-0520
1477-0539
DOI:10.1039/c7ob02335a