1,3-Dioxa-[3,3]-sigmatropic Oxo-Rearrangement of Substituted Allylic Carbamates: Scope and Mechanistic Studies.
J Org Chem
; 83(24): 14861-14881, 2018 12 21.
Article
en En
| MEDLINE
| ID: mdl-30457341
ABSTRACT
An unexpected 1,3-dioxa-[3,3]-sigmatropic rearrangement during the treatment of aryl- and alkenyl-substituted allylic alcohols with activated isocyanates is reported. The reorganization of bonds is highly dependent on the electron density of the aromatic ring and the nature of isocyanate used. This metal-free tandem reaction from branched allyl alcohols initiated by a carbamoylation reaction and followed by a sigmatropic rearrangement thus offers a new access to ( E)-cinnamyl and conjugated ( E, E)-diene carbamates, such as N-acyl and N-sulfonyl derivatives. A computational study was conducted in order to rationalize this phenomenon, and a rearrangement progress kinetic analysis was performed.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
J Org Chem
Año:
2018
Tipo del documento:
Article
País de afiliación:
España