Departamento de Química Orgánica I and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Química , Universidad del País Vasco/Euskal Herriko Unibertsitatea (UPV/EHU) and Donostia International Physics Center (DIPC) , P° Manuel Lardizabal 3 , 20018 San Sebastián/Donostia , Spain.
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)-UMR 6226 , 263, avenue du Général Leclerc, Campus de Beaulieu , F-35000 Rennes , France.
J Org Chem. 2018 Dec 21;83(24):14861-14881. doi: 10.1021/acs.joc.8b01320. Epub 2018 Dec 4.
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.
本文报道了在活化异氰酸酯作用下，芳基和烯基取代的烯丙醇发生 1,3-二恶-[3,3]-σ重排的意外反应。键的重排高度依赖于芳环的电子密度和所用异氰酸酯的性质。这种无金属的串联反应由氨基甲酰化反应引发，随后发生 σ重排，从而为（E）-肉桂基和共轭（E，E）-二烯氨基甲酸酯（如 N-酰基和 N-磺酰基衍生物）提供了新的途径。进行了计算研究以解释这一现象，并进行了重排进展动力学分析。
