RT info:eu-repo/semantics/article
T1 Experimental and Computational Study of the 1,5-O → N Carbamoyl Snieckus–Fries-Type Rearrangement
A1 Feberero García, Claudia
A1 Sedano Labrador, Carlos
A1 Suarez Pantiga, Samuel
A1 Silva López, Carlos
A1 Sanz Díez, Roberto
K1 Aromatic compounds
K1 Organic compounds
K1 Rearrangement
K1 Reaction products
K1 Genetics
K1 Química orgánica
K1 Chemistry, Organic
AB The reactions of o-lithiated O-aryl N,N-diethylcarbamateswith different C−N multiple bond electrophiles have beenthoroughly studied. A 1,5-O → N carbamoyl shift, a new variationof the anionic Fries-type rearrangement, takes place when nitriles,imines, or alkylcarbodiimides are employed. In these cases, thecarbamoyl group plays a dual role as a directing group, building upa variety of functional groups through the 1,5-O → N carbamoylmigration. On the other hand, the use of iso(thio)cyanates andarylcarbodiimides led to non-rearranged o-functionalized Oarylcarbamates.This reactivity was further computationallyexplored, and the governing factor could be traced back to therelative basicity of the alternative products (migrated vs nonmigratedsubstrates). This exploration also provided interesting insights about the degree of complexation of the lithium cations ontothese substrates. A new access to useful 2-hydroxybenzophenone derivatives has also been developed.
PB American Chemical Society
SN 0022-3263
YR 2020
FD 2020-10
LK http://hdl.handle.net/10259/5532
UL http://hdl.handle.net/10259/5532
LA eng
NO Junta de Castilla y León and FEDER (BU291P18) and Ministerio de Ciencia e Innovación and FEDER (CTQ2016-75023-C2-1-P and 2-P)
DS Repositorio Institucional de la Universidad de Burgos
RD 27-abr-2024