2026-04-17T19:19:37Zhttps://riubu.ubu.es/oai/requestoai:riubu.ubu.es:10259/55322021-11-02T12:05:29Zcom_10259_3593com_10259_5086com_10259_2604col_10259_3594
2020-10-29T11:06:19Z
urn:hdl:10259/5532
Experimental and Computational Study of the 1,5-O → N Carbamoyl Snieckus–Fries-Type Rearrangement
Feberero, Claudia
Sedano Labrador, Carlos
Suarez Pantiga, Samuel
Silva López, Carlos
Sanz Díez, Roberto
Aromatic compounds
Organic compounds
Rearrangement
Reaction products
Genetics
The reactions of o-lithiated O-aryl N,N-diethylcarbamates
with different C−N multiple bond electrophiles have been
thoroughly studied. A 1,5-O → N carbamoyl shift, a new variation
of the anionic Fries-type rearrangement, takes place when nitriles,
imines, or alkylcarbodiimides are employed. In these cases, the
carbamoyl group plays a dual role as a directing group, building up
a variety of functional groups through the 1,5-O → N carbamoyl
migration. On the other hand, the use of iso(thio)cyanates and
arylcarbodiimides led to non-rearranged o-functionalized Oarylcarbamates.
This reactivity was further computationally
explored, and the governing factor could be traced back to the
relative basicity of the alternative products (migrated vs nonmigrated
substrates). This exploration also provided interesting insights about the degree of complexation of the lithium cations onto
these substrates. A new access to useful 2-hydroxybenzophenone derivatives has also been developed.
2020-10-29T11:06:19Z
2020-10-29T11:06:19Z
2020-10
info:eu-repo/semantics/article
0022-3263
http://hdl.handle.net/10259/5532
10.1021/acs.joc.0c01732
1520-6904
eng
The Journal of Organic Chemistry. 2020, V. 85, n. 19, p. 12561–12578
https://doi.org/10.1021/acs.joc.0c01732
info:eu-repo/grantAgreement/JCyL/BU291P18
info:eu-repo/grantAgreement/MICINN/CTQ2016-75023-C2-1-P
info:eu-repo/grantAgreement/MICINN/CTQ2016-75023-C2-2-P
info:eu-repo/semantics/openAccess
American Chemical Society