2026-04-17T10:25:31Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/55322021-11-02T12:05:29Zcom_10259_3593com_10259_5086com_10259_2604col_10259_3594

00925njm 22002777a 4500 dc Feberero, Claudia author Sedano Labrador, Carlos author Suarez Pantiga, Samuel author Silva López, Carlos author Sanz Díez, Roberto author 2020-10 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. 0022-3263 http://hdl.handle.net/10259/5532 10.1021/acs.joc.0c01732 1520-6904 Aromatic compounds Organic compounds Rearrangement Reaction products Genetics Experimental and Computational Study of the 1,5-O → N Carbamoyl Snieckus–Fries-Type Rearrangement