2026-04-29T20:03:34Zhttps://riubu.ubu.es/oai/requestoai:riubu.ubu.es:10259/42792022-04-29T12:02:48Zcom_10259_3593com_10259_5086com_10259_2604col_10259_3594
Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
Velasco, Rocío
Silva López, Carlos
Nieto Faza, Olalla .
Sanz Díez, Roberto
density functio nal calculations
lithiation
oxygenheterocycles
reaction mechanisms
Wittig rearrangement
Chemistry, Organic
Química orgánica
By carefullycontrolling the reactiontemperature,treatment of aryl benzylethers with tBuLi selectivelyleadsto a-lithiation, generating stable organolithiums that can bedirectlytrapped with avariety of selected electro philes,before they can undergo the expected [1,2]-Wittigrear-rangement. This rearrangement has been deeplystudied,both experimentally and computationally,with aryl a-lithiat-ed benzyl ethers bearing different substituents at the arylring. The obtained resultssupport the competence of acon-certedanionic intramolecular addition/elimination sequenceand aradical dissociation/recombination sequence for ex-plaining the tendency of migrationfor aryl groups.Themore favored rearrangementsare found for substrates withelectron-poor aryl groups that favor the anionic pathway
Junta de Castilla yLejnandFEDER (BU237U13 and BU076U16) and Ministerio de Econom&ayCompetitividad (MINECO) and FEDER (CTQ2013-48937-C2-1Pand 2-P)
2016-11-22T09:36:20Z
2017-10-10T02:45:06Z
2016-10
info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
0947-6539
http://hdl.handle.net/10259/4279
eng
Chemistry-a european journal. 2015, V. 22, n. 42, p. 15058–15068
http://dx.doi.org/10.1002/chem.201602254
info:eu-repo/semantics/openAccess
application/pdf
Wiley-VCH Verlag