Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited

2026-09-06T17:18:27Zhttps://riubu.ubu.es/oai/request

oai: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 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 2016-11-22 2017-10-10 2016-10 info:eu-repo/semantics/article 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 Wiley-VCH Verlag