Deprotonative Metalation of Methoxy-Substituted Arenes Using Lithium 2,2,6,6-Tetramethylpiperidide Experimental and Computational Study - Université de Rennes Access content directly
Journal Articles Journal of Organic Chemistry Year : 2018

Deprotonative Metalation of Methoxy-Substituted Arenes Using Lithium 2,2,6,6-Tetramethylpiperidide Experimental and Computational Study

Abstract

The reaction pathways of lithium 2,2,6,6-tetramethylpiperidide (LiTMP)-mediated deprotonative metalation of methoxy-substituted arenes were investigated. Importantly, it was experimentally observed that, whereas TMEDA has no effect on the course of the reactions, the presence of more than the stoichiometric amount of LiCl is deleterious, in particular without an in situ trap. These effects were corroborated by the DFT calculations. The reaction mechanisms, such as the structure of the active species in the deprotonation event, the reaction pathways by each postulated LiTMP complex, the stabilization effects by in situ trapping using zinc species, and some kinetic interpretation, are discussed herein.
Fichier principal
Vignette du fichier
Akimoto_Deprotonative Metalation of Methoxy-Substituted.pdf (4.48 Mo) Télécharger le fichier
Origin Files produced by the author(s)

Dates and versions

hal-01935364 , version 1 (03-12-2018)

Identifiers

Cite

Gaku Akimoto, Mai Otsuka, Ryo Takita, Masanobu Uchiyama, Madani Hedidi, et al.. Deprotonative Metalation of Methoxy-Substituted Arenes Using Lithium 2,2,6,6-Tetramethylpiperidide Experimental and Computational Study. Journal of Organic Chemistry, 2018, 83 (21), pp.13498-13506. ⟨10.1021/acs.joc.8b02397⟩. ⟨hal-01935364⟩
139 View
174 Download

Altmetric

Share

Gmail Mastodon Facebook X LinkedIn More