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.
Document type :
Journal articles
Complete list of metadatas

https://hal-univ-rennes1.archives-ouvertes.fr/hal-01935364
Contributor : Laurent Jonchère <>
Submitted on : Monday, December 3, 2018 - 1:08:31 PM
Last modification on : Thursday, October 3, 2019 - 1:41:33 PM
Long-term archiving on : Monday, March 4, 2019 - 2:35:09 PM

File

Akimoto_Deprotonative Metalati...
Files produced by the author(s)

Identifiers

Citation

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, American Chemical Society, 2018, 83 (21), pp.13498-13506. ⟨10.1021/acs.joc.8b02397⟩. ⟨hal-01935364⟩

Share

Metrics

Record views

142

Files downloads

81