Electrochemical deconstructive methoxylation of arylalcohols–A synthetic and mechanistic investigation

Maashi, Hussain A., Lewis‐Atwell, Toby, Harnedy, James, Grayson, Matthew N. and Morrill, Louis C. ORCID: https://orcid.org/0000-0002-6453-7531 2024. Electrochemical deconstructive methoxylation of arylalcohols–A synthetic and mechanistic investigation. Chemistry - A European Journal , e202403413. 10.1002/chem.202403413

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Abstract

Herein, we report a mechanistic investigation of a recently developed electrochemical method for the deconstructive methoxylation of arylalcohols. A combination of synthetic, electroanalytical, and computational experiments have been performed to gain a deeper understanding of the reaction mechanism and the structural requirements for fragmentation to occur. It was found that 2‐arylalcohols undergo anodic oxidation to form the corresponding aromatic radical cations, which fragment to form oxocarbenium ions and benzylic radical intermediates via mesolytic cleavage, with further anodic oxidation and trapping of the benzylic carbocation with methanol to generate the observed methyl ether products. It was also found that the electrochemical fragmentation of 2‐arylalkanols is promoted by structural features that stabilize the oxocarbenium ions and/or benzylic radical intermediates formed upon mesolytic cleavage of the aromatic radical cations. With an enhanced understanding of the reaction mechanism and the structural features that promote fragmentation, it is anticipated that alternative electrosynthetic transformations will be developed that utilize this powerful, yet underdeveloped, mode of substrate activation.

Item Type:	Article
Date Type:	Published Online
Status:	In Press
Schools:	Chemistry
Additional Information:	License information from Publisher: LICENSE 1: URL: http://creativecommons.org/licenses/by/4.0/
Publisher:	Wiley
ISSN:	0947-6539
Date of First Compliant Deposit:	31 October 2024
Date of Acceptance:	17 September 2024
Last Modified:	04 Nov 2024 10:25
URI:	https://orca.cardiff.ac.uk/id/eprint/173545

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