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An SN1‑Approach to Cross-Coupling: Deoxygenative Arylation Facilitated by the β‑Silicon Effect

We report a dual metal-catalyzed method for the cross-coupling of unprotected alcohols by exploiting the β-Si effect. This deoxygenative Suzuki-Miyaura reaction tolerates a range of primary, secondary, and tertiary alcohol substrates along with diverse functional groups and heterocycles. Mechanistic...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2024-07, Vol.146 (29), p.19929-19938
Main Authors: Cook, Adam, Kassymbek, Aishabibi, Vaezghaemi, Aref, Barbery, Carlos, Newman, Stephen G.
Format: Article
Language:English
Online Access:Get full text
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Summary:We report a dual metal-catalyzed method for the cross-coupling of unprotected alcohols by exploiting the β-Si effect. This deoxygenative Suzuki-Miyaura reaction tolerates a range of primary, secondary, and tertiary alcohol substrates along with diverse functional groups and heterocycles. Mechanistic experiments including KIE, VTNA, and Eyring analyses suggest the existence of a carbocation intermediate on the reaction pathway, consistent with a rare SN1 pathway for the activation of an electrophile in cross-coupling reactions. A novel bis-imidazolium N-heterocyclic carbene (NHC) ligand was found to be optimal for reactivity, and nickel(0)-, nickel­(I)- and nickel­(II)- complexes of this ligand were isolated and characterized. In contrast to more well-established shorter chain ligands, these long-chain NHCs are found to have characteristically large bite angles, which may be critical for enabling the deoxygenative arylation of aliphatic alcohols.
ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/jacs.4c03197