Loading…
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...
Saved in:
Published in: | Journal of the American Chemical Society 2024-07, Vol.146 (29), p.19929-19938 |
---|---|
Main Authors: | , , , , |
Format: | Article |
Language: | English |
Online Access: | Get full text |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
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 |