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Conversion of Aldehydes to Branched or Linear Ketones via Regiodivergent Rhodium-Catalyzed Vinyl Bromide Reductive Coupling–Redox Isomerization Mediated by Formate

Author:
Swyka, Robert A., Shuler, William G., Spinello, Brian J., Zhang, Wandi, Lan, Chunling, Krische, Michael J.
Source:
Journal of the American Chemical Society 2019 v.141 no.17 pp. 6864-6868
ISSN:
1520-5126
Subject:
aldehydes, amides, formates, isomerization, ketones, ligands, morpholine, organobromine compounds, rhodium
Abstract:
A regiodivergent catalytic method for direct conversion of aldehydes to branched or linear alkyl ketones is described. Rhodium complexes modified by PᵗBu₂Me catalyze formate-mediated aldehyde–vinyl bromide reductive coupling–redox isomerization to form branched ketones. Use of the less strongly coordinating ligand, PPh₃, promotes vinyl- to allylrhodium isomerization en route to linear ketones. This method bypasses the 3-step sequence often used to convert aldehydes to ketones involving the addition of pre-metalated reagents to Weinreb or morpholine amides.
Agid:
6392175