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

Autor: Swyka RA; Department of Chemistry , University of Texas at Austin , Austin , Texas 78712 , United States., Shuler WG; Department of Chemistry , University of Texas at Austin , Austin , Texas 78712 , United States., Spinello BJ; Department of Chemistry , University of Texas at Austin , Austin , Texas 78712 , United States., Zhang W; Department of Chemistry , University of Texas at Austin , Austin , Texas 78712 , United States., Lan C; Department of Chemistry , University of Texas at Austin , Austin , Texas 78712 , United States., Krische MJ; Department of Chemistry , University of Texas at Austin , Austin , Texas 78712 , United States.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2019 May 01; Vol. 141 (17), pp. 6864-6868. Date of Electronic Publication: 2019 Apr 18.
DOI: 10.1021/jacs.9b03113
Abstrakt: A regiodivergent catalytic method for direct conversion of aldehydes to branched or linear alkyl ketones is described. Rhodium complexes modified by P t Bu 2 Me catalyze formate-mediated aldehyde-vinyl bromide reductive coupling-redox isomerization to form branched ketones. Use of the less strongly coordinating ligand, PPh 3 , 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.
Databáze: MEDLINE
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