Intermolecular metal-catalyzed C‒C couplings of unactivated primary alcohols or aldehydes to form ketones are catalogued. Reactions are classified on the basis of pronucleophile. Protocols involving premetalated reagents or reactants that incorporate directing groups are not covered. These methods represent an emerging alternative to classical multi-step protocols for ketone construction that exploit premetalated reagents, and/or steps devoted to redox manipulations and carboxylic acid derivatization.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10923551 | PMC |
http://dx.doi.org/10.1021/acscatal.3c02209 | DOI Listing |
Chem Rev
December 2024
University of Texas at Austin, Department of Chemistry, 105 E 24th St., Welch Hall (A5300), Austin, Texas 78712, United States.
ACS Catal
August 2023
University of Texas at Austin, Department of Chemistry, Welch Hall (A5300), 105 E 24 St., Austin, TX 78712, USA.
Intermolecular metal-catalyzed C‒C couplings of unactivated primary alcohols or aldehydes to form ketones are catalogued. Reactions are classified on the basis of pronucleophile. Protocols involving premetalated reagents or reactants that incorporate directing groups are not covered.
View Article and Find Full Text PDFChem Sci
November 2022
Department of Chemistry, University of Texas at Austin, Welch Hall (A5300) 105 E 24th St. Austin TX 78712 USA
Ruthenium-catalyzed hydrogen auto-transfer reactions for the direct enantioselective conversion of lower alcohols to higher alcohols are surveyed. These processes enable completely atom-efficient carbonyl addition from alcohol proelectrophiles in the absence of premetalated reagents or metallic reductants. Applications in target-oriented synthesis are highlighted, and a brief historical perspective on ruthenium-catalyzed hydrogen transfer processes is given.
View Article and Find Full Text PDFJ Org Chem
April 2023
University of Texas at Austin, Department of Chemistry Welch Hall (A5300), 105 E 24th St, Austin, Texas 78712, United States.
In this Perspective, the use of methanol and ethanol as C1 and C2 feedstocks in metal-catalyzed C-C couplings to π-unsaturated pronucleophiles via hydrogen auto-transfer is surveyed. In these processes, alcohol oxidation to form an aldehyde electrophile is balanced by reduction of an π-unsaturated hydrocarbon to form a transient organometallic nucleophile. Mechanistically related reductive couplings of paraformaldehyde mediated by alcohol reductants or formic acid also are described.
View Article and Find Full Text PDFJ Am Chem Soc
May 2022
University of Texas at Austin, Department of Chemistry, 105 East 24th Street, Austin, Texas 78712, United States.
The first enantioselective ruthenium-catalyzed carbonyl vinylations via hydrogen autotransfer are described. Using a ruthenium-JOSIPHOS catalyst, primary alcohols - and 2-butyne are converted to chiral allylic alcohols - with excellent levels of absolute stereocontrol. Notably, 1°,2°-1,3-diols participate in site-selective C-C coupling, enabling asymmetric carbonyl vinylation beyond premetalated reagents, exogenous reductants, or hydroxyl protecting groups.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!