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/PMC10923551PMC
http://dx.doi.org/10.1021/acscatal.3c02209DOI Listing

Publication Analysis

Top Keywords

premetalated reagents
12
intermolecular metal-catalyzed
8
metal-catalyzed c‒c
8
alcohols aldehydes
8
ketone construction
8
c‒c coupling
4
coupling unactivated
4
unactivated alcohols
4
aldehydes convergent
4
convergent ketone
4

Similar Publications

Article Synopsis
  • * These innovative methods utilize a redox process, allowing for the production of organometallic nucleophiles without needing traditional reagents like carbonyl additives or chiral auxiliaries.
  • * The approach allows selective dehydrogenation of primary alcohols when secondary alcohols are present, facilitating carbon-carbon coupling without the need for protecting groups.
View Article and Find Full Text PDF

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 PDF

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 PDF

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 PDF

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 PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!