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. 2023 Aug 18;13(16):10976-10987.
doi: 10.1021/acscatal.3c02209. Epub 2023 Aug 4.

Intermolecular Metal-Catalyzed C‒C Coupling of Unactivated Alcohols or Aldehydes for Convergent Ketone Construction beyond Premetalated Reagents

Brian J Spinello  1 , Zachary H Strong  1 , Eliezer Ortiz  1 , Maddie M Evarts  1 , Michael J Krische  1
Affiliations

Intermolecular Metal-Catalyzed C‒C Coupling of Unactivated Alcohols or Aldehydes for Convergent Ketone Construction beyond Premetalated Reagents

Brian J Spinello et al. ACS Catal. .

Abstract

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.

Keywords: Alcohol; Aldehyde; C-C Coupling; Green Chemistry; Ketone.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Classical vs catalytic methods for convergent ketone construction.
Scheme 1.
Scheme 1.
Ruthenium-catalyzed C-C coupling of dienes with primary alcohols or aldehydes to form β,γ-unsaturated ketones.
Scheme 2.
Scheme 2.
Rhodium-catalyzed C-C coupling of dienes with primary alcohols or aldehydes to form ketones.
Scheme 3.
Scheme 3.
Cobalt-catalyzed C-C coupling of dienes with aldehydes to form ketones.
Scheme 4.
Scheme 4.
Ruthenium-catalyzed C-C coupling of allyl acetate with alcohols to form ketones.
Scheme 5.
Scheme 5.
Ruthenium-catalyzed aldol-type couplings of alcohols and aldehydes to form β-hydroxy ketones and 1,3-diones.
Scheme 6.
Scheme 6.
Nickel- and ruthenium-catalyzed C-C couplings of alkynes with aldehydes or alcohols to form ketones.
Scheme 7.
Scheme 7.
Iridium- and ruthenium-catalyzed C-C couplings of alkynes with aldehydes or alcohols to form ketones via alkyne-to-allene isomerization.
Scheme 8.
Scheme 8.
Ruthenium-catalyzed C-C couplings of alkynes with aldehydes or alcohols to form ynones.
Scheme 9.
Scheme 9.
Palladium-catalyzed C-C couplings of aryl bromides with aldehydes to form aryl ketones.
Scheme 10.
Scheme 10.
Nickel-catalyzed C-C couplings of aryl iodides and triflates with aldehydes or alcohols to form aryl ketones.
Scheme 11.
Scheme 11.
Rhodium-catalyzed reductive coupling–redox isomerization of vinyl bromides or vinyl triflates with aldehydes to form ketones.
Scheme 12.
Scheme 12.
Cobalt-catalyzed C-C couplings of aryl halides with aldehydes to form aryl ketones.
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