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Published in final edited form as: ACS Catal. 2023 Aug 4;13(16):10976–10987. doi: 10.1021/acscatal.3c02209

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
PMCID: PMC10923551  NIHMSID: NIHMS1925802  PMID: 38464997

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: Ketone, Aldehyde, Alcohol, C-C Coupling, Green Chemistry

<< TABLE OF CONTENTS GRAPHIC >>

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I. Introduction and Scope of Review

Primary alcohols are among the most frequently found functional groups in nature1 and pervade commodity chemical synthesis.2 Aldehydes are highly abundant platform chemicals that are accessible via hydroformylation3 and related reductive carbonylation processes.4 Both primary alcohols and aldehydes are important precursors for the convergent construction of ketones, which are of broad utility across the pharmaceutical, agrochemical and flavor-fragrance industries.5 Classical convergent ketone syntheses often require multi-step protocols involving premetalated reagents and discrete redox manipulations (Figure 1).6 Metal-catalyzed cross-couplings of carboxylic acid derivatives also require premetalated reagents.7 Direct catalytic methods for the conversion of unactivated primary alcohols or aldehydes to ketones remain highly uncommon.8

Figure 1.

Figure 1.

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Classical vs catalytic methods for convergent ketone construction.

In this monograph, direct intermolecular metal-catalyzed C‒C couplings of unactivated primary alcohols or aldehydes to form ketones are catalogued.8 Carbonylative cross-couplings of organotin, organoboron, organosilicon compounds and other organometallics are not included,9 nor are organocatalyzed/organococatalyzed reactions (such as the Stetter and benzoin reactions)10 and acyl radical additions.11 Coverage is focused on intermolecular couplings of unactivated alcohols or aldehydes (no directing groups or vicinal dicarbonyl compounds). The large body of literature on metal-catalyzed alkene hydroacylation,12 and other C‒H activation-initiated processes that convert alcohols or aldehydes to ketones,13 which often require chelating/directing groups, has been extensively reviewed and is not surveyed.12,13 Multicomponent processes (for example, 2:1 couplings of allenes with aldehydes to form ketones)14 and those involving ring formation or ring cleavage are not covered,15 nor are step-wise processes in which C-C bond formation and alcohol oxidation are mechanistically uncoupled.16

II. Catalytic Ketone Synthesis from Alcohols or Aldehydes

II.A. Diene Pronucleophiles

Following the seminal report of late transition metal-catalyzed diene-carbonyl reductive coupling to form homoallylic allylic alcohols (which employed a ruthenium catalyst),17 the use of dienes as allylmetal pronucleophiles in C=X (X = O, NR) addition expanded significantly.18 Despite these advances, related convergent ketone syntheses using diene pronucleophiles have remained uncommon, as carbonyl allylation generates a homoallylic alkoxide that chelates the metal center to impede or entirely suppress β-hydride elimination to generate the ketone (as in Scheme 1, catalytic intermediate IV). In line with reasoning, for the parent ruthenium-based catalyst system,17 it was posited that a greater degree of coordinative unsaturation would unlock β-hydride elimination to form the β,γ-enones. Indeed, upon use of trifluoroacetate as counterion, which fluctuates between bidentate and monodenate binding modes, and the absence of exogenous ligand, the β,γ-unsaturated ketones form as single regioisomers (without isomerization to the α,β-enones) using alcohol proelectrophiles19a or aldehydes19a,b (Scheme 1A & 1B, respectively). As corroborated by deuterium labelling (not shown),19a the reaction mechanism involves dehydrogenation of the primary alcohol via ruthenium alkoxide I to generate the ruthenium hydride II, which upon diene hydrometalation delivers the allylruthenium nucleophile III. Carbonyl addition by way of the primary σ-allyl haptomer provides the homoallylic ruthenium alkoxide IV. Although β-hydride elimination from the kinetic homoallylic alkoxide IV cannot be disqualified, competing formation of the homoallylic alcohol suggests ruthenium alkoxide IV forms reversibly and that the β,γ-enone is generated in a separate/discrete hydrogen transfer from the homoallylic alcohol to the diene by way of alkoxide IV (Scheme 1C).

Scheme 1.

Scheme 1.

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Ruthenium-catalyzed C-C coupling of dienes with primary alcohols or aldehydes to form β,γ-unsaturated ketones.

In a related rhodium-catalyzed reaction, ketone synthesis is achieved using diene pronucleophiles in combination with allylic alcohol proelectrophiles (Scheme 2A).20 As corroborated by deuterium labeling studies, allyl alcohol dehydrogenation provides a rhodium hydride and an aldehyde. Diene hydrometalation delivers an allylrhodium nucleophile, which upon aldehyde addition delivers a homoallylic alkoxide. β-Hydride elimination provides a transient dienone, which upon conjugate reduction and base-catalyzed isomerization furnishes the α,β-enone. This atom efficient method was applicable to the feedstock dienes isoprene and myrcene. A similar mode of reactivity is observed in reactions of butadiene with benzylic or aliphatic primary alcohol proelectrophiles (Scheme 2B).21 Here, β-hydride elimination from the homoallylic rhodium alkoxide provides a transient β,γ-unsaturated ketone and a rhodium hydride. As demonstrated by crossover experiments, redox-isomerization of the homoallylic alkoxide to the isobutyl ketone product occurs without dissociation of rhodium at any intervening stage. Related aldehyde-butadiene reductive couplings to form isobutyl ketones were achieved using formate as the terminal hydrogen source under otherwise identical conditions (Scheme 2C).21

Scheme 2.

Scheme 2.

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Rhodium-catalyzed C-C coupling of dienes with primary alcohols or aldehydes to form ketones.

Abundant, inexpensive cobalt catalysts convert substituted dienes and aromatic aldehydes to β,γ-unsaturated ketones, which are formed with complete levels of (Z)-alkene stereoselectivity (Scheme 3A).22a Like the preceding ruthenium- and rhodium-catalyzed reactions,19–21 these processes may be viewed as formal diene hydroacylations, thus overcoming a major limitation associated with traditional hydroacylation; the requirement of β-chelating aldehydes to suppress decarbonylation of acylmetal intermediates.12 Mechanistically, the cobalt-catalyzed reactions occur through diene-aldehyde oxidative coupling to form a π-allyl-containing oxacobaltacycle. β-Hydride elimination from the primary σ-allyl haptomer followed by C-H reductive elimination delivers the (Z)-β,γ-unsaturated ketones. Complete stereo- and regioselectivities were only observed in reactions of aromatic aldehydes. Intervention of the putative π-allyl-containing oxacobaltacycle finds precedent in earlier work using isoelectronic ruthenium(0) catalysts, which promote in diene-aldehyde oxidative coupling to form analogous π-allyl-containing oxaruthenacycles, which were isolated and characterized by X-ray diffraction.23 In a significant advance, it was subsequently demonstrated that cationic cobalt catalysts modified by (S,S)-Ph-BPE promote the highly enantioselective coupling of dienes and aldehydes to form γ,δ-unsaturated ketones, albeit with incomplete levels of regiocontrol (Scheme 3B).22b For the cationic cobalt catalyst, the additional coordinative site enables internal chelation to the ketone at the stage of the hydride intermediate, which biases reductive elimination from the tertiary σ-allyl haptomer, resulting in the observed inversion of regioselectivity.

Scheme 3.

Scheme 3.

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Cobalt-catalyzed C-C coupling of dienes with aldehydes to form ketones.

II.B. Allyl-X Pronucleophiles

Exposure of primary alcohols to allyl acetate in the presence of a ruthenium catalyst assembled from RuCl2(PPh3)2 and carbon monoxide results in formation of α,β-unsaturated ketones (Scheme 4).24 A mechanism was proposed in which π-allyl formation is followed by alcohol dehydrogenation to generate an aldehyde, which upon carbonyl addition-β-hydride elimination furnishes a β,γ-unsaturated ketone. Base-catalyzed conjugation then furnishes the α,β-enone. The related ruthenium complexes Ru(CO)3(PPh3)2 and Ru(OAc)2(CO)2(PPh3)2 also are competent catalysts under these conditions. To our knowledge, this work, which was reported in 1991, represents the earliest example of the metal-catalyzed conversion of alcohols to ketones. The use of carbon monoxide (CO) as a spectator ligand may increase Lewis acidity at ruthenium to facilitate carbonyl addition or, as illustrated in the work of Bäckvall, it may provide a kinetic pathway for chloride substitution by alkoxide.25

Scheme 4.

Scheme 4.

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Ruthenium-catalyzed C-C coupling of allyl acetate with alcohols to form ketones.

II.C. Enone and Acrylate Pronucleophiles

In an unusual variation of the metal-catalyzed reductive aldol reaction,26 exposure of enals to RuHCl(CO)(PPh3)3 in the presence of 2-propanol resulted in homo-coupling accompanied by redox isomerization to form β-hydroxy ketones (Scheme 5A).27a The reaction mechanism involves initial enal hydroruthenation to furnish a ruthenium(II) enolate, which upon aldehyde addition delivers the ruthenium aldolate. Internal redox isomerization followed by reduction of the transient β-ketoaldehyde provides the β-hydroxy ketones. Related redox-neutral homo-couplings (Scheme 5B)27b and cross-couplings (Scheme 5C)27c have been described wherein unsaturated alcohols serve dually as reductants and aldehyde proelectrophiles (Scheme 5). Finally, it was found that conjugated enones and aldehydes undergo redox-neutral enolate-mediated C-C coupling to furnish 1,3-dicarbonyl compounds (Scheme 5D).28a,b Notably, such processes can be conducted using γ,δ-unsaturated ketone pronucleophiles via tandem redox-isomerization-enolate-mediated carbonyl addition to deliver 1,3-dicarbonyl compounds with high levels of efficiency (Scheme 5E).28c

Scheme 5.

Scheme 5.

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Ruthenium-catalyzed aldol-type couplings of alcohols and aldehydes to form β-hydroxy ketones and 1,3-diones.

II.D. Alkyne Pronucleophiles

In 1990, the nickel(0)-catalyzed coupling of alkynes and aldehydes to form α,β-unsaturated ketones was reported (Scheme 6A).29a The reaction is initiated via alkyne-aldehyde oxidative coupling to form a nickeladihydrofuran. This event is facilitated by the nucleophilic metalacyclopropene character of the alkyne π-complex conferred by π-backbonding.30 Stoichiometric reactions of Ni(cod)2, butyne and benzaldehyde in the presence of PCy3 form isolable nickeladihydrofurans that have been characterized by X-ray diffraction analysis.31 Related hydrogen auto-transfer processes were subsequently disclosed, wherein alcohols function dually as aldehyde proelectrophiles and reductants (Scheme 6B).29b Here, the initially formed allylic alcohols suffer alcohol-mediated transfer hydrogenation, which concomitantly generates the aldehyde and saturated ketone products. Ruthenium catalysts also promote the coupling of alkynes with aldehydes (Scheme 6C) or alcohols (Scheme 6D) to form α,β-unsaturated ketones.32 Specifically, exposure of 2-butyne to aromatic or aliphatic aldehydes in the presence of Ru(TFA)2(CO)(PPh3)2 and 2-propanol (100 mol%) results in enone formation. Unlike the nickel-catalyzed reactions, the ruthenium-catalyzed process occurs through alkyne hydroruthenation to form a vinylruthenium nucleophile. Aldehyde addition followed by β-hydride elimination from the resulting alkoxide provides the ketone. Although the reaction is redox-neutral, dehydrogenation of 2-propanol is required to generate the ruthenium hydride required for entry into the catalytic cycle. When the reaction is conducted using alcohol proelectrophiles, 2-propanol is not required. Both the nickel- and ruthenium-catalyzed reactions are restricted to symmetric alkynes so as to prevent formation of regioisomers.

Scheme 6.

Scheme 6.

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Nickel- and ruthenium-catalyzed C-C couplings of alkynes with aldehydes or alcohols to form ketones.

Under the conditions of iridium catalysis, alkynes engage in C-C couplings to aldehydes or alcohols to form α,β-unsaturated ketones (Scheme 7A).33a Although the authors propose an alternate mechanism, subsequent work34 suggests these reactions proceed via iridium hydride-mediated alkyne-to-allene isomerization. Allene hydroiridation then forms an allyliridium nucleophile, which upon aldehyde addition and β-hydride elimination from the resulting homoallylic iridium alkoxide furnishes a β,γ-unsaturated ketone. Finally, base-catalyzed isomerization of the β,γ-enone by excess trioctylphosphine provides the α,β-unsaturated ketones. In support of these later steps in the mechanism, the authors demonstrate that exposure of homoallylic alcohols to the reaction conditions results in formation of the α,β-enones. For reactions conducted from the alcohol oxidation level, the aldehyde is likely generated via alcohol-to-alkyne hydrogen transfer (Scheme 7b). Following this work, ruthenium-catalyzed alkyne-aldehyde C-C couplings were developed that occur by an analogous mechanism (Scheme 7C).33b In these reactions, β,γ-unsaturated ketones are formed. This study appeared contemporaneously alongside related reactions that furnish enantiomerically enriched homoallylic alcohols (not shown).34a

Scheme 7.

Scheme 7.

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Iridium- and ruthenium-catalyzed C-C couplings of alkynes with aldehydes or alcohols to form ketones via alkyne-to-allene isomerization.

Iodide-bound ruthenium catalysts modified by rac-BINAP catalyze the C-C coupling of terminal alkynes with aldehydes (Scheme 8A) or alcohols (Scheme 8B) to form α,β-acetylenic ketones.35 As corroborated by deuterium labeling experiments, oxidative alkynylation occurs through a novel mechanism in which alkyne hydroruthenation delivers a transient vinylruthenium complex that deprotonates the terminal alkyne to form the alkynylruthenium nucleophile. Aldehyde addition followed by β-hydride elimination of the resulting propargylic ruthenium alkoxide forms the ynone product. When reactions are conducted from the aldehyde oxidation level, deprotonation of the terminal alkyne by the π-allyl moiety of the precatalyst, RuI(CO)3(η3-C3H5) initiates catalysis. These processes represent the first metal-catalyzed oxidative alkynylations of primary alcohols or aldehydes.

Scheme 8.

Scheme 8.

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Ruthenium-catalyzed C-C couplings of alkynes with aldehydes or alcohols to form ynones.

II.E. Aryl and Vinyl C-X σ-Pronucleophiles

II.E.1. Palladium

The palladium-catalyzed acylation of aryl halides mediated by unactivated aldehydes, that is, the “oxa-Heck” reaction, is a challenging process due to the low oxaphilicity of palladium and consequent inefficiency of carbonyl insertion into arylpalladium bonds. Hence, most reported palladium-catalyzed C-C couplings of aryl halides with aldehydes to form ketones require chelating aldehydes,36a,b,i,j derivatization of the aldehyde as the hydrazone36c or enamine,36d,e,f,g,h or intervention of acyl radicals.36k,l These methods fall beyond the scope of this review and the reader is directed to the primary literature. To our knowledge, the first documented use of unactivated aldehydes in palladium- catalyzed oxa-Heck reactions appeared in 2013 and exploits an NHC-modified palladium catalyst (Scheme 9A).37a However, the requirement of excess base suggests these reactions may proceed via enolate carbopalladation. Indeed, the alkyl-aryl ketones are formed as regioisomeric mixtures along with products of α-arylation. Subsequently, a palladium catalyst modified by a heterobidentate P-S donor ligand was used in combination with a milder carbonate base, enabling formation of oxa-Heck products in higher yields (Scheme 9B).37b Finally, an alternate approach to the acylation of aryl halides using unactivated aldehydes lacking directing or activating groups takes advantage of palladium catalysts modified by N-cyclohexyl picolinamide ligands (Scheme 9C).37c Computational studies corroborate a reaction mechanism in which aldehyde C-H activation via concerted metalation-deprotonation (CMD) is followed by palladium(II)-mediated aryl bromide oxidative addition to generate an arylpalladium(IV) species, which upon C-C reductive elimination provides the diaryl ketone. Notably, decarbonylation of the putative acylpalladium intermediate does not occur.

Scheme 9.

Scheme 9.

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Palladium-catalyzed C-C couplings of aryl bromides with aldehydes to form aryl ketones.

II.E.2. Nickel

Many of the limitations associated with the palladium-catalyzed oxa-Heck reaction also are evident in nickel-catalyzed variants. Due to its electropositive nature and small atomic radius, reductive elimination and β-hydride elimination from nickel complexes are often slow or even rate-determining, which complicates nickel-catalyzed Heck reactions and related processes.38,39 Hence, like palladium, nickel-catalyzed oxa-Heck reactions often require directing groups,40a involve non-classical pathways, including the use of epoxides as aldehyde proelectrophiles,40b or photochemical conversion of aldehydes to acyl radicals.40c The first true nickel-catalyzed oxa-Heck reaction of unactivated aldehydes appeared in 2002, and involved the coupling of aryl iodides with aliphatic or aromatic aldehydes using the nickel catalyst generated via zinc-mediated reduction of Ni(dppe)Br2 (Scheme 10A).41a The reaction proceeds via Ni(0)-mediated aryl iodide oxidative addition followed by iodide abstraction by ZnBr2 to furnish a cationic arylnickel(II) complex. The cationic nature of the arylnickel(II) intermediate promotes aldehyde coordination and induces a more pronounced LUMO-lowering effect to facilitate the carbonyl insertion event. β-Hydride elimination from the resulting cationic alkoxynickel(II) complex releases the aryl ketone and delivers a Ni(II) hydride, which upon zinc-mediated reduction regenerates the catalyst. Subsequently, nickel-triphos complexes were identified by high-throughput experimentation as effective catalysts for aryl triflate-mediated oxa-Heck reactions (Scheme 10B).41b,c As corroborated by DFT calculations,42 these reactions are facilitated by the weakly-coordinating triflate counterion, which confers cationic character and coordinative unsaturation to the organonickel(II) intermediates. Notably, the nickel-triphos-catalyzed oxa-Heck reactions can be applied to alcohol proelectrophiles (Scheme 10C).41b,c In these dehydrogenative processes, acetone functions as the terminal oxidant and deprotonation of the nickel(II) hydride enables regeneration of the nickel(0) catalyst. Finally, nickel-triphos-catalysts also promote aryl triflate-mediated oxa-Heck reactions in which olefinic alcohols generate aldehydes via internal redox isomerization (Scheme 10D).41d

Scheme 10.

Scheme 10.

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Nickel-catalyzed C-C couplings of aryl iodides and triflates with aldehydes or alcohols to form aryl ketones.

II.E.3. Rhodium

Direct rhodium-catalyzed coupling of aryl halides with aldehydes to form ketones are rare and require derivatization of the aldehyde as the N-pyridyl imine,43a or use of chelating salicylaldehydes43b or 2-(sulfonylamino)benzaldehydes,43b which falls outside the scope of this review. However, the rhodium-catalyzed coupling of vinyl halides with unactivated aldehydes was achieved in 2019 via formate-mediated carbonyl reductive coupling-redox isomerization (Scheme 11A & B).44a Notably, using 2-bromopropene as the pronucleophile, a ligand-dependent divergence in regioselectivity was observed that enables formation of either branched or linear propyl ketones. Specifically, using the strong σ-donor ligand, PtBu2Me, oxidative addition of 2-bromopropene to the rhodium(I) catalyst generates a vinylrhodium(III) nucleophile, which upon aldehyde addition furnishes an allylic alkoxide. Subsequent redox isomerization gives rise to the branched ketones (Scheme 11A). In contrast, dissociation of the weak σ-donor ligand, PPh3, triggers β-hydride elimination to form a transient allene and a rhodium(III) hydride, which combine to furnish an allylrhodium(III) nucleophile, ultimately providing the linear propyl ketones (Scheme 11B). This catalytic system was later adapted to vinyl triflate pronucleophiles, enabling construction of cycloalkyl ketones (Scheme 11C).44b

Scheme 11.

Scheme 11.

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Rhodium-catalyzed reductive coupling–redox isomerization of vinyl bromides or vinyl triflates with aldehydes to form ketones.

II.E.4. Cobalt

To our knowledge, only one cobalt-catalyzed “oxa-Heck” reaction has been developed, in which substoichiometric quantities of CoCl3 are bound by an NHC ligand to a nano-silica support (Scheme 12).45 The authors propose a reaction mechanism in which aryl halide oxidative addition to cobalt(I) is followed by concerted metalation-deprotonation (CMD) of the aldehyde formyl C-H bond. Reductive elimination from the resulting acylcobalt complex then delivers the ketone and regenerates the cobalt(I) catalyst to close the catalytic cycle. While the oxidation state of cobalt is not indicated by the authors, cobalt(I) is likely required for aryl halide oxidative addition and may be generated in situ by reductive elimination of bis-NHC cobalt(III) complexes.

Scheme 12.

Scheme 12.

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Cobalt-catalyzed C-C couplings of aryl halides with aldehydes to form aryl ketones.

III. Conclusion and Outlook

The ketone functional group is prominent among pharmaceutical ingrediants,45 and is a gateway to other functional groups of still greater commercial importance, including chiral α-stereogenic amines (via biocatalysis),46 which comprise roughly 40% of small molecule pharmaceutical agents and 20% of agrochemicals.47 Despite their fundamental significance, the vast majority of methods for convergent ketone construction are multi-step protocols that require premetalated reagents and redox reactions.6,7 It is the authors’ hope that the present catalog of metal-catalyzed methods for convergent ketone construction will impel studies that unlock the two foremost challenges that remain in this field of research: (a) the longstanding challenge of designing hydroacylation catalysts that are applicable to α-olefins (and higher polyunsaturated hydrocarbon pronucleophiles), display catalyst-directed linear or branched regioselectivity, and do not require non-native directing/chelating groups;12 (b) The direct dehydrogenative coupling of unactivated aryl C-H compounds (vis-à-vis C-H activation-initiated generation of arylmetal nucleophiles)13 for the formal acylation of aromatic and heteroaromatic compounds using alcohol proelectrophiles or aldehydes in which the reactants do not require any non-native directing/chelating groups.

ACKNOWLEDGMENT

The Robert A. Welch Foundation (F-0038) and the NIH-NIGMS (RO1-GM069445) are acknowledged for partial support of this research.

The Robert A. Welch Foundation (F-0038) and the NIH-NIGMS (RO1-GM069445) are acknowledged for financial support.

Footnotes

The authors declare no competing financial interest.

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