Categories: C-C Bond Formation > Oxygen-containing molecules > Carbonyl compounds > Acylation

Hydroacylations

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Recent Literature

A nickel-catalyzed intermolecular hydroacylation reaction of alkenes with simple aldehydes offers an approach to the selective preparation of branched ketones in high yields and selectivities. The origin of the reactivity and regioselectivity of this reaction was investigated computationally.
L.-J. Xiao, X.-N. Fu, M.-J. Zhou, J.-H. Xie, L.-X. Wang, X.-F. Xu, Q.-L. Zhou, J. Am. Chem. Soc., 2016, 138, 2957-2960.

A Ni-catalyzed dehydrogenative cross-coupling reaction cascade between readily available alcohols and olefins enables a direct synthesis of α-arylated ketones. This cost-effective method provides monoarylated ketones in good yields with exclusive selectivity without using any advanced synthetic intermediates.
P.-F. Yang, W. Shu, Org. Lett., 2020, 22, 6203-6208.

Acylphosphonates with a 5,5-dimethyl-1,3,2-dioxophosphinanyl skeleton are efficient intermolecular radical acylation reagents, which enable cobalt-catalyzed Markovnikov hydroacylations of unactivated alkenes at room temperature under mild conditions. The protocol offers wide functional group compatibility and broad substrate scope, providing branched ketones in good yields.
B. Zhang, J. He, Y. Li, T. Song, Y. Fang, C. Li, J. Am. Chem. Soc., 2021, 143, 4955-4961.

Hybrid phosphorus ligands enable a Rh-catalyzed enantioselective anti-Markovnikov hydroformylation of unfunctionalized 1,1-disubstituted alkenes to provide linear aldehydes with β-chirality in high yields and enantioselectivities under mild conditions. In a large-scale synthesis, a very low catalyst loading (0.05 mol %) furnished the desired product in good yield and undiminished selectivity.
C. You, S. Li, X. Li, J. Lan, Y. Yang, L. W. Chung, H. Lv, X. Zhang, J. Am. Chem. Soc., 2018, 140, 4977-4981.

An effective and operationally simple palladium-catalyzed regioselective hydroformylation of olefins with formic acid provides linear aldehydes in good yield with excellent regioselectivity. 1,3-Bis(diphenylphosphino)propane (dppp) as the ligand plays a crucial role in directing the reaction pathway. The process requires no syngas.
W. Ren, W. Chang, J. Dai, Y. Shi, J. Li, Y. Shi, J. Am. Chem. Soc., 2016, 138, 14864-14867.

Hydroformylation of alkenes can be carried out in a few minutes under microwave activation at a relatively low pressure (2.7 atm) using commercially available catalysts and ligands. After 4 min of microwave irradiation, the corresponding aldehyde is formed in high yield.
E. Petricci, A. Mann, A. Schoenfelder, A. Rota, M. Taddei, Org. Lett., 2006, 8, 3725-3727.

The 6-DPPon/rhodium catalyst allows for the first time a room temperature/ambient pressure hydroformylation of various, structurally diverse terminal alkenes with low catalyst loadings. This protocol omits the need for special pressure equipment and should find wide application in organic synthesis.
W. Seiche, A. Schuschkowski, B. Breit, Adv. Syn. Catal., 2005, 1488-1494.

A direct asymmetric copper hydride (CuH)-catalyzed coupling of α,β-unsaturated carboxylic acids with aryl alkenes provides chiral α-aryl dialkyl ketones. The reaction tolerates various substrate substitution patterns, sensitive functional groups, and heterocycles.
Y. Zhou, J. S. Bandar, S. L. Buchwald, J. Am. Chem. Soc., 2017, 139, 8126-8129.

A nickel-catalyzed, multicomponent regio- and enantioselective hydroformylation and carbonylation using chloroformate as a safe CO source provides a wide variety of unsymmetrical dialkyl ketones bearing a functionalized α-stereocenter, including enantioenriched chiral α-aryl ketones and α-amino ketones.
J. Chen, S. Zhu, J. Am. Chem. Soc., 2021, 143, 14089-14096.

A visible light mediated coupling of benzoic acid derivatives with alkenes provides dihydrochalcone via deoxygenation using diphenyl sulfide as O-transfer reagent. Under mild photoredox conditions, a series of dihydrochalcone derivatives were produced in good yields.
X. Fan, X. Sun, M. Ji, H. Tong, W. Zhang, Z. Sun, W. Chu, Org. Lett., 2022, 24, 7271-7275.

A general protocol for the hydroacylation of styrenes from aliphatic carboxylic acids proceeds via β-scission of a phosphoranyl radical that is accessed by photoredox catalysis, followed by addition of the resulting acyl radical to the styrenyl olefin.
J. I. M. Alvarado, A. B. Ertel, A. Stegner, E. E. Stache, A. G. Doyle, Org. Lett., 2019, 21, 9940-9944.

A visible light-promoted hydroacylation facilitates an efficient preparation of ketones from alkenes and 4-acyl-1,4-dihydropyridines via an acyl radical addition and hydrogen atom transfer pathway under photocatalyst-free conditions to provide highly functionalized ketone derivatives in very good yields. The presence of NiCl₂·DME enables the synthesis of 1,4-dicarbonyl compounds via diacylation.
X. Zhao, B. Li, W. Xia, Org. Lett., 2020, 22, 1056-1061.

Rhodium-catalyzed regioselective arylzincation of terminal allenes affords synthetically useful functionalized allylzinc reagents, which can be protonated or react with various electrophiles such as carbonyl compounds and acetonitrile.
Y. Yoshida, K. Murakami, H. Yorimitsu, K. Oshima, J. Am. Chem. Soc., 2010, 132, 8878-8879.

A regioselective intermolecular hydroacylation of vinalarenes, in which symmetric and mixed carboxylic anhydrides are used as acyl donors, is promoted by a cationic rhodium catalyst ligated by triphenylarsine.
Y.-T. Hong, A. Barchuk, M. J. Krische, Angew. Chem. Int. Ed., 2006, 45, 6885-6888.

A nickel hydride-catalyzed hydroacylation of aryl alkenes using aroyl fluorides proceeds without recourse to an exogenous ligand under mild conditions. The synthetic utility of the present method is demonstrated by a glovebox-free, gram-scale reaction and late-stage derivatizations of complex molecules.
J. Kim, J. Jang, Y. Lee, K. Shin, Org. Lett., 2022, 24, 5412-5416.

Rhodium (I) bis-olefin complexes catalyzes the addition of electron-rich aromatic aldehydes to olefins to form ketones. Use of a more electron-deficient Rhodium catalyst results in faster reaction rates, better selectivity for linear ketone products and broader reaction scope.
A. H. Roy, C. P. Lenges, M. Brookhart, J. Am. Chem. Soc., 2007, 129, 2082-2093.

A Rh/(S,S)-DTBM-YanPhos complex catalyzes an asymmetric anti-Markovnikov hydroformylation of α-substituted acrylates/acrylamides to provide a series of β-chiral linear aldehydes in high yields and enantioselectivities.
S. Li, Z. Li, C. You, X. Li, J. Yang, H. Lv, X. Zhang, Org. Lett., 2020, 22, 1108-1112.

A coordination-assisted strategy enables a rhodium-catalyzed regio- and enantioselective addition of unfunctionalized aldehydes to internal alkenes such as enamides and β,γ-unsaturated amides. Valuable α-amino ketones and 1,4-dicarbonyl compounds were directly obtained with high enantioselectivity from readily available materials.
X. Sun, P.-C. Gao, Y.-W. Sun, B.-J. Li, J. Am. Chem. Soc., 2024, 146, 723-732.

A cationic rhodium(I)/dppb complex catalyzed direct intermolecular hydroacylation of N,N-dialkylacrylamides with both aliphatic and aromatic aldehydes represents a versatile route to γ-ketoamides in view of high atom economy and commercial availability of substrates.
K. Tanaka, Y. Shibata, T. Suda, Y. Hagiwara, M. Hirano, Org. Lett., 2007, 9, 1215-1218.

A cationic rhodium(I)/(R,R)-QuinoxP* complex catalyzes a highly enantioselective direct intermolecular hydroacylation of α-substituted acrylamides with unfunctionalized aliphatic aldehydes to yield the corresponding γ-ketoamides in high yields with excellent ee values.
Y. Shibata, K. Tanaka, J. Am. Chem. Soc., 2009, 131, 12552-12553.

Various oxo acid derivatives were obtained directly from the reaction of aliphatic and aromatic aldehydes with ω-alkenoic acid derivatives in the presence of rhodium(I) complexes and 2-amino-3-picoline.
E.-A. Jo, C.-H. Jun, Eur. J. Org. Chem., 2006, 2504-2507.

An efficient and general hydroacylation of cyclopropenes provides various 2-acylcyclopropanes under mild reaction conditions via photoinduced decarboxylation of α-ketoacids followed by acyl radical addition to cyclopropenes. This diastereoselective protocol features a regioselective addition of the acyl radical at the least substituted olefinic carbon center and offers high functional group tolerance.
S. Biswas, P. Chandu, S. Garai, D. Sureshkumar, Org. Lett., 2023, 25, 7863-7867.

A highly enantio- and diastereoselective intramolecular Stetter reaction has been developed. Aliphatic and aromatic aldehydes and a broad range of trisubstituted Michael acceptors have been found to afford the desired products in good overall yield with high enantio- and diastereoselectivity.
J. Read de Alaniz, T. Rovis, J. Am. Chem. Soc., 2005, 127, 6284-6289.

Related

Using a Pd-NHC catalyst for cross-coupling of phenyl esters and alkyl boranes, alkyl ketones can be prepared in good yields via a Suzuki-Miyaura reaction proceeding by activation of the C(acyl)-O bond, whereas a Pd-dcype catalyst provides alkylated arenes by a modified pathway with extrusion of CO.
J. Masson-Makdissi, J. K. Vandavasi, S. G. Newman, Org. Lett., 2018, 20, 4094-4098.

A Cu-catalyzed hydrocarbonylative C-C coupling of unactivated alkyl iodides with terminal alkynes enables a highly chemo- and regioselective synthesis of unsymmetrical dialkyl ketones. A variety of functional groups are tolerated, and both primary and secondary alkyl iodides react well.
L.-J. Cheng, N. P. Mankad, J. Am. Chem. Soc., 2017, 139, 10200-10203.

Visible-light-driven hydroacylations and epoxyacylations in water using methylene blue as photoredox catalyst and persulfate as oxidant deliver ketones and epoxyketones from a range of aromatic and aliphatic aldehydes as well as conjugated and nonconjugated olefins as abundant and inexpensive chemical feedstocks.
G. F. P. de Souza, J. A. Bonacin, A. G. Salles, Jr., J. Org. Chem., 2018, 83, 8331-8340.

Under the synergistic actions of photocatalyst Ru(bpy)₃Cl₂, tert-butyl hydroperoxide, cesium carbonate, and visible light irradiation, a range of styrenes and benzaldehydes smoothly form α,β-epoxy ketones via visible-light-enabled photocatalytic generation of acyl radicals as key intermediates.
J. Li, D. Z. Wang, Org. Lett., 2015, 17, 5260-5263.