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Synthesis of 1,4-diketones

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A Pd-catalyzed addition of organozinc reagents to enones in the presence of carbon monoxide provides 1,4-diketones in good yield. Cyclic and acyclic α,β-unsaturated ketones as well as aldehydes can be converted.
D. W. Custar, H. Le, J. P. Morken, Org. Lett., 2010, 12, 3760-3763.

Conjugated addition of primary nitroalkanes to α,β-unsaturated ketones or α,β-unsaturated esters, in the presence of two equivalents of DBU, allows the one-pot prepration of γ-diketones or γ-keto esters, respectively. The reaction of 2-aryl-1-nitroethane derivatives with α,β-unsaturated ketones gives cyclopentenones.
R. Ballini, L . Barboni, G. Bosica, D. Fiorini, Synthesis, 2002, 2725-2728.

A palladium-catalyzed cross-coupling of cyclopropanols and acyl chlorides enables a convenient method for preparing attractively functionalized 1,4-diketones. The utility of this method has been demonstrated in an enantioselective synthesis of (+)-myrmicarin 217.
B. B. Parida, P. P. Das, M. Niocel, J. K. Cha, Org. Lett., 2013, 15, 1752-1783.

Oxidative addition of In/InCl₃ to enones proceeds exclusively in aqueous media and leads to water-tolerant, ketone-type indium homoenolates. The synthetic utility of the indium homoenolates was demonstrated through the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling with acid chlorides.
Z.-L. Shen, K. K. K. Goh, H.-L. Cheong, C. H. A. Wong, Y.-C. Lai, Y.-S. Yang, T.-P. Loh, J. Am. Chem. Soc., 2010, 132, 15852-15855.

A simple light-driven three-component aryl halide CO insertion, alkene insertion, and protonation process, utilizing Co₂(CO)₈ as an abundant solid carbonyl source, provides 1,4-keto esters and 1,4-diketones in good yields. The products can easily be subjected to further functionalization in synthesis. Mechanism studies indicated that this reaction is initiated by the generation of an aryl radical.
Q. Mou, T. Han, M. Liu, Org. Lett., 2024, 26, 2169-2174.

Iridium photoredox catalysis enables a decarboxylative 1,4-addition of 2-oxo-2-(hetero)arylacetic acids to various Michael acceptors including α,β-unsaturated ester, ketone, amide, aldehyde, nitrile, and sulfone at room temperature. 2-Oxo-2-(hetero)arylacetic acids are easily accessible precursors of acyl anions through photoredox-catalyzed radical decarboxylation.
G.-Z. Wang, R. Shang, W.-M. Cheng, Y. Fu, Org. Lett., 2015, 17, 4830-4833.

A Michael addition type reaction between aroyl chlorides and chalcones was realized in the presence of samarium metal in N,N-dimethylformamide as solvent. Various 1,4-diketones were synthesized in moderate to good yields. A possible mechanism is also discussed.
Y. Liu, Y. Li, Y. Qi, J. Wan, Synthesis, 2010, 4188-4192.

Visible light irradiation promotes the synthesis of α-substituted γ-ketoester derivatives through carbene insertion and the decarbonylation of enaminones and diazoesters. These reactions use readily available starting materials and transition-metal-free, eco-friendly procedures that are amenable to gram-scale synthesis and wide functional group tolerance.
W. Li, Y. Yang, Z. Tang, X. Yu, J. Lin, Y. Jin, J. Org. Chem., 2022, 87, 13352-13362.

The merger of photoredox catalysis and primary amine catalysis enables a direct construction of all-carbon quaternary stereocenters via α-photoalkylation of β-ketocarbonyls with high efficacy and enantioselectivities.
Y. Zhu, L. Zhang, S. Luo, J. Am. Chem. Soc., 2014, 136, 14642-14645.