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