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Synthesis of 1,3-diketones


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Baker-Venkataraman Rearrangement

Recent Literature

2,2,2-Trifluoroethyl formate reacts rapidly at -78 °C with preformed ketone enolates to give α-formyl ketones in good yields with complete reversal of the regioselectivity of the classical Claisen reaction. The method also enables an α'-formylation of α,β-unsaturated ketones.
G. H. Zayia, Org. Lett., 1999, 1, 989-991.

Ketones and thioesters undergo soft enolization and acylation with crude acid chlorides to provide 1,3-diketones and β-keto thioesters, respectively. The use of crude acid chlorides adds efficiency and cost reduction by avoiding the need to purify and/or purchase them. The process is conducted in a direct fashion in the presence of MgBr2ˇOEt2 and i-Pr2NEt without prior enolate formation.
S. O. Aderibigbe, D. M. Coltart, J. Org. Chem., 2019, 84, 9770-9777.

Ketones undergo soft enolate formation and acylation on treatment with MgBr2ˇOEt2, i-Pr2NEt, and various acylating agents to give 1,3-diketones. A particularly simple and efficient acylation with N-acylbenzotriazoles and O-Pfp esters can be conducted in untreated, reagent-grade CH2Cl2 open to the air.
D. Lim, F. Fang, G. Zhou, D. M. Coltart, Org. Lett., 2007, 9, 4139-4142.

A broad range of aryl and alkyl-substituted tertiary amides react with ketones in the presence of LiHMDS to give the corresponding 1,3-diketone products in very good yields at room temperature under transition-metal-free conditions. N-Tosyl-, N-triflyl-, N-mesyl-, and N-Boc-substituted tertiary amides showed good activity. The reaction offers good functional group tolerance and scalability.
J. Chen, Y. Xia, S. Lee, Org. Chem. Front., 2020, 7, 2931-2937.

1-Acylbenzotriazoles are efficient C-acylation reagents for the regioselective conversion of ketone enolates into β-diketones.
A. R. Katritzky, A. Pastor, J. Org. Chem., 2000, 65, 3679-3682.

Mild and Efficient Pentafluorophenylammonium Triflate (PFPAT)-Catalyzed C-Acylations of Enol Silyl Ethers or Ketene Silyl (Thio)Acetals with Acid Chlorides
A. Iida, J. Osada, R. Nagase, T. Misaki, Y. Tanabe, Org. Lett., 2007, 9, 1859-1862.

Treatment of an γ-acyloxy-α,β-unsaturated ketone with bis(iodozincio)methane leads to a novel tandem reaction consisting of three steps: 1,4-addition of the dizinc reagent to the enone, intramolecular nucleophilic attack by the enolate on the ester group, and Grob-type fragmentation of the adduct to give 1,3-diketones efficiently.
M. Sada, S. Matsubara, J. Am. Chem. Soc., 2010, 132, 432-433.

Substituted 1,3-diketones were synthesized from α,β-unsaturated ketones by treatment with acid chlorides and Et2Zn in the presence of RhCl(PPh3)3. The reaction offers a very simple and chemoselective acylation at the α-position of α,β-unsaturated ketones.
K. Sato, S. Yamazoe, R. Yamamoto, S. Ohata, A. Tarui, M. Omote, I. Kumadaki, A. Ando, Org. Lett., 2008, 10, 2405-2408.

A tandem addition of two molecules of zinc alkanoate to a carbonyl compound gives a series of δ-hydroxy-β-ketoesters. The key to accelerate such a double Reformatsky reaction is considered to be a complex-induced proximity effect of the in situ generated zinc alkoxide coordinated with a bidentate amine. A feature of the reaction system is its high tolerance of functional groups due to the moderate nucleophilicity of organozinc reagents.
M. Mineno, Y. Sawai, H. Kanno, N. Sawada, H. Mizufune J. Org. Chem., 2013, 78, 5843-5850.

A recyclable, convenient, and efficient catalytic system allows the C-acylation of 1,3-dicarbonyl compounds and malononitrile with acid chlorides in moderate to excellent yields under mild conditions.
Q. Shen, W. Huang, J. Wang, X. Zhou, Org. Lett., 2007, 9, 4491-4494.

A convenient two-step preparation of alkylidenepyrrolidines is reported.
M. C. Elliot, S. V. Wordingham, Synthesis, 2006, 1162-1170.

Various 1,3,5-tricarbonyl derivatives were prepared by a mild reaction of 1,3-bis(silyl enol ethers) with acid chlorides. Reactions of both aromatic and aliphatic acid chlorides and bis(acid chlorides) were conducted.
T. Rahn, V. T. H. Nguyen, T. H. T. Dang, Z. Ahmed, K. Methling, M. Lalk, C. Fischer, A. Spannenberg, P. Langer, J. Org. Chem., 2007, 72, 1957-1961.


A short, mild, and highly chemoselective addition of organolithium reagents to BF2 complexes of 3-oxopropanoates allows a straightforward preparation 1,3-diketones.
B. Štefane, Org. Lett., 2010, 12, 2900-2903.

An oxidative coupling method for alkyne difunctionalization under metal-catalyst-free conditions affords various β-ketodithianes in very good yields with high regioselectivities. The reaction provides valuable dithianes with controlled formation of a new C-C bond and a C-O bond via a radical coupling pathway.
J. Lai, L. Tian, X. Huo, Y. Zhang, X. Xie, S. Tang, J. Org. Chem., 2015, 80, 5894-5899.