Categories: C-C Bond Formation > Oxygen-containing molecules > Carbonyl compounds >
Synthesis of 1,3-diketones
Related: |
Name Reactions
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.
Related
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.