Categories: C-C Bond Formation > Oxygen-containing molecules > Carbonyl compounds >
Synthesis of 1,4-diketones
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Recent Literature
A Ru2+-photocatalyzed, visible-light-mediated ATRA reaction of α-bromoketones
with alkyl enol ethers provides 1,4-ketoaldehydes, 1,4-diketones, and
1,4-ketoesters, which are difficult to access. This method enables the
construction of secondary, tertiary, and challenging quaternary centers. A
construction of substituted pyrroles is also described.
W. H. García-Santos, H. B. Mateus-Ruiz, A. Cordero-Vargas,
Org. Lett., 2019, 21, 4092-4096.
Dibrominated 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) is an
organic photocatalyst with similar optoelectronic, electrochemical, and
performance properties to those of Ru(bpy)3Cl2, commonly
used in radical-ionic transformation, such as the formation of 1,4-dicarbonyl
compounds. BODIPY also catalyzes syntheses of γ-alkoxylactones, monoprotected
1,4-ketoaldehydes, and dihydrofurans.
W. H. García-Santos, J. Ordóñez-Hernández, M. Farfán-Paredes,
H. M. Castro-Cruz, N. A. Macías-Ruvalcaba, N. Farfán, A.
Cordero-Vargas, J. Org. Chem., 2021, 86,
16315-16326.
A visible-light-induced radical coupling reaction of silyl enol ethers with
α-bromocarbonyl compounds provides 1,4-dicarbonyls. The reaction was effectively
accelerated using an inexpensive organic dye (eosin Y) as a photoredox catalyst.
N. Esumi, K. Suzuki, Y. Nishimoto, M. Yasuda, Org. Lett.,
2016, 18, 5704-5707.
A silver-catalyzed controlled intermolecular cross-coupling of silyl enolates
displays good functional group tolerance and allows efficient preparation of a
series of synthetically useful 1,4-diketones. Preliminary mechanistic
investigations suggest that the reaction proceeds through a one-electron process
involving free radical species in which PhBr acts as the oxidant.
L. Xu, X. Liu, G. R. Alvey, A. Shatskiy, J.-Q. Liu, M. D. Kärkäs, X.-S. Wang, Org. Lett.,
2022, 24, 4513-4518.
In a Co-catalyzed reaction for the construction of 1,4-dicarbonyls, a cascade
organocobalt addition/trapping/Kornblum-DeLaMare rearrangement were involved.
The reaction offers easy availability of starting materials, wide substrate
scope, high functionality tolerance, and operational simplicity.
F. Zhang, P. Du, J. Chen, H. Wang, Q. Luo, X. Wan, Org. Lett., 2014,
16, 1932-1935.
The perovskite colloid CsPbBr3 can
selectively photocatalyze α-alkylation of aldehydes with a
turnover number (TON) of over 52,000 under visible light illumination.
X. Zhu, Y. Lin, Y. Sun, M. C. Beard, Y. Yan, J. Am. Chem. Soc.,
2019,
141, 733-738.
Singly occupied molecular orbital (SOMO) catalysis allows an enantioselective
organocatalytic α-enolation of aldehydes. A chiral secondary amine catalyst
reacts with aldehydes to form transient enamines that undergo selective
one-electron oxidation to generate SOMO-activated electrophilic radical cations
which are susceptible to attack by ketone-derived enol silanes.
H.-Y. Jang, J.-B. Hong, D. W. C. MacMillan, J. Am. Chem. Soc., 2007,
129, 7004-7005.
A tandem reaction consisting of a Wittig reaction-ring contraction process
between α-hydroxycyclobutanone and phosphonium ylides provides highly
functionalized cyclopropanecarbaldehydes in very good yield.
F. Cuccu, L. Serusi, A. Luridiana, F. Secci, P. Caboni, D. J. Aitken, A.
Frongia,
Org. Lett., 2019, 21, 7755-7758.
CuO catalyzes a three-component reaction of α-ketoaldehydes, 1,3-dicarbonyl
compounds, and organic boronic acids in water to provide a wide range of
products containing 1,3- and 1,4-diketones. The method offers use of readily
available starting materials, wide substrate scope, excellent yields, gram-scale
synthesis, and mild reaction conditions.
Q. Xia, X. Li, X. Fu, Y. Zhou, Y. Peng, J. Wang, G. Song, J. Org. Chem., 2021, 86,
9914-9923.