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Categories: C-C Bond Formation > Heteroatom-containing Molecules > Trihalomethyl Ketones, Trifluoromethylation

Synthesis of α-trifluoromethyl carbonyl compounds

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An organocatalytic α-trifluoromethylation and α-perfluoroalkylation of aldehydes with commercially available perfluoroalkyl halides in the presence of a readily available iridium photocatalyst and a chiral imidazolidinone catalyst delivers products with high efficiency and enantioselectivity. α-Trifluoromethyl aldehydes are versatile precursors for the construction of enantioenriched trifluoromethylated building blocks.
D. A. Nagib, M. E. Scott, D. W. C. MacMillan, J. Am. Chem. Soc., 2009, 131, 10875-10877.


A Cu-catalyzed trifluoromethylation of silyl enol ethers with Togni's reagent as electrophilic trifluoromethylating agent produces α-trifluoromethyl ketones in good yields.
L. Li, Q.-Y. Chen, Y. Guo, J. Org. Chem., 2014, 79, 5145-5152.


In a continuous-flow, two-step procedure for the preparation of α-CF3-substituted carbonyl compounds, carbonyl substrates were converted in situ into the corresponding silyl enol ethers, mixed with a CF3 radical source, and then irradiated with visible light using transparent tubing and a household compact fluorescent lamp. The continuous protocol uses Eosin Y as an inexpensive photoredox catalyst and requires only 20 min for both steps.
D. Cantillo, O. D. Frutos, J. A. Rincón, C. Mateos, C. O. Kappe, Org. Lett., 2014, 16, 876-879.


The use of 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine achieves a salt-free stereoselective synthesis of silyl enol ethers from α-halo carbonyl compounds. In this reaction, easily removable tetramethylpyrazine and trimethylsilyl halides were generated as byproducts. The inertness of the reaction byproducts enables one-pot transformations of the in situ generated silyl enol ethers into various α-functionalized carbonyls.
S. Pramanik, S. Rej, S. Kando, H. Tsurugi, K. Mashima, J. Org. Chem., 2018, 83, 2395-2401.


An electrochemical synthesis of fluorinated ketones from enol acetates and RfSO2Na in an undivided cell under constant current conditions proceeds via perfluoroalkyl radical generation from sodium perfluoroalkyl sulfinate followed by addition to the enol acetate and transformation of the resulting C radical to a fluorinated ketone.
V. A. Vil', V. M. Merkulova, A. I. Ilovaisky, S. A. Paveliev, G. I. Nikishin, A. O. Terent'ev, Org. Lett., 2021, 23, 5107-5112.


An anthraquinone-catalyzed photooxidative keto-trifluoromethylation of styrenes with the readily available Langlois reagent (CF3SO2Na) under an oxygen atmosphere proceeds smoothly to give α-trifluoromethyl ketones in good yield with good selectivity.
E. Yamaguchi, Y. Kamito, K. Matsuo, J. Ishihara, A. Itoh, Synthesis, 2018, 50, 3161-3168.


Photoredox catalysis enables a direct oxidative addition of CF3 and H2O to alkynes to provide α-trifluoromethyl ketones via rapid enol-keto tautomerization. The reaction exhibits high functional group tolerance and regioselectivity. In addition, trifluoromethylated heterocycles of various sizes were synthesized from α-CF3-substituted diketones.
Y. R. Malpani, B. K. Biswas, H. S. Han, Y.-S. Jung, S. B. Han, Org. Lett., 2018, 20, 1693-1697.

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A regioselective gold-catalyzed hydration of CF3- and SF5-alkynes provides the corresponding trifluoromethylated and pentasulfanylated ketones in good yield as single regioisomers. CF3 and SF5 serve as highly efficient directing groups.
M. Cloutier, M. Roudias, J.-F. Paquin, Org. Lett., 2019, 21, 3866-3870.


A nickel-catalyzed asymmetric reductive cross-coupling trifluoroalkylation of acyl chlorides enables an enantioselective synthesis α-trifluoromethylated ketones. A one-pot reduction furnished alcohols bearing β-CF3-substituted stereogenic carbons with excellent diastereoselectivity. The reactions offer high yields/enantioselectivity, mild conditions, and good functional group compatibility.
B.-B. Wu, J. Xu, K.-J. Bian, Q. Gao, X.-S. Wang, J. Am. Chem. Soc., 2022, 144, 6543-6550.


A nickel-catalyzed reductive cross-coupling reaction of acyl chlorides with racemic secondary α-trifluoromethyl bromides provides structurally interesting chiral α-CF3 carbonyl compounds with great enantioselectivity and good functional group tolerance.
J. Wu, H. Wu, X. Liu, Y. Zhang, G. Huang, C. Zhang, Org. Lett., 2022, 24, 4322-4327.


N-Heterocyclic Carbene Catalyzed Highly Chemoselective Intermolecular Crossed Acyloin Condensation of Aromatic Aldehydes with Trifluoroacetaldehyde Ethyl Hemiacetal
B. T. Ramanjaneyulu, S. Mahesh, R. V. Anand, Org. Lett., 2015, 17, 6-9.