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Synthesis of α-Bromoketones

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1-Arylethanones and related compounds are rapidly brominated in dioxane with the H2O2-HBr aq system, resulting in the replacement of two hydrogen atoms in the methyl group with bromine. The reaction is also accompanied by bromination of the aromatic ring provided that the latter contains electron-donating substituents.
A. O. Terent'ev, S. V. Khodykin, I. B. Krylov, Y. N. Ogibin, G. I. Nikishin, Synthesis, 2006, 1087-1092.

Utilizing the full potential of IBX, a mild, selective, and facile method enables a direct conversion of olefins into the corresponding α-bromo ketones in the presence of 1.1 equivalents each of o-iodoxybenzoic acid and tetraethylammonium bromide.
S. S. Deshmukh, K. H. Chaudhari, K. G. Akamanchi, Synlett, 2011, 81-83.

HTIB mediates an oxidative transposition of vinyl halides to provide α-halo ketones as useful and polyvalent synthetic precursors. Insights into the mechanism and an enantioselective transformation are reported too.
A. Jobin-Des Lauriers, C. Y. Legault, Org. Lett., 2016, 18, 108-111.

A very rapid and efficient method enables a one-pot synthesis of α,α-dibromoalkanones and β-bromoenol alkanoates directly from alkynes using N,N-dibromo-p-toluenesulfonamide. The protocol offers ambient temperature, high regioselectivity, operational simplicity, and metal- and catalyst-free conditions.
R. Chawla, A. K. Singh, L. D. S. Yadav, Synlett, 2013, 24, 1558-1562.

Efficient oxidative α-halogenation of 1,3-dicarbonyl compounds has been achieved by employing a system comprising of sub-stoichiometric amounts of TiX4 (X = Cl, Br) in the presence of environmentally benign hydrogen peroxide (H2O2) or peracetic acid (MeCO3H) as the oxidants. The end point of the reaction is accompanied by a sharp colour change.
R. Akula, M. J. Galligan, H. Ibrahim, Synthesis, 2011, 347-351.

Active methylene compounds can be chemoselectively brominated in high yields using potassium bromide, hydrochloric acid, and hydrogen peroxide at room temperature.
M. Kirihara, S. Ogawa, T. Noguchi, K. Okubo, Y. Monma, I. Shimizu, R. Shimosaki, A. Hatano, Y. Hirai, Synlett, 2006, 2287-2289.

1,3-keto esters and 1,3-diketones have been effectively and regioselectively α-monobrominated using bromodimethylsulfonium bromide as reagent.
A. T. Khan, M. A. Ali, P. Goswami, L. H. Choudhury, J. Org. Chem., 2006, 71, 8961-8963.

An efficient one-pot transformation of β-hydroxycarbonyl compounds to α-brominated 1,3-dicarbonyl compounds is achieved with MoO2Cl2 in the presence of N-bromosuccinimide. All the reactions were carried out under mild conditions and provide good yields. No bromination occurs at benzylic and allylic positions.
K. Jeyakumar, D. K. Chand, Synthesis, 2009, 306-310.

K. Jeyakumar, D. K. Chand, Synthesis, 2009, 306-310.

A mild and rapid formal electrophilic α-azidation of 1,3-dicarbonyl compounds using commercially available Bu4NN3 as the azide source is mediated by (diacetoxyiodo)benzene. The reaction conditions are Bäcklund to the ones employed in analogous halogenations with Et4NX (X = Cl, Br, I).
M. J. Galligan, R. Akula, H. Ibrahim, Org. Lett., 2014, 16, 600-603.

Poly{[4-(hydroxy)(tosyloxy)iodo]styrene} was efficient in the halotosyloxylation reaction of alkynes with iodine or NBS or NCS. The polymer reagent could be regenerated and reused.
J.-M. Chen, X. Huang, Synthesis, 2004, 1557-1558.


Au-catalyzed hydration of haloalkynes enables an atom-economical synthesis of a wide range of α-halomethyl ketones as an alternative to conventional α-halogenation of ketones. Other outstanding features include excellent yields from both alkyl- and aryl-substituted haloalkynes and wide functional group tolerance.
L. Xie, Y. Wu, W. Yi, L. Zhu, J. Xiang, W. He, J. Org. Chem., 2013, 78, 9190-9191.