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Synthesis of α-iodoketones

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Under neutral reaction conditions, aromatic ketones were transformed into the corresponding α-iodo ketones in high yields by the combination of copper(II) oxide and iodine. Copper(II) oxide acts as catalyst to convert iodine into the reactive iodonium ion and as a base to neutralize hydrogen iodide, and reoxidizes iodide into molecular iodine.
G. Yin, M. Gao, N. She, S. Hu, A. Wu, Y. Pan, Synthesis, 2007, 3113-3116.

Selective introduction of an iodine atom at the α-carbonyl position in various aryl alkyl ketones was effectively achieved by reaction of target molecules with elemental iodine in the presence of N-F reagents such as F-TEDA-BF4 (Selectfluor) as iodination mediators and methanol as the solvent.
M. Jereb, S. Stavber, M. Zupan, Synthesis, 2003, 853-858.

A direct asymmetric iodination reaction of aldehydes with NIS catalyzed by a novel axially chiral bifunctional amino alcohol represents a rare example of a highly enantioselective synthesis of optically active α-iodoaldehydes.
T. Kano, M. Ueda, K. Maruoka, J. Am. Chem. Soc., 2008, 130, 3728-3729.

By utilizing N-heterocyclic carbenes as stabilizer through electrostatic interaction rather than electron donation, a visible-light-triggered radical-radical cross-coupling of N-alkenoxypyridinium salts and NaI provides a variety of α-iodo ketones.
H. Sheng, Q. Liu, X.-D. Su, Y. Lu, Z.-X. Wang, X.-Y. Chen, Org. Lett., 2020, 22, 7187-7192.

An efficient approach to α,β-unsaturated α′-iodo ketones directly from α,β-unsaturated ketones by selective iodination at the α′-position in the presence of copper(II) oxide/iodine offers high yields, short reaction times, inexpensive reagents, mild reaction conditions, ease of manipulation, and the formation of cleaner products.
Z. Wang, G. Yin, J. Qin, M. Gao, L. Cao, A. Wu, Synthesis, 2008, 3565-3568.

Primary, secondary, tertiary, benzylic, propargylic and α-functionalized alkyl fluorides react in chlorinated or aromatic solvents at room temperature or upon heating with inexpensive lithium iodide to give the corresponding iodides in very good yields. The reaction is selective for aliphatic monofluorides and can be coupled with in situ nucleophilic iodide replacements.
K. Balaraman, S. Kyriazakos, R. Palmer, F. Y. Thanzeel, C. Wolf, Synthesis, 2022, 54, 4320-4328.

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.


Sodium benzene sulfinate catalyzed a visible-light-driven aerobic oxidative cleavage of olefins to provide the corresponding aldehydes and ketones under transition-metal-free conditions. Notably, α-halo-substituted styrenes proceeded with photoinduced oxidation to finally afford α-halo-acetophenones with halogen migration.
Y.-X. Chen, J.-T. He, M.-C. Wu, Z.-L. Liu, K. Tang, P.-J. Xia, K. Chen, H.-Y. Xiang, X.-Q. Chen, H. Yang, Org. Lett., 2022, 24, 3920-3925.