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Hypervalent Iodine Compounds

Weaker and longer than covalent linkages, hypervalent bonds are the result of a linear three-center, four-electron (3c-4e) electronic distribution (hypervalent model). Hypervalent iodine reagents are useful synthetic tools due to their low toxicity, ready availability, and ease of handling.

Specific hypervalent iodine reagents: Dess-Martin Periodinane, Iodosobenzene diacetate, Iodosobenzene bis(trifluoroacetate), Iodosylbenzene, 2-Iodoxybenzoic Acid, Iodobenzene Dichloride


Recent Literature


[dibmim][BF4] can be used for the oxidation of alcohols to carbonyl compounds. This oxidizing agent offers a high degree of selectivity for the oxidation of primary alcohols to carbonyl compounds without oxidation to carboxylic acids in ionic liquids. [dibmim][BF4] can be reused after oxidation with peracetic acid.
W. Qian, E. Jin, W. Bao, Y. Zhang, Angew. Chem. Int. Ed., 2005, 44, 952-955.


A highly efficient 2,2,6,6-tetramethylpiperidin-1-yloxy (TEMPO) catalyzed reaction using recyclable 1-chloro-1,2-benziodoxol-3(1H)-one as the terminal oxidant allows the conversion of various alcohols to their corresponding carbonyl compounds in high to excellent yields at room temperature in ethyl acetate, which is an environmentally friendly organic solvent.
X.-Q. Li, C. Zhang, Synthesis, 2009, 1163-1169.


2-Iodoxybenzenesulfonic acid, which can be generated in situ from 2-iodobenzenesulfonic acid sodium salt, is a much more active catalyst than modified IBXs for the oxidation of alcohols with Oxone. Highly efficient and selective methods for the oxidation of alcohols to carbonyl compounds such as aldehydes, carboxylic acids, and ketones were established.
M. Uyanik, M. Akakura, K. Ishihara, J. Am. Chem. Soc., 2009, 131, 251-262.


Stable, microcrystalline 2-iodylphenol ethers were prepared by the dimethyldioxirane oxidation of the corresponding 2-iodophenol ethers. 2-Iodylphenol ethers can selectively oxidize sulfides to sulfoxides and alcohols to the respective aldehydes or ketones.
A. Y. Koposov, R. R. Karimov, I. M. Geraskin, V. N. Nemykin, V. V. Zhdankin, J. Org. Chem., 2006, 71, 8452-8458.


A mild, efficient and environmentally friendly oxidation of sulfides to sulfoxides with a recyclable ion-supported hypervalent iodine reagent tolerates hydroxyl, nitrile, methoxy, carbon-carbon double bonds, and ester functionalities. Aliphatic and aromatic sulfides are selectively oxidized to the corresponding sulfoxides at room temperature in excellent yields without over-oxidation.
W. Qian, L. Pei, Synlett, 2006, 709-712.


Various α-tosyloxyketones were efficiently prepared in high yields from the reaction of ketones with m-chloroperbenzoic acid and p-toluenesulfonic acid in the presence of a catalytic amount of iodobenzene.
Y. Yamamoto, H. Togo, Synlett, 2006, 798-800.


α-Acetoxylation of ketones catalyzed by iodobenzene using acetic anhydride and 30% aqueous hydrogen peroxide as the oxidant is an effective and economical method for the preparation of α-acetoxy ketones in good yields.
J. Sheng, Y. Li, M. Tang, B. Gao, G. Huang, Synthesis, 2007, 1165-1168.


Oxidation of alkyl aryl ketones in the presence of Oxone, trifluoroacetic anhydride and a catalytic amount of iodobenzene affords α-hydroxyalkyl aryl ketones in good yield. This method provides an effective and economical entry for the α-hydroxylation of ketones.
C. Chen, X. Feng, G. Zhang, Q. Zhao, G. Huang, Synthesis, 2008, 3205-3208.


A new and reliable method for the direct construction of biologically important aryl lactones and phthalides from carboxylic and benzoic acids is based on selective benzylic C-H abstraction in the presence of hypervalent iodine(III) reagents and KBr.
T. Dohi, N. Takenaga, A. Goto, A. Maruyama, Y. Kita, Org. Lett., 2007, 9, 3129-3132.


Alkylcarboxamides can be converted to the respective alkylcarbamates by Hofmann rearrangement using hypervalent iodine species generated in situ from PhI and Oxone in methanol. In addition, substituted benzamides can be converted to the respective quinone derivatives by treatment with Oxone and iodobenzene in aqueous acetonitrile.
A. A. Zagulyaeva, C. T. Banek, M. S. Yusubov, V. V. Zhdankin, Org. Lett., 2010, 12, 4644-4647.


Dehydrosulfurization using a hypervalent iodine(III) reagent enables a simple and efficient preparation of symmetrical and unsymmetrical carbodiimides from the corresponding thioureas. The oxidation afforded carbodiimides in excellent yields and high selectivity. A possible mechanism for the transformation is proposed.
C. Zhu, D. Xu, Y. Wei, Synthesis, 2011, 711-714.


Iodobenzene can be used as a recyclable catalyst in combination with m-chloroperbenzoic acid as the terminal oxidant for an efficient and regioselective monobromination of electron-rich aromatic compounds. The bromination of electron-rich aromatic compounds with lithium bromide was fast in tetrahydrofuran at room temperature, providing regioselective monobrominated products in good yields.
Z. Zhou, X. He, Synthesis, 2011, 207-209.


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.


A Rh(II)-catalyzed oxidative coupling of aldehydes and sulfonamides provides N-sulfonylcarboxamides in one step. Various sulfonamides were found to react with aromatic and aliphatic aldehydes to afford the desired products in very good yields.
J. Chan, K. D. Baucom, J. A. Murry, J. Am. Chem. Soc., 2007, 129, 14106-14107.


A desulfurizing difluorination reaction of benzyl sulfides having an electron-withdrawing group such as an ester, a ketone, a nitrile, or an amide in the presence of IF5 gave gem-difluoro compounds in good yield.
T. Fukuhara, S. Hara, Synlett, 2009, 198-200.


Hypervalent Iodine Chemistry