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Chemicals >> Oxidizing Agents > Hypervalent Iodine Compounds

Dess-Martin periodinane, DMP

The Dess-Martin periodinane (DMP) is commercially available and decomposes only slowly. But DMP is heat- and shock-sensitive, and shows an exotherm when heated >130 C. 2-Iodoxybenzoic acid (IBX), the impact-sensitive intermediate in the synthesis of the Dess-Martin periodinane, is available in a DMSO solution and is also used as an oxidizing agent.

Name Reactions


Recent Literature

Partial hydrolysis of DMP or incomplete acetylation gives a more effective oxidant, explaining why impure samples of DMP in many cases provide better results than the pure reagent. When reliable and convenient rate enhancement is desired, pure DMP may be decomposed with an equivalent of water immediately before or during its use.
S. D. Meyer, S. L. Schreiber, J. Org. Chem., 1994, 59, 7549-7552.

Alcohols are oxidized to the corresponding carbonyl compounds with iodoxybenzoic acid (IBX) or with Dess-Martin-Periodinane (DMP) in [bmim]BF4 and [bmim]PF6 ionic liquids at room temperature in excellent yields with high selectivity. These oxidations are faster in ionic liquids as compared to conventional solvents. The byproduct iodosobenzoic acid (IBA) and the ionic liquid are readily recovered.
J. S. Yadav, B. V. S. Reddy, A. K. Basak, A. V. Narsaiah, Tetrahedron, 2004, 60, 2131-2135.

A mimic of the Wacker process initiated by a combination of Pd(II) and Dess-Martin periodinane provides methyl ketones from terminal olefins. This operationally simple and scalable method offers Markovnikov selectivity, has good functional group compatibility, and is mild and high yielding.
D. A. Chaudhari, R. A. Fernandes, J. Org. Chem., 2016, 81, 2113-2121.

Versatile trichloromethyl carbinols can be prepared in one pot from primary alcohols by treatment with Dess-Martin periodinane in CHCl3 followed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD).
M. K. Gupta, Z. Li, T. S. Snowden, J. Org. Chem., 2012, 77, 4854-4860.

Among the reported examples of new reactivity of the hypervalent iodine reagent DMP (Dess-Martin periodinane) are the one-step oxidation of secondary amides to imides and N-acyl vinylogous carbamates or ureas and the direct oxidation of benzylic and related primary amines to the corresponding nitriles.
K. C. Nicolaou, C. J. N. Mathison, Angew. Chem. Int. Ed., 2005, 44, 5992-5997.

K. C. Nicolaou, C. J. N. Mathison, Angew. Chem. Int. Ed., 2005, 44, 5992-5997.

K. C. Nicolaou, C. J. N. Mathison, Angew. Chem. Int. Ed., 2005, 44, 5992-5997.

Dess-Martin periodine in combination with organosulfonic acids reacted with ketones and dicarbonyl compounds under reflux temperature in acetonitrile to give α-organosulfonyloxylated compounds in good yields.
U. S. Mahajan, K. G. Akamanchi, Synlett, 2008, 987-990.

o-Iodoxybenzoic acid (IBX) and Dess-Martin periodinane (DMP) mediate the conversion of thiols to thiosulfonates at rt. DMP is better than IBX in terms of reaction rate, conversion, and required equivalents. IBX-mediated oxidation of benzyl thiols produced thiosulfonates, whereas DMP afforded O-benzyl esters.
A. Chandra, N. Yadav, S. Payra, K. N. Parida, Org. Lett., 2023, 25, 6256-6261.

Dess-Martin periodinane (DMP) efficiently mediates the intramolecular cyclization of phenolic azomethines at ambient temperature leading to substituted benzoxazoles and benzothiazoles. Treatment of the reaction mixtures sequentially with Amberlyst A-26 thiosulfate resin and diisopropylaminomethyl resin (PS-DIEA) removes excess reagent and byproducts, to give pure products.
D. S. Bose, M. Idrees, Synthesis, 2010, 398-402.

A new, mild, and efficient method for the synthesis of 2-substituted benzothiazoles proceeds via the intramolecular cyclization of thioformanilides by using hypervalent iodine reagents in CH2Cl2 at ambient temperature.
D. S. Bose, M. Idrees, J. Org. Chem., 2006, 71, 8261-8263.