Dess–Martin Oxidation refers to the oxidation of alcohols to the corresponding carbonyl compounds using Dess–Martin periodinane (DMP). The reaction is named after American chemists Daniel Benjamin Dess and James Cullen Martin.

Dess–Martin periodinane (DMP), full name: 1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one, was developed in 1983 by the aforementioned chemists. The Dess–Martin oxidation can proceed at room temperature and is known for its excellent functional group selectivity and environmentally friendly conditions.

• Reagent: Dess–Martin periodinane (DMP)

• Reactant: Alcohol

• Products: Aldehyde, Ketone

• Reaction Type: Oxidation reaction

Experimental Tips:

• Preparation of DMP: DMP is synthesized by first oxidizing 2-iodobenzoic acid to IBX (o-iodoxybenzoic acid), which is then acetylated.

• Both DMP and IBX are potentially explosive, and appropriate safety precautions must be taken during handling and reactions.

• The reaction generates 2 equivalents of acetic acid; if the product or reaction system is acid-sensitive, it’s advisable to use a buffer or mild base such as pyridine or sodium bicarbonate.

• Benzylic and allylic alcohols generally react faster than saturated alcohols [1]. DMP also oxidizes aldoximes and ketoximes to aldehydes and ketones more rapidly than it does primary, secondary, or benzylic alcohols [2].

Reaction Mechanism:

Mechanism of the Dess–Martin Oxidation Reaction

Original Publication:

• Dess, Daniel B.; Martin, James Cullen. J. Org. Chem., 1983, 48 (22), 4155–4156.

Key References:

• Synthesis of Imides, N-Acyl Vinylogous Carbamates and Ureas, and Nitriles by Oxidation of Amides and Amines with Dess–Martin Periodinane, Angew. Chemie, 2005, 44 (37), 5992–5997.

• A Mild, Chemoselective Protocol for the Removal of Thioketals and Thioacetals Mediated by Dess–Martin Periodinane, Org. Lett., 2003, 5 (4), 575–578.

Additional References:

• Dess, D. B.; Martin, J. C.; Angew. Chem. Int. Ed., 1991, 113 (19), 7277–7287.

• Chaudhari, S.S.; Akamanchi, K.G.; Synthesis, 1999 (5), 760–764.