The Dess–Martin oxidation is an

organic reaction Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, mechanistic organ ...

for the

oxidation Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...

of primary

alcohol Alcohol may refer to: Common uses * Alcohol (chemistry), a class of compounds * Ethanol, one of several alcohols, commonly known as alcohol in everyday life ** Alcohol (drug), intoxicant found in alcoholic beverages ** Alcoholic beverage, an alco ...

s to

aldehyde In organic chemistry, an aldehyde () (lat. ''al''cohol ''dehyd''rogenatum, dehydrogenated alcohol) is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred ...

s and secondary alcohols to

ketone In organic chemistry, a ketone is an organic compound with the structure , where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group (a carbon-oxygen double bond C=O). The simplest ketone is acetone ( ...

s using

Dess–Martin periodinane Dess–Martin periodinane (DMP) is a chemical reagent used in the Dess–Martin oxidation, Alcohol oxidation, oxidizing primary alcohols to aldehydes and secondary Alcohol (chemistry), alcohols to ketones. This periodinane has several advantages o ...

. It is named after the American chemists Daniel Benjamin Dess and

James Cullen Martin James Cullen Martin (January 14, 1928 – April 20, 1999) was an American chemist. Known in the field as "J.C.", he specialized in physical organic chemistry with an emphasis on main group element chemistry. Martin received his undergraduat ...

, who developed the periodinane reagent in 1983. The reaction uses a

hypervalent iodine Unlike its lighter congeners, the halogen iodine forms a number of stable organic compounds, in which iodine exhibits higher formal oxidation states than −1 or coordination number exceeding 1. These are the hypervalent organoiodines, often cal ...

reagent similar to

2-iodoxybenzoic acid 2-Iodoxybenzoic acid (IBX) is an organic compound used in organic synthesis as an oxidizing agent. This periodinane is especially suited to oxidize alcohols to aldehydes. IBX is most often prepared from 2-iodobenzoic acid and a strong oxidant su ...

to selectively and mildly oxidize alcohols to aldehydes or ketones. The reaction is commonly conducted in chlorinated solvents such as

dichloromethane Dichloromethane (DCM, methylene chloride, or methylene bichloride) is an organochlorine compound with the formula . This colorless, volatile liquid with a chloroform-like, sweet odor is widely used as a solvent. Although it is not miscible with ...

chloroform Chloroform, or trichloromethane (often abbreviated as TCM), is an organochloride with the formula and a common solvent. It is a volatile, colorless, sweet-smelling, dense liquid produced on a large scale as a precursor to refrigerants and po ...

. The reaction can be done at room temperature and is quickly complete. Many other functional groups will not be affected by this reaction. Reaction_scheme

The Dess–Martin oxidation may be preferable to other oxidation reactions as it is very mild, avoids the use of toxic

chromium Chromium is a chemical element; it has Symbol (chemistry), symbol Cr and atomic number 24. It is the first element in Group 6 element, group 6. It is a steely-grey, Luster (mineralogy), lustrous, hard, and brittle transition metal. Chromium ...

reagents, does not require large excess or co-oxidants, and has a relatively easy workup. : Dess-Martin oxidation

The reaction produces two equivalents of

acetic acid Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main compone ...

. It can be buffered with

pyridine Pyridine is a basic (chemistry), basic heterocyclic compound, heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom . It is a highly flammable, weak ...

sodium bicarbonate Sodium bicarbonate ( IUPAC name: sodium hydrogencarbonate), commonly known as baking soda or bicarbonate of soda (or simply “bicarb” especially in the UK) is a chemical compound with the formula NaHCO3. It is a salt composed of a sodium cat ...

in order to protect acid-labile compounds. The rate of oxidation can be increased by the addition of water to the reaction mixture.

References

Organic oxidation reactions Name reactions {{DEFAULTSORT:Dess-Martin oxidation