Dess-Martin periodinane

Dess-Martin periodinane

Dess-Martin periodinane (DMP) is an oxidizing agent used in organic chemistry for the oxidation of primary and secondary alcohols to aldehydes and ketones, respectively, with a notable exception being the oxidation of α,β-unsaturated alcohols to the corresponding enones. It is named after its discoverers, Daniel Benjamin Dess and James Cullen Martin, who first reported its use in 1983. The reagent is advantageous over other oxidizing agents due to its mildness, selectivity, and the fact that it operates under relatively non-harsh conditions.

Chemistry

Dess-Martin periodinane is a stable, crystalline solid that is soluble in organic solvents such as chloroform, dichloromethane, and acetone. The active component of DMP is the iodinane ring, which is responsible for its oxidizing properties. The mechanism of oxidation involves the formation of an alkoxyl-iodinane intermediate, which then undergoes a reductive elimination to form the oxidized product and regenerate the iodinane species.

Applications

Dess-Martin periodinane has found widespread use in the synthesis of complex molecules, including natural products and pharmaceuticals. Its ability to selectively oxidize alcohols without affecting other functional groups makes it a valuable tool in the synthesis of sensitive molecules. Additionally, DMP can be used in the presence of water and under atmospheric conditions, further highlighting its utility in organic synthesis.

Advantages

The main advantages of using Dess-Martin periodinane include:

• High selectivity and efficiency in the oxidation of alcohols to aldehydes and ketones.
• Mild reaction conditions, which are compatible with a wide range of functional groups.
• The production of by-products that are easily separable from the reaction mixture.

Safety and Handling

While Dess-Martin periodinane is considered less hazardous than many other oxidizing agents, it should still be handled with care. Precautions should be taken to avoid inhalation and contact with skin or eyes. It is also important to work in a well-ventilated area and to wear appropriate personal protective equipment.

See Also

• Oxidation reactions
• Organic synthesis
• Alcohol oxidation