Dess-Martin periodinane

Description

Dess-Martin Periodinane (DMP) is a versatile hypervalent iodine compound renowned for its mild oxidation capabilities, making it a preferred choice for converting primary and secondary alcohols into aldehydes and ketones, amides into imides, and amines into nitriles. It also facilitates the dehydrogenation of disulfides to sulfones and selectively oxidizes alkenes to form epoxides, a reaction pivotal for creating three-membered cyclic ethers. Furthermore, DMP is instrumental in the oxidative cleavage of 1,2-diols to yield aldehydes or ketones and is utilized in lactone synthesis. As an acylated variant of the oxidizing agent IBX, DMP boasts enhanced solubility in organic solvents due to its acyl groups. Its mild nature allows for use under neutral conditions, ensuring high selectivity and compatibility with various functional groups. DMP is also favored for its lower toxicity compared to chromium-based reagents and its relatively straightforward work-up process. However, it does come with certain drawbacks, such as its potential for explosive reactions and a higher cost. Additionally, due to its high molecular weight, larger quantities of DMP may be required for reactions, which can be a consideration in its practical application.

Chemical properties

White Crystalline powder

The Uses of Dess-Martin periodinane

Dess-Martin periodinane solution is a widely employed reagent for the mild oxidation of alcohols to aldehydes and ketones. Dess Martin periodinane oxidises primary alcohols to aldehydes and secondary alcohols to ketones. It is also used as an oxidant for complexes with multifunctional alcohols. It is actively involved in oxidising N-protected amino alcohols without epimerization and allylic alcohols.

Reaction profile

Dess–Martin Periodinane (DMP) is routinely used to oxidize alcohols to aldehydes and ketones. Albeit to a lesser extent, DMP has also been used in other synthetically oxidative transformations, such as oxidative cascade cyclisation of anilines with double bonds, synthesis of benzothiazole via oxidative cyclisation of thioformanilides, synthesis of 2-amino-1,4-benzoquinone-4-phenylimides from anilines, α-organosulfonyloxylation of ketones using DMP and organosulfonic acid, oxidative allylation of Morita–Baylis–Hillman adducts with allyltrimethylsilane promoted by DMP/BF3·OEt2, oxidation of amides and amines, oxidation of 2-pyridylseleno to form terminal alkenes, one-pot synthesis of trichloromethyl carbinols from primary alcohols, oxidation of terminal olefins to methyl ketones, oxidative rearrangement for the preparation of α-keto thioesters, and synthesis of thiazole-5-carbaldehyde via oxidative cascade annulation of potassium thiocyanate and tertiary enaminones.

Advantages

Benefits of using Dess-Martin periodinane (DMP) as an oxidizing reagent:
milder reaction conditions (room temperature, neutral pH)
shorter reaction times and higher yields
high chemoselectivity
tolerance of sensitive functional groups, and a long shelf life
simplified workups