What Is Dess-Martin Oxidation?
The Dess-Martin periodate oxidation reaction refers to the oxidation of primary or secondary alcohols to aldehydes or ketones using the Dess-Martin reagent [DMP, 1,1,1-triacetoxy-1,1-dihydro-1,2-benzidoyl-3-(1H)-one]. Compared with other oxidation methods, this method has the characteristics of short reaction time, mild conditions, and small amount of oxidant.
- Reagents: Dess-Martin periodinane (DMP).
- Reactants: Primary or secondary alcohols.
- Products: Aldehydes or ketones.
- Reaction type: Oxidation reaction.
- Related reactions: Swern oxidation.
Fig 1. Dess-Martin oxidation reaction and its mechanism. [1]
Mechanism of Dess-Martin oxidation
The acetoxy group in the Dess-Martin reagent replaces the alkoxy group of the alcohol, another acetoxy group leaves, and the proton of the carbon atom connected to the alcohol hydroxyl group is transferred to the acetoxy group, and the alcohol is oxidized to the corresponding aldehydes and ketones.
Dess-Martin Reagent
DMP is a mild, environmentally friendly, and highly selective pentavalent iodine oxidant, first reported by Dess and Martin. During the use, chemists found that DMP has better solubility than IBX. It can selectively oxidize primary alcohols or secondary alcohols to aldehydes or ketones in organic solvents such as CH2Cl2. Other sensitive groups such as vinyl and amino groups in the substrate molecules are not affected. Another very useful feature of DMP oxidation is that after the alcohol hydroxyl groups in its oxidized optically active substrates are converted into aldehydes or ketones, it can still maintain very good optical purity.
As chemists studied DMP, they found that in addition to oxidizing alcohols to aldehydes or ketones, it can also complete some other oxidation reactions. In 2002, Nicolaou et al. reported that aniline compounds can be easily oxidized to benzoquinone by DMP in water. They found that this method can be used to conveniently synthesize some complex benzoquinones or polycyclic molecules. At the same time, they successfully used this method to complete the total synthesis of natural products Epoxyquinomycin B and BE-10988.
In 2005, Nicolaou's group reported another important oxidation reaction of DMP, that is, it can obtain imines, N-acylethenic carbamic acids, urea and nitrile compounds by oxidizing amines or amino compounds. This further expands the application of DMP oxidation reaction in synthesis.
Application Examples of Dess-Martin Oxidation
- Example 1: In the total synthesis of hestisine-type C20-diterpenoid alkaloids, the crude reaction mixture (aryl iodide 21) is directly oxidized with Dess-Martin periodinane to obtain diketoaldehyde 10. [2]
- Example 2: In the total synthesis of cefotaxime 1, the gram-scale synthesis of south part included the Baeyer-Villiger oxidation of hecogenin to 16,20-diol, the selective oxidation of the C16 single-bonded OH with Dess-Martin periodinane, the Rh(I)-catalyzed C15 single-bond C16 double bond migration to the C14 single-bond C15 position, and the Hg(OAc)2-mediated formation of a spiroketal from a cyclic enol ether with an olefinic side chain at the 2-position. [3]
Fig 2. Synthetic examples via Dess-Martin oxidation reaction.
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References
- Li, Jie Jack, et al. Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications Sixth Edition, 2021, 157-161.
- Pflueger J J, et al. Organic letters, 2017, 19(17), 4632-4635.
- Shi Y, et al. Tetrahedron, 2019, 75(12), 1722-1738.
