Dise-Martin Oxidant (DMP)
Reaction Mechanism Download link: http://chem.kingdraw.cn/Shortlink?id=20221025164829
【English name】 1,1,1-Triacetoxy-1,1-Dihydro-1,2-Benziodoxol-3(1H)-One
【Molecular formula】 C13H13IO8
【Molecular weight】 424.15
【CAS number】 87413-09-0
【Abbreviation and alias】 DMP, TAPI, Dess-Martin periodinane
[Physical Properties] White Crystal, mp 130-133℃. Slightly soluble in CH2Cl2, CHCl3, MeCN and THF, insoluble in aromatic hydrocarbons or aliphatic hydrocarbons and ether solvents, usually used in CH2Cl2.
[Preparation and Commodity] International large reagent companies are sold. Orthoiodobenzoic acid can also be used as a raw material and synthesized through a two-step reaction. Since there is a possibility of explosion during the synthesis, it is best to follow the standard experimental steps reported in recent literature.
[Precautions] It is more sensitive to air and moisture, but the degree of sensitivity will not affect the transfer process of the reagent. Save under low temperature and nitrogen protection and react in a fume hood.
Dys-martin periodoizane (DMP) is one of the most widely used, mild and highly selective oxidants in the organic synthesis of . It is mainly used to oxidize alcohols into corresponding aldehydes and ketones. The widespread use of this reagent is subject to some obstacles, but these obstacles do not come from the properties of the reagent, but because the preparation of reagents is potentially explosive and the cost of commercial reagents.
In the reaction mechanism of the alcohol being oxidized by DMP to carbonyl , the first step is to replace the alkoxy group of the alcohol with one of the acetoxy groups in DMP. When another acetoxy group leaves, the protons on the carbon atom connected to the alcohol hydroxyl group are transferred to the acetoxy group, and the alcohol is oxidized to the corresponding aldehydes and ketones. Therefore, this oxidation process not only completely avoids the occurrence of over-oxidation reactions, but also has a very high chemical selectivity.
DMP has very mild oxidation reaction conditions for alcohol. It is usually added at low temperature and reacted at room temperature. Most reactions are completed within minutes to hours, and the yield is normally maintained at high or very high levels. Since acetic acid and iodine are generated after the oxidation reaction is completed, acetic acid and iodine can be washed and removed by using aqueous solutions of Na2CO3 and Na2S2O3 during post-treatment.
For alcohol compounds with acid-sensitive functional groups, adding an appropriate amount of pyridine to the oxidation reaction of DMP to neutralize the generated acetic acid will significantly increase the yield of the reaction product. Under this condition, acid-sensitive hydroxyl protecting groups, acetal , double bond , alkyne bond and ester functional groups were not affected in any way. In a natural product full synthesis route reported in the literature, the oxidation reaction of DMP to alcohol was applied three times.
Excerpted from: "Modern Organic Synthesis Reagents - Oxidation Reagents", edited by Hu Yuefei.
