Dess-Martin periodinane

Description

Dess-Martin periodinane (DMP) is a hypervalent iodine compound widely used as a mild reagent for the oxidation of primary/secondary alcohols to aldehydes/ketones; oxidation of amides into imides; the dehydrogenation of amines to nitriles, and disulfides to sulfones. It is also used to selectively oxidize alkenes to epoxides. This is a useful reaction for generating three-membered cyclic ethers. Additionally, DMP is used to oxidatively cleave 1,2-diols to form aldehydes or ketones and in the synthesis of lactones.

Chemical Properties

White Crystalline powder

Uses

Oxidizing reagent.

Uses

Dess Martin periodinane is used to oxidize 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 the oxidation of N-protected-amino alcohols without epimerization and allylic alcohols.

Uses

Dess-Martin Periodinaneis a very usefulreagent used in the oxidation of primary alcohols to aldehydes and secondary alcohols to ketones.

reaction suitability

reagent type: oxidant

Synthesis

2-Iodobenzoic acid (50.0 g,0.20 mol) was added to cyclobutanesulfone (250 mL), and the solution was heated to 50 C. 90% of the above solution was slowly added dropwise to an aqueous solution of potassium persulfate (147.4g,0.24mol,1.2eq) at 50C (300mL) and the reaction was held for 3 hours. Subsequently, the reaction solution was heated to 95 C and the remaining 10% 2-iodobenzoic acid solution was slowly added dropwise to the reaction solution and the reaction was continued for 3 hours. Upon completion of the reaction, the reaction was cooled to 5 C and stirring was continued at this temperature for 1.5 hours. Under stirring, 1 L of water was added, filtered (the filtrate was to be recycled for set use), the filter cake was washed with water and acetone sequentially, and dried at room temperature for 16 hours to obtain 53.2 g of 2-iodobenzoic acid (yield 95.04%), white solid, with a purity of 99.7% (confirmed by NMR and HPLC). The solid was identified as 2-iodoacylbenzoic acid by HNMR.

2-Iodoacylbenzoic acid (45 g, 0.16 mol) was added to acetic anhydride (49 g, 0.48 mol) and dioxane (90 mL), followed by B(C6F5)3 (0.0016 mol) followed by B(C6F5)3 (0.0016 mol), and the reaction solution was heated to 50 C and stirred for 10 min, then the solvent was evaporated off by spin-drying under reduced pressure, and the reaction solution was added to methyl tert-butyl ether (400 mL). Filtered and dried at room temperature to obtain a white solid (61.1 g, yield: 90%). The purity of Desmartin oxidizer was 99.1% (confirmed by NMR).

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