Dess-Martin periodinane

Chembox new
Name = Dess-Martin periodinane
ImageFile = Dess-Martin periodinane.svg
ImageName = Chemical structure of the Dess-Martin periodinane
ImageFile1 = Dess-Martin-periodinane-3D-balls.png ImageName1 = Ball-and-stick model of the Dess-Martin periodinane
IUPACName = 1,1,1-Triacetoxy-1,1-dihydro-
1,2-benziodoxol-3(1H)-one
OtherNames = Dess-Martin periodinane
Section1 = Chembox Identifiers
SMILES = O=C2C1=CC=CC=C1I
(OC(C)=O)(OC(C)=O)
(OC(C)=O)O2
CASNo = 87413-09-0
Section2 = Chembox Properties
Formula = C₁₃H₁₃IO₈
MolarMass = 424.14 g/mol
Appearance = white powder, chips,
crystals or crystalline
powder and/or chunks
Density = 1.362 g/cm³ solid
Solubility =
MeltingPt = 103 - 133 °C
Section7 = Chembox Hazards
ExternalMSDS =
MainHazards =
Section8 = Chembox Related
OtherCpds = 2-Iodoxybenzoic acid

Dess-Martin periodinane is a chemical reagent used to oxidize primary alcohols to aldehydes and secondary alcohols to ketones. [cite journal | author = Dess, D. B.; Martin, J. C. | title = Readily accessible 12-I-5 oxidant for the conversion of primary and secondary alcohols to aldehydes and ketones | journal = J. Org. Chem. | year = 1983 | volume = 48 | pages = 4155 | doi = 10.1021/jo00170a070] [Boeckman, R. J. In "Encyclopedia of Reagents for Organic Synthesis"; Paquette, L. A., Ed.; Wiley: Chichester, UK, 1995, Vol. 7, pp. 4982-4987. (Review)] This periodinane has several advantages over chromium- and DMSO-based oxidants that include milder conditions, shorter reaction times, higher yields, and simplified workups. It is named after the American chemists Daniel Benjamin Dess and James Cullen Martin.

Preparation

2-Iodobenzoic acid is oxidized preferably by Oxone, or by KBrO₃ to 2-iodoxybenzoic acid. (Caution: 2-Iodoxybenzoic acid has been found to be impact and heat sensitive, decomposing explosively.) [OrgSynth |title = The Dess-Martin Periodinane | 1,1,1-Triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one | author = Boeckman, Jr., R. K.; Shao, P.; Mullins, J. J. | collvol = 10 | collvolpages = 696 | year = 2004 | prep = v77p0141] The 2-Iodoxybenzoic acid is then treated with a mixture of acetic anhydride, acetic acid and "p"-toluenesulfonic acid at 80-100 °C for 40 min. The resulted solids can be obtained via filtration and washing with ether.

To avoid the explosive nature of 2-iodoxybenzoic acid, other methods of preparation [cite journal | author = Ireland, R. E.; Liu, L. | title = An improved procedure for the preparation of the Dess-Martin periodinane | journal = J. Org. Chem. | year = 1993 | volume = 58 | pages = 2899 | doi = 10.1021/jo00062a040] [cite journal | author = Meyer, S. D.; Schreiber, S. L. | title = Acceleration of the Dess-Martin Oxidation by Water | journal = J. Org. Chem. | year = 1994 | volume = 59 | pages = 7549 | doi = 10.1021/jo00103a067] as well as other periodinanes [cite journal | author = Dess, D. B.; Martin, J. C. | title = A useful 12-I-5 triacetoxyperiodinane (the Dess-Martin periodinane) for the selective oxidation of primary or secondary alcohols and a variety of related 12-I-5 species | journal = J. Am. Chem. Soc. | year = 1991 | volume = 113 | pages = 7277 | doi = 10.1021/ja00019a027] have been described.

Properties and uses

Dess-Martin periodinane is mainly used as an oxidant for complex, sensitive and multifunctional alcohols. One of the reasons for its effectiveness is its high selectivity towards complexation of the hydroxylic group, which allows alcohols to rapidly perform ligand exchange; the first step in the oxidation reaction.

Its effectiveness as an oxidant is also due to its versatility; having a broad scope of being able to convert alcohols to carbonyl derivatives. Its reactions and yield are also known to be clean and high respectively. Work up is also clean and simple. Byproducts from the reaction can be removed easily by precipitation, filtration or chromatography.

References

ee also

* Pyridinium chlorochromate