Martin Periodinane Oxidation

Oxidation of alcohols to the corresponding carbonyl compounds using triace-toxyperiodinane. The Dess-Martin periodinane, l,l,l-triacetoxy-l,l-dihydro-l,2-benziodoxol-3(l//)-one, is one of the most useful oxidant for the conversion of primary and secondary alcohols to their corresponding aldehyde or ketone products, respectively. 

Preparation, The oxone preparation is much safer and easier than KB1O3. The IBX intermediate that eomes out of it has proven to be far less explosive  

However, The Dess-Martin periodinane is hydrolyzed by moisture to o-iodoxybenzoic acid (IBX), which is a more powerful oxidating agent  

Name Reactions, 4Ui ed., DOI 10.1007/978-3-642-01053-8 78, Springer-Verlag Berlin Heidelberg 2009 

Example 2, An atypieal Dess-Martin periodinane reaetivity  

Name Reactions A Collection of Detailed Mechanisms and Synthetic Applications DOI 10.1007/978-3-319-03979-4 86, Springer International Publishing Switzerland 2014 

Example 2, An atypical Dess-Martin periodinane reactivity 

Oxidation of alcohols to the corresponding carbonyl compounds using triace-toxyperiodinane. 

The Dieckmann condensation is the intramolecular version of the Claisen condensation. 

The Diels-Alder reaction, reverse electronic demand Diels-Alder reaction, as well as the hetero-Diels-Alder reaction, belong to the category of [4 2]-cycloaddition reactions, which are concerted processes. The arrow-pushing here is merely illustrative. 

EDG = electron-donating group EWG = electron-withdrawing group 

Inverse electronic demand Diels-Alder reaction EWG 

The search for mild oxidizing reagents that convert alcohols to aldehydes or ketones under neutral or near neutral conditions has produced a new type of reagent that contains a hypervalent iodine. Dess and Martin showed that 2-iodobenzoic acid (75) reacted with KBrOs in sulfuric acid to give a 93% yield of 76. Subsequent heating (100°C) with acetic anhydride and acetic acid produced 77 in 93% yield, the so-called Dess-Martin periodinane. This reagent converted alcohols to ketones or aldehydes, illustrated by the transformation of cyclohexanol to cyclohexanone in 90% yield, in dichloromethane at 25°C. In this particular 

The Dess-Martin reagent can be shock sensitive under some conditions and it explodes above 200°C. An improved procedure for its preparation is available.  

There are many synthetic applications in the recent literature. The most common application is the oxidation of primary alcohols where the substrate can tolerate only a narrow range of reaction conditions or is part of a highly functionalized molecule. 26 Secondary alcohols can also be oxidized under very mild conditions. A synthetic example is taken from Tadano s synthesis of (-)-mniopetal E, 27 in which the primary alcohol unit in 79 was oxidized to the aldehyde unit in 80. 

Diels-Alder reaction, inverse electronic demand Diels-Alder reaction, hetero-Diels-Alder reaction 

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Martin, J. C. Arhart, R. J. J. Am. Chem. Soc. 1971, 93, 2339, 2341. J. C. Martin was a professor at the University of Illinois at Urbana, where he discovered the Martin s snl-furane dehydrating reagent. Martin also developed the Dess-Martin periodinane oxidation (page 195) with his student Daniele Dess. 

Dess-Martin Periodinane Oxidation General Procedure 15 160... 

Dess-Martin periodinane oxidizes lactols to lactones.41 In molecules containing both an alcohol and a lactol, sometimes it is possible to perform a selective oxidation of the alcohol in the presence of a lactol.13 Although, a case is known in which this selectivity is reversed and a lactol is oxidized to the corresponding lactone, while an alcohol in the same molecule remains unaffected.42... 

The Dess-Martin periodinane oxidation of alcohols can be carried out in the presence of free phenols 43... 

Dess-Martin periodinane oxidizes the alcohol without affecting the primary aliphatic amine, which reacts in situ with the intermediate aldehyde, resulting in the formation of a new... 

Steo 1 Dess-Martin periodinane oxidation. Step 2 Reductive amination. 

Corey and Roberts reported a total synthesis of the dysidiolide 46, a marine sponge metabolite with biological activities against A-549 human lung carcinoma and P388 murine leukemia cancer cell lines20 (Scheme 4.3p). The unwanted alcohol (47) was converted to the ketone 48 via Dess-Martin periodinane oxidation. The asymmetric reduction of 48 with the CBS catalyst 28b efficiently gave the alcohol 49, which was transformed into the dysidiolide 46 via photochemical oxidation. 

The Dess-Martin periodinane oxidation of diol 150 and subsequent thermal equilibration at 45 °C gives the dihydrooxocine 151 in 92% yield (Scheme 39) <20020L3891>. 

Diarylisoxazoles were easily halogenated at the C-4 position with -halosuccinimides in acetic acid (37-97% yields) <03S1586>. The Dess-Martin periodinane oxidation of a-, P-, and y-hydroxy isoxazoles into the corresponding ketones 34 was easily performed in good to excellent yields <03SL2213>. 

Another modification of the Dess-Martin periodinane oxidation is the use of ionic liquids such as hydrophilic [bmim]BF4 and hydrophobic [bmim]BF6 to increase the rate of reaction." These solvents are more environmentally friendly than conventional organic solvents and avoid the use of high boiling polar organic solvents such as DMSO or DMF. 

The Dess-Martin periodinane oxidation is the method of choice for complex molecular systems. For example, during the total synthesis of the antitumor agent OSW-1, it was observed that oxidation of the alcohol (42) provided the aldehyde in 86% yield. Under Swem conditions, the aldehyde (43) was obtained in an inseparable mixture with another epimer.16... 

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