Dess-Martin periodane

Except for the Dess-Martin periodane, which has been widely employed as a selective oxidant in various synthetic protocols (97MI1, 02CRY2523), organoiodine(Y) compounds have received much less attention than their iodine(III) counterparts for organic synthesis. However, recent publications in this area indicate that this is likely to change. 

There are problems associated with the expensive disposal of toxic waste from metal-based oxidations of alcohols. Thus, the focus has been largely on catalytic reactions as typified by Ley and Griffith s tetrapropylammonium perruthenate oxidant (section 7.1.6). Completely metal-free oxidations have much potential for environment-friendly oxidations, particularly if the reagent can be recovered and recycled. The most common metal-free oxidation of alcohols are TEMPO/oxone or TEMPO/N-chlorosuccinimide oxidation, Dess-Martin periodane oxidation (section 7.1.5) and Swern oxidation (section 7.1.4) and its several variants. 

Methyl 3-C-allyl-4,6-0-benzylidene-3-deoxy-a-D-glucopyranoside has been used as a common starting material for preparing annulated sugars involving intramolecular Homer-Wadsworth-Emmons reactions. Thus successive reaction of the allyl derivative with osmium tetroxide, lithium dimethylmethylphosphonate, Dess-Martin periodane then potassium carbonate furnished 51. Whereas successive reaction of the allyl derivative with borane-THF, PCC oxidation, lithium dimethylmethylphosphonate, Dess-Martin periodane then potassium carbonate afforded 52. Analogous chemistry was also performed on methyl 2-C-allyl-4,6-0-benzylidene-2-deoxy-a-D-allopyranoside. ... 

Scheme 7. Synthesis of (—)-3-demethoxytetrahydroeiysotramidine (68) (61) a) toluene/A b) XiCl4 in CH2CI2/—78°C c) i Dess-Martin periodane in CH2CI2 ii Rh(PPh3)2(CO)Cl/ l,3-bis(diphenylphosphino)propane/xylene/A in H2/Pd-C, EtOH...

Dess-Martin periodane oxidation of l,3,5-tri-0-benzoyl-a-i>-ribofuranose affords the corresponding 2-keto derivative which reacts with MeTiCla (formed in situ from titanium tetrachloride and methylmagnesium bromide) to afford the C-2-branched derivative 1 together with the benzoate migration product 2. Perbenzoylation of a mixture of 1 and 2 produced an intermediate useful for making C-2 -methylribonucleosides by way of standard Vorbrugen coupling procedures with a number of nucleobases. ... 

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