(an oxidizing reagent commonly used for the cleavage of 1,2-diols and the oxidation of sulfides to sulfoxides or sulfones)
Alternate Name: polymer-supported ammonium metaperiodate, polymer-supported quaternary ammonium periodate, polymer-supported quaternary ammonium metaperiodate.
Form Supplied in: commercially available as (polystyrylmethyl)trimethylammonium metaperiodate [polymer matrix is copoly(styrenedivinylbenzene) 20-50 mesh].
Purification: the polymer is washed with an appropriate solvent and dried in vacuo.
Handling, Storage, and Precautions: keep cool and dry, store under argon. Prolonged storage at <-18°C.
Sodium and potassium periodates are frequently used to oxidize a variety of functional groups. However, due to the poor solubility of these salts, reactions are generally performed in protic media. In contrast, polymer-supported ammonium periodates can be used in a variety of solvents, including aprotic solvents, with the additional practical advantage that work-up is a simple filtration.
Harrison et al. demonstrated that polymer-supported ammonium periodate prepared from Amberlite IRA 904 or Amberlyst A26 cleaved 1,2-diols in high yield in a variety of solvents.1 For the cleavage of cyclohexane-1,2-diol in dichloromethane (
The synthesis of a series of trihydroxy nucleosides, using polymer-supported ammonium periodate prepared from Amberlyst A27 (chloride form), represents the first example of the concomitant use of two antagonistic reagents (
A solution of the diol was pumped through a column containing a mixture of the periodate and borohydride resins, which brought about the cleavage and in situ reduction of the unstable dialdehyde as soon as it formed.
A mixture of the polymer-supported ammonium periodate and borohydride reagents has also been used for the reduction of other diols to primary alcohols (
The oxidation of benzylic alcohols to carbonyl compounds has been achieved with clay (K10-montmorillonite)-supported tetrabutylammonium periodate (TBAPI) (
Interestingly, the addition of Lewis acid catalysts is not required, unlike solution-phase tetrabutylammonium periodate which alone is incapable of achieving these oxidations in aprotic solvents.
A number of quinols (
Polymer-supported ammonium periodate has been used for the oxidation of sulfides to sulfoxides, for example, the oxidation of methylpenicillin V was efficiently achieved in 89% using a periodate reagent prepared from Amberlyst A26 (
Similarly, a variety of aromatic and aliphatic sulfides were oxidized by periodate supported on strong anion exchange resin Amberlite IRA-400.5
Clay (K10-montmorillonite)-supported tetrabutylammonium periodate is a mild reagent for the facile oxidation of sulfides to sulfoxides in water.4 The oxidation is faster and more efficient than its periodate or tetrabutyl ammonium periodate/aluminum trichloride solution-phase counterparts.
The versatility of the polymer-supported periodate has been demonstrated by the oxidation of a-haloketones to acids (
Salunkhe et al. have used a polymer-supported periodate generated from Amberlyst A26 to oxidize hydrazides to 1,2-diacyl hydrazines (
In addition, triphenylphosphine, hydrazobenzene, and benzohydroxamic acid are oxidized to triphenyl phosphine oxide, azobenzene, and nitrosocarbonylbenzene, respectively, using a supported ammonium periodate prepared from Amberlyst A26.1
tetrabutylammonium periodate has been immobilized on montmorillonite clay; sodium periodate has also been immobilized on a variety of mineral supports, such as alumina, clay, and silica.8
University of Cambridge, Cambridge, UK