Polymer-Supported Ammonium Periodate

(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.

Introduction

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.

Oxidative Cleavage of 1,2-Diols

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 (eq 1), it was observed that trace amounts of water accelerated the reaction, possibly by creating a favorable microenvironment in the resin.

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 (eq 2).3

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 (eq 3).3

Oxidation of Alcohols to Carbonyls

The oxidation of benzylic alcohols to carbonyl compounds has been achieved with clay (K10-montmorillonite)-supported tetrabutylammonium periodate (TBAPI) (eq 4).4 A series of primary and secondary alcohols were oxidized to the corresponding aldehydes or ketones with reasonable yields.

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.

Oxidation of Quinols

A number of quinols (eq 5) and catechols (eq 6) have been oxidized using supported periodate, prepared from Amberlite IRA 904 (chloride form), to give quinones in good yield.1

Oxidation of Sulfides to Sulfoxides

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 (eq 7).1

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.

Miscellaneous Reactions

The versatility of the polymer-supported periodate has been demonstrated by the oxidation of a-haloketones to acids (eq 8) and the oxidative decarboxylation of arylacetic acids and a-hydroxy acids to carbonyl compounds (eq 9 and 10).6 The reactions were performed in ethanol using the periodate form of IRA-400.

Salunkhe et al. have used a polymer-supported periodate generated from Amberlyst A26 to oxidize hydrazides to 1,2-diacyl hydrazines (eq 11).7 It was found that the resin could be used repeatedly, as it was regenerated to its initial activity by treatment with dilute hydrochloric acid.

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

Related Reagents.

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


1. Harrison, C. R.; Hodge, P., J. Chem. Soc., Perkin Trans 1 1982, 509.
2. Bessodes, M.; Antnakis, K., Tetrahedron Lett. 1985, 26, 1305.
3. Hebert, N.; Beck, A.; Lennox, R. B.; Just, G., J. Org. Chem. 1992, 57, 1777.
4. Venkatachalapathy, C.; Rajarajan, M.; Banu, H. S.; Pitchumani, K. Tetrahedron 1999, 55, 4071.
5. Karalkar, N. B.; Salunkhe, M. M.; Talekar, K. P.; Maldar, N. N., Ind. J. Chem., Sect B: Org. Chem. Incl. Med. Chem. 1998, 37, 1184.
6. Kanade, A. S.; Mane, R. B.; Salunkhe, M. M., Ind. J. Chem., Sect B: Org. Chem. Incl. Med. Chem. 1991, 30, 984.
7. Salunkhe, D. G.; Jagdale, M. H.; Swami, S. S.; Salunkhe, M. M., Curr. Sci. 1986, 55, 922.
8. (a) Lui, K. T.; Tong, Y. C., J. Org. Chem. 1978, 43, 2717. (b) Gupta, D. N.; Hodge, P.; Davies, J. E., J. Chem. Soc., Perkin Trans. 1 1981, 2970. (c) Zhong, Y. L.; Shing, T. K. M., J. Org. Chem. 1997, 62, 2622. (d) Varma, R. S.; Saini, R. K.; Meshram, H. M., Tetrahedron Lett. 1997, 38, 6525. (e) Varma, R. S.; Dahiya, R.; Saini, R. K., Tetrahedron Lett. 1997, 38, 8819. (f) Painter, G. F.; Falshaw, A., J. Chem. Soc., Perkin Trans. 1. 2000, 1157.

Steven V. Ley & Andrew J. Hazelwood

University of Cambridge, Cambridge, UK



Copyright 1995-2000 by John Wiley & Sons, Ltd. All rights reserved.