Tris[trinitratocerium(IV)] Paraperiodate1a,b

[(NO3)3Ce]3H2IO6

[94316-41-3]  · Ce3H2IN9O33  · Tris[trinitratocerium(IV)] Paraperiodate  · (MW 1203.37)

(mild oxidizing reagent for oxidation of several functional groups;2 efficient catalyst for dimerization of thiols and selenols3 and ring opening of epoxides4)

Alternate Name: TTCPP.

Solubility: insol cold H2O, THF, EtOH, acetone.

Form Supplied in: yellow solid, easily prepared.

Preparative Methods: a cold solution of potassium periodate (0.01 mol) in H2O (100 mL) is added dropwise to a solution of Cerium(IV) Ammonium Nitrate (0.03 mol) in H2O (30 mL) cooled in ice-bath. The precipitate is filtered and washed with H2O and acetone, and dried (70%).

Handling, Storage, and Precautions: very air stable and can be stored for months without losing its activity; periodate and cerium are both reputed to have low toxicity.

Introduction.

TTCPP is a convenient reagent for the oxidation of several different functional groups in protic and aprotic solvents under heterogeneous conditions. Separation of the oxidant and isolation of the product are achieved simply by filtration, evaporation, and chromatographic purification. Cerium(IV) reagents usually suffer from disadvantages,1,5,6 but many of these drawbacks are not observed when using TTCPP.2

Oxidations.

Benzylic hydroxyl groups are oxidized to carbonyl compounds in high yields (eq 1) with this reagent.2

a-Hydroxy ketones are oxidized to diketones and decarboxylation occurs with a-hydroxy carboxylic acids to produce aldehydes (eqs 2 and 3).2

Oxidative cleavage of C-C bonds occurs in the reaction of arylethylene glycols (eq 4); TTCPP is also effective for the high-yield oxidation of phosphines (eq 5).2

The reagent has also been employed for the oxidation of thiols to disulfides (eq 6).

Electron-Transfer Reactions.

Catalytic amounts of TTCPP in THF dimerize both thiols and selenols efficiently at room temperature (eq 7).3

Epoxides in different types of alcohols are cleaved by catalytic amounts of TTCPP to afford b-alkoxy alcohols (eq 8).4

Catalytic amounts of TTCPP in acetic acid promote acetolysis of epoxides followed by abstraction of the a-hydrogen adjacent to a carbonyl group to produce b-hydroxyaryl succinates in good yields (eq 9).4

In comparison with the oxidative ability of TTCPP, Cerium(IV) Ammonium Nitrate (CAN) is relatively inactive in benzene. A comparison between TTCPP, CAN,16,7,-10 and zinc bismuthate (ZB)11 is shown in Table 1.


1. (a) Molander, G. A. CRV 1992, 92, 29. (b) Ho, T. L. In Organic Synthesis by Oxidation with Metal Compounds; Mijs, W. J.; De Jonge, C. R. H. I., Eds.; Plenum: New York, 1986, Chap. 11.
2. Firouzabadi, H.; Iranpoor, N.; Hajipoor, G.; Toofan, J. SC 1984, 14, 1033.
3. Iranpoor, N.; Salehi, P.; Shiriny, F. OPP 1995, 27, in press.
4. Iranpoor, N.; Shiriny, F. SC 1994, 24, 1959.
5. Syper, L. TL 1966, 4493.
6. Laing, S. B. JCS(C) 1968, 2915.
7. Ho, T. L. S 1973, 347.
8. Trahanovsky, K.; Young, L. B.; Brown, G. L. JOC 1967, 32, 3865.
9. Iranpoor, N.; Mohammadpour-Baltork, I. T 1991, 47, 9861.
10. Iranpoor, N.; Mohammadpour-Baltork, I. K. SC 1990, 20, 2789.
11. Firouzabadi, H.; Mohammadpour-Baltork, I. BCJ 1992, 65, 1131.

Habib Firouzabadi & Naser Iranpoor

Shiraz University, Iran



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