T-BuOOH

The standard Sharpless reagent [Ti(OPr-i)4/(R, R)-diethyl tartrate (DET)/t-BuOOH] oxidizes methyl p-tolyl sulphide into a mixture of racemic sulphoxide and sulphone286. 

This mechanism is the same as that of 19-23 the products differ only because tertiary amine oxides cannot be further oxidized. The mechanism with other peroxyacids is probably the same. Racemic (3-hydroxy tertiary amines have been resolved by oxidizing them with t-BuOOH and a chiral catalyst one enantiomer reacts faster than the other.This kinetic resolution gives products with enantiomeric excesses of > 90%. 

Sharpless epoxidation involves treating an allylic alcohol with titanium(IV) tetraisopropoxide [Ti(0-/Pr)4], tert-butyl hydroperoxide [t-BuOOH], and a specific enantiomer of a tartrate ester. 

Synthesis of 31 by Method I (107,108) and its conversion to the related anti and syn diol epoxide derivatives (32,33) has been reported (108). The isomeric trans-1,lOb-dihydrodiot 37) and the corresponding anti and syn diol epoxide isomers (38,39) have also been prepared (108) (Figure 19). Synthesis of 37 from 2,3-dihydro-fluoranthene (109) could not be accomplished by Prevost oxidation. An alternative route involving conversion of 2,3-dihydrofluoranthene to the i8-tetrahydrodiol (3-J) with OsO followed by dehydration, silylation, and oxidation with peracid gave the Ot-hydroxyketone 35. The trimethylsilyl ether derivative of the latter underwent stereoselective phenylselenylation to yield 36. Reduction of 3 with LiAlH, followed by oxidative elimination of the selenide function afforded 3J. Epoxidation of 37 with t-BuOOH/VO(acac) and de-silylation gave 38, while epoxidation of the acetate of JJ and deacetylation furnished 39. 

Figure 7. Dependence of BP oxidation by ram seminal vesicle micro-somes on the concentration of different hydroperoxides. Abbreviations used are 20 4, arachidonic acid 15-HPEA, 15-hydroperoxy-eicosatetraenoic acid t-BuOOH, t-butyl hydroperoxide. The structure is PGG2 is given in Figure 1.

Addition of H202 or t-BuOOH to aqueous solutions of iron(III)-TAML complexes 1 produces brownish-green colors. The spectral changes can be measured by UV/Vis spectroscopy (Fig. 10). Less than a stoichiometric amount of peroxide causes a major increase in the absorbance in the range 350-550 nm. It requires several minutes to obtain invariable spectra at pH below 8.5, but the reaction becomes much faster at pH >9. Two isosbestic points... 

Scheme 7 Reagents, i, PDC, t-BuOOH, Celite, PhH ii, H2, [Ir(cod)py(Pcy3)]PF6, CH2CI2, 1 atm iii, MCPBA.

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