Hexamethylphosphoric peroxide

Mimoun and co-workers419 prepared a series of stable covalent Mo (VI) and W(VI) peroxides of structure (VIII), by reaction of the corresponding peracids with organic bases, such as pyridine, hexamethylphosphorous triamide (HMPA),... 

Epoxidation I-Butylhydroperoxide. m-Chloroperbenzoic add. Hexamethylphosphorous triamide. Hydrogen peroxide. p-Nitroperbenzoic acid. Peracetic acid. Perbenzoic acid. Permaleic acid. Perphthalic acid. Sodium hypochlorite. 

OXIDATION, REAGENTS Acetyl nitrate. Bis(tri-n-butyltin)oxide. Bromine-Hexameth-ylphosphoric triamide. f-Butyl perbenzoate. Ceric ammonium nitrate. N-chlorosuc-cinimide-Dimethyl sulfide. Chromic add. Chromic anhydride. Chromic anhydride-Acetic anhydride. Chromic anhydride-Hexamethylphosphoric triamide. 2,3-Dichloro-5,6-dicyano-l,4-benzoquinone. Dimethyl sulfoxide. Dimethyl sulfoxide-Trifluoro-acetic anhydride. Diphenylseleninlc anhydride. Iodine tris(trifluoroacetate). Lead tetraacetate. N-Methylmorpholine -N-oxide. p-NitrobenzenesulfonyI peroxide. Oxygen, singlet. Palladlumfll) chloride. Peroxybcnzimidic acid. Phenylseleninyl chloride. N-Phenyl-l,2,4-triazoline-3,5-dione. Potassium chromate. Potassium superoxide. Pyri-dinium chlorodiromate. Salcomine. Silver carbonate-Celite. Sodium hypochlorite. Sulfuryl chloridc-Silica gel. Thallium(III) acetate. ThaUium(III) nitrate. Triphenyl phosphite ozonide. Trltyl tetrafluoroborate. Uranium hexafluoride. 

More recent work has shown that direct hydroxylation of enolate anions can be achieved with a molybdenum peroxide reagent, which consists of M0O5 as a complex with pyridine (C5H5N) and hexamethylphosphoric acid triamide (hexameth-ylphosphoramidate [HMPA], 0=P[N(CH3)2]3). As shown in Scheme 8.12, phenylcy-clohexanone is first converted to the corresponding anion (e.g., with n-butyUithium, BuLi, CH3CH2CH2CH2Li) and the latter is treated with the molybdenum complex... 

Other procedures for a oxidation of ketones are based on prior generation of the enolate. The most useful oxidant in these procedures is a molybdenum compound, MoOs-pyridine-HMPA, which is prepared by dissolving M0O3 in hydrogen peroxide, followed by addition of HMPA (hexamethylphosphoric triamide). This reagent oxidizes the enolates of aldehydes, ketones, esters, and lactones to the corresponding a-hydroxy compound.Another method for enolate... 

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