MoOPH

BuLi, THF, -78° O2 or MoOPH, [oxodiperoxymolybdenum-(hexa-methylphosphorictriamide)(pyridine)], 30-68% yield. This method uses the amide carbonyl to direct benzylic metalation. 

Oxidative desulfonylation polyenes. Oxidation of the anion of a primary sulfone with MoOPH results in a p-hydroxy sulfone formed by condensation of... 

A hydroxyl group has been introduced at the bridgehead of the bicyclic compound (146) by treating the carbanion with the reagent oxodiperoxy-molybdenum hexamethylphosphoric triamide, pyridine (MoOPH), to give compound (147) (81TL2341). 

The preparation of a-hydroxy carbonyl compounds has been accomplished by the oxidation of enolates using both oxygen6 and MoC PyHMPA-(MoOPh).7 Acyl anion equivalents offer another route to this useful class of compounds. The procedure presented here for the synthesis of 6-hydroxy-3,5,5-tr1methyl-2-cyclohexen-l-one illustrates the use of MCPBA oxidation of an enol silyl ether as a method for obtaining an a-hydroxy enone. The procedure is a scaleup of a published synthesis. ... 

Mo05-Py.tflPA (MoOPH) l,7,7-TRIMETHYL-3-HYDR0XYBICYCL0[2.2.1]HEPTAN-2-0NE (Bicyclo[2.2.1]heptan-2-one, 3-hydroxy-l,7,7-trimethyl-)... 

The product is stored in a dark glass jar inside a second container partly filled with Drierite, and the container is kept in the refrigerator. Before opening the jar, the container 1s allowed to warm to room temperature to avoid condensation of moisture inside. Properly stored MoOPH is a freely flowing crystalline powder and can be used over a period of several months (Note 10). 

The MoOPH reagent also hydroxylates branched or unbranched ester, amide, and nitrile anions. 7 For unknown reasons, MoOPH hydroxylations often do not give complete conversion of enolates into products, and recovery of 5-15% of the starting carbonyl substrate is to be expected. 

Methyl ketone enolates are hydroxylated by MoOPH, but the products tend to undergo condensation with the starting enolate, resulting in poor yields. Methyl ketone hydroxylation has been described by Moriarty, using c6H5I=0/CH30H-°He.a... 

The method described for MoOPH hydroxylation of the camphor enolate Is representative for ketone enolate hydroxylations, but optimization in each Individual case to determine the best temperature and concentration is recommended. Large scale oxidations may benefit from addition of reagent in several portions over time, and enolates which are sensitive to selfcondensation may give higher yields if enolate is added slowly to excess MoOPH. 

HYDROXYLATION OF ENOLATES WITH OXODIPEROXYMOLYBDENUM(PYRIDINE)-(HEXAMETHYLPHOSPHORIC TRIAMIDE), MoOc-Py-HMPA (MoOPH) ... 

Asymmetric hydroxylation of chiral imides The (Z)-spdium enolates of the chiral imides 2 and 3 undergo asymmetric hydroxylation on reaction with 2-(phen-ylsulfonyl)-3-phenyloxaziridine (1). The products [(R)-4 and (S)-6] are solvo-lyzed to (R)- and (S)-a-hydroxy esters. This hydroxylation can also be effected with MoOPh, which is much less reactive than 1 but slightly more stereoselective. In general 1 is preferred to MoOPh because of the higher yields. 

Etiolate hydroxylatton. Complete details are available for preparation of MoOPH (equation I). The reagent can be stored with protection from moisture and light in a refrigerator for several months. Partially decomposed reagent cannot be purified. 

MoOPh at 0° to the orf/to-hydroxylated aldehyde (4). Higher yields obtain if 3 is converted to the tributylboronic ester followed by oxidation with 30% H202. 

AD-mix-P 9-BBN Bn Boc Bz BOM CDI m-CPBA CSA Cy DBU DDQ DEAD DIAD DIBAL-H DIPT DME DMF DMAP DMSO EDC HMPA HOBT KHMDS LDA MEM MOM MoOPH NaHMDS NBS NMM NMO Piv PMB Reagent for Sharpless asymmetric dihydroxylation 9-Borabicyclo[3.3.1 ]nonyl Benzyl t-Butoxy carbonyl Benzoyl B enzyloxy methyl Carbonyldiimidazole m-Chloroperoxybenzoic acid Camphorsulfonic acid Cyclohexyl 1,8 -Diazabicy clo[5.4.0] undec-7-ene 2,3 -Dichloro-5,6-dicyano-p-benzoquinone Diethyl azodicarboxylate Diisopropyl azodicarboxylate Diisobutylaluminum hydride Diisopropyl tartrate Dimethoxyethane A,N-Dimethylformamide 4-Dimethylaminopyridine Dimethyl sulfoxide N-(3-Dimethylaminopropyl)-A -ethylcarbodiimide Hexamethylphosphoramide 1 -Hydroxybenzotriazole Potassium hexamethyldisilazane Lithium diisopropylamide Methoxyethoxymethyl Methoxymethyl Oxidodiperoxymolybdenum(pyridine)(hexamethylphophoramide) Sodium hexamethyldisilazane N - Bromosuccinimide A-Methylmorpholine A-Methylmorpholine A-oxide Pivaloyl /j-Methoxybenzyl... 

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