Magnesium monoperoxyphthalate oxidant

The magnesium monoperoxyphthalate oxidation of indole, catalysed by the meso-tetraphenyl porphyrin FeClj, in H20-MeCN is of fractional order in both substrate and catalyst and the rate decreases with increasing H+ ion concentration and percentage of MeCN.22... 

It is possible to oxidize dimethylhydrazones R—C=N—NMe2 to the corresponding nitrile (R—C=N) with MeRe03/H202 magnesium monoperoxyphthalate... 

Pyrazolo[l,2-r-][l,3,4]oxadiazine derivative 188 is converted to the corresponding (V-oxide 189 by oxidation with magnesium monoperoxyphthalate (MMPP) or -chloroperbenzoic acid (MCPBA) (Equation 23) <2004CEJ737>. 

Alternatively, Ballini devised a new strategy to synthesize tri-alkylated pyrroles from 2,5-dialkylfurans and nitroalkanes <00SL391>. This method involves initial oxidation of 2,5-dimethylfuran with magnesium monoperoxyphthalate to cA-3-hexen-2,5-dione (6). Conjugate addition of the nitronate anion derived from the nitro compound 7 to 6 followed by chemoselective hydrogenation of the C-C double bond of the resulting enones 8 (obtained by elimination of nitrous acid from the Michael adduct) completes the conversion to the alkylated y-diketones 9. Final cyclization to pyrroles 10 featured improved Paal-Knorr reaction conditions involving reaction of the diketones with primary amines in a bed of basic alumina in the absence of solvent. 

A general oxidative cleavage reaction of ketone-derived SAMP-hydrazones can be realized without racemization by reaction with magnesium monoperoxyphthalate (MMPP) hexahydrate in methanol or in methanol/pH 7 phosphate buffer within 2 hours26. 

Alkylated Ketones by Cleavage of Alkylated SAMP-Hydrazones General Procedure for Oxidation with Magnesium Monoperoxyphthalate Hexahydrate2 ... 

After optical resolution by lipase, the silylated furanol with a trifluoromethyl group, was converted into the corresponding butenolide by oxidation with magnesium monoperoxyphthalate (MMPP). Ring opening of this butenolide... 

In the original patent published by Merck in 1995, rofecoxib (2) was synthesized in three steps from the known 4-(methylthio)acetophenone (10), prepared from the Friedel-Crafts acylation of thioanisole. As depicted in Scheme 2, oxidation of sulfide 10 using an excess of magnesium monoperoxyphthalate hexahydrate (MMPP, an inexpensive, safe and commercially available surrogate for w-CPBA) gave rise to sulfone 11, which was subsequently brominated with bromine and AICI3 to afford 2-bromo-l-(4-(methylsulfonyl)phenyl)ethanone (12). After recrystallization from 1 1 EtOAc/hexane, the pure phenylacyl bromide 12 was then cyclo-condensed with phenylacetic acid under the influence of l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to deliver rofecoxib (2) in... 

The synthesis of rofecoxib can be achieved by several different routes (Drugs Fut., 1998). A highly efficient synthesis for rofecoxib was recently described (Therien et al., 2001). As illustrated in Scheme 79, acetophenon (i) is prepared according to the literature, by Friedel-Crafts acylation with thioanisole. Oxidation with MMPP (magnesium monoperoxyphthalate hexahydrate) affords the sulfone (ii), which is reacted with bromine in chloroform in the presence of a trace amount of AICI3, to give (iii). Bromoketone (iii) is than coupled and cyclized in a second step, one-pot procedure with phenylacetic acid. Firstly, the mixture of bromoacetophenone (iii) and phenylacetic acid in acetonitrile is treated with... 

Resin-Bound 2-Methanesulfinyl-6-piperidinopyrimidine (9b) (R2NR2 = Piperidine) (lib). Resin 16 (500 mg, 0.50 mmol/ g loading, 0.25 mmol) is swollen in DMF (20 ml) for 30 min. The mixture is cooled to 0° and a solution of magnesium monoperoxyphthalate (MMPP, 212 mg, 0.34 mmol) in DMF (5 ml) is added dropwise and shaking continues for 2 h at 0°. After the resin is washed and dried in the usual manner, an aliquot of the resin (5 mg) is taken and cleaved off. RP-HPLC analysis indicates that approximately 6% starting material remained unreacted and a new oxidation cycle is performed with MMPP (0.14 mmol) for 1 h at 0°. Analysis confirmed the total conversion of resin 16 into a mixture of resin-bound sulfoxide (lib) ( 79%) and sulfone (11c) ( 15%). A theoretical loading of 0.50 mmol/g is assumed for subsequent work. 

Many of these iodanes are formed by oxidation of ortho-iodobenzoic acids or certain orf/zo-iodophenylated alcohols with Cl2, AcOOH, f-BuOCl, CF3OF or magnesium monoperoxyphthalate. Among A3-iodanes more important are those derived from o-iodosobenzoic acid which is obtained from the mild oxidation of o-iodobenzoic acid. An improved yield for o-iodosobenzoic acid was obtained by hydrolysis of its acetyl derivative which in turn was prepared from o-iodobenzoic acid and acetyl nitrate in acetic anhydride, at room temperature (Scheme 14) [52]. 

Another one-step addition reaction to C=C double bonds that forms three-membered rings is the epoxidation of alkenes with percarboxylic acids (Figure 3.19). Most often, meta-chloroperbenzoic acid (MCPBA) is used for epoxidations. Magnesium monoperoxyphthalate (MMPP) has become an alternative. Imidopercarboxylic acids are used to epoxidize olefins as well. Their use (for this purpose) is mandatory when the substrate contains a ketonic C=0 double bond in addition to the C=C double bond. In compounds of this type, percarboxylic acids preferentially cause a Baeyer-Villiger oxidation of the ketone (see Section 14.4.2), whereas imidopercarboxylic acids selectively effect epoxidations (for an example see Figure 14.35). 

Chemoselective oxidation of sulfenimines 2 is a useful method for the preparation of sulfinimines 3.10-12 The oxidation was usually carried out with m-CPBA (3-chlo-roperbenzoic acid) in a biphasic mixture of chloroform and aqueous sodium bicarbonate and a variety of sulfinimines have been prepared in this way. Sulfinimines 3 were usually obtained as a single -isomer despite the fact that their precursors 2 may exist as mixtures of E- and Z-isomers.10 Other oxidants which have been demonstrated to be effective for oxidation include MMPP (magnesium monoperoxyphthalate)13 and chlorine.14,15... 

A wide range of sulfides has been oxidized to the sulfoxide or sulfone in high yield using magnesium monoperoxyphthalate (MMPP) (Figure 3.97).389-392... 

Isothiazolium salts 226, which are prepared from P-thiocyanatovinyl aldehydes and anilines, can be oxidized with magnesium monoperoxyphthalate (MMPP) in water or alcohols to give 2-aryl-3-hydroxy-sultames 227 <03S2265>. This publication also reviews, in its introduction, a variety of other methods to form highly oxidized isothiazoles and their biological properties. 

Detoxification procedures from mustard gas are difficult because of its insolubility and also because of the drastic effects it can have on lung epithelial tissue following inhalation. During World War I, physicians had no curative means of treating the victims of mustard gas exposure. The only method of detoxification that was known involved a rather extreme oxidation procedure using superchlorinated bleaches, such as 5% sodium hypochlorite. Today, several novel methods of detoxification have been developed to counter the effects of mustard gas and these include the use of sulphur-amine solutions and magnesium monoperoxyphthalate. The most effective method to date employs peroxy acids, because they are able to react quickly with the mustard gas. 

The first asymmetric total synthesis of (+)-maritimol, a diterpenoid natural product that possesses a unique tetracyclic stemodane framework was accomplished by P. Deslongchamps. To introduce the C12 stereocenter, the Enders SAMP/RAMP hydrazone alkylation was used. This stereocenter played a crucial role in controlling the diastereoselectivity of the key transannular Diels-Alder reaction later in the synthesis. The required SAMP hydrazone was formed under standard conditions using catalytic p-toluenesulfonic acid. Subsequent protection of the free alcohol as a f-butyidiphenylsilyl ether, deprotonation of the hydrazone with LDA and alkylation provided the product in high yield and excellent diastereoselectivity. The hydrazone was converted to the corresponding nitrile by oxidation with magnesium monoperoxyphthalate. 

Enders, D., Plant, A. Enantioselective synthesis of a-substituted nitriles by oxidative cleavage of aldehyde SAMP-hydrazones with magnesium monoperoxyphthalate. Syn/eff 1994,1054-1056. 

Chen, M.-Y., Patkar, L. N., Lin, C.-C. Selective Oxidation of Glycosyl Sulfides to Sulfoxides Using Magnesium Monoperoxyphthalate and Microwave Irradiation. J. Org. Chem. 2004, 69, 2884-2887. 

Therefore, the classical rrani-dioxoRu(VI) - oxoRu(IV) catalytic cycle [2] (Fig. 1) can be ruled out as the primary reaction pathway in case of rapid catalytic oxygenation. The apparent zero-order kinetics observed are consistent with a steady-state catalytic regime accessible from different initial states of ruthenium metalloporphyrin. Indeed, common oxidants, other than aromatic iV-oxides, such as iodosylbenzene, magnesium monoperoxyphthalate, Oxone and tetrabutylammonium periodate produced the trans-dioxoRu(VI) species from Ru (TPFPP)(CO) under reaction conditions but were ineffective for the rapid catalysis. 

Isothiazolium salts react by S-oxidation and C-3 oxyfunctionalization with H202 (30%)/acetic acid or magnesium monoperoxyphthalate (MMPP) to stable mono-and bicyclic 3-hydroperoxysultims, -sultams, 3-hydroxysultams and 3-oxosultams, retaining the heterocyclic ring system. 

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