Magnesium monoperoxyphthalate MMPP

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>. 

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. 

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... 

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. 

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). 

A third one-step addition reaction to C=C double bonds that forms three-membered rings is the epoxidation of olefins with percarboxylic acids (Figure 3.14). Suitable percarboxylic acids must, however, not be (too) explosive. Thus, aromatic percarboxylic adds are preferable. Until recently one epoxidized almost exclusively with mefa-chloroper-benzoic acid (MCPBA). An alternative has become magnesium monoperoxyphthalate (MMPP). In the transition state of this type of epoxidation, four electron pairs are shifted simultaneously (which is a record in this book except for the Corey-Winter elimination in Figure 4.42). 

Magnesium monoperoxyphthalate (MMPP) epoxidizes alkenes much like MCPBA. MMPP is more stable, however, and it may be safer to use for large-scale and industrial reactions. Propose a mechanism for the reaction of fraw,s-2-methylhept-3-ene with MMPP, and predict the structure of the product(s). 

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. 

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. 

The synthesis of enantiopure 4-unsubstituted 3-alkoxy- and 3-amino (3-lactams has been reported to be performed in two steps (a) and (b). (a) The [2+2] cycloaddition reaction of chiral formaldehyde N, W-dialkylhydrazones to alkoxy or aminoketenes. (b) The magnesium monoperoxyphthalate (MMPP)-promoted oxidative N N bond cleavage of the resulting hydrazides (Scheme 10), [58]. 

The peroxyacid epoxidation is quite general, with electron-rich double bonds reacting fastest. The following reactions are difficult transformations made possible by this selective, stereospecific epoxidation procedure. The second example uses magnesium monoperoxyphthalate (MMPP), a relatively stable water-soluble peroxyacid often used in large-scale epoxidations. 

Additional examples of this fascinating chemistry are listed in Table 1 [9, 10]. For Entries 1-3, the initially formed m-chlorobenzoate product is methanolized to the methyl ether (not shown). Entry 3 represents an attractive synthesis of pyrrolo[3,2-d]pyrimidines [11]. Water is the nucleophile in Entry 4, not m-chlorobenzoate, in a sequence that provides pyrrolo[3,2-c]coumarins [12]. Entry 5 describes the preparation of pyrrolo[3,2-c] [1] benzothi-opyran-4-ones, which is a new ring system and where water has captured the intermediate 3-methylene-2-hydroxy indoline [13]. Entry 6 features the synthesis of pyrrolo[3,2-c]pyrones [14]. Entry 7 describes a similar rearrangement of A-alkyl-A-allenylmethylanihnes with magnesium monoperoxyphthalate (MMPP) to afford 2-vinylindoles [15], This reaction presumably follows the one described earlier, although none of the presumed intermediates could be isolated. 

For these reasons, many products were developed in the past but were never commercialized. In the late 1980s, diperoxydodecanedioic acid (DPDDA) was test marketed as a laundry bleach. Magnesium monoperoxyphthalate (MMPP) was also tested in the 1990s as a bleach in detergent formulations. Today, the only peracid that has been commercialized on a limited scale is 8-phthalimidoperoxycaproic acid or PAP (trade name Eureco). 

The reaction occurs between the aqueous solution of MCPBA and the emulsified substrate (Ch. 9, p. 348). A comparison was made with the similar reaction using magnesium monoperoxyphthalate (MMPP), in aqueous ethanol suspensions. In general, MCPBA reacts faster and is more selective and higher yielding than MMPP. Most of the reactions go to completion within a few minutes, while the silent process requires several hours. Excellent selectivities are observed, and terminal olefins can be kept intact in the presence of central ones. Under the experimental conditions, methyl zso-ricinoleate imdergoes epoxidation followed by cyclization to the tetrahydrofuranic compoimd. 

Give the expected major product of reaction of magnesium monoperoxyphthalate (MMPP) with each alkene. In each case, also give the structure of the material formed upon hydrolysis in aqneons acid of the initial product. 

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