Iodosylbenzene epoxidation with

The Mn(III) complex 31b was tested as a catalyst for the epoxidation of various alkenes using sodium hypochlorite or iodosylbenzene as oxidants. Although oxidation took place, no selectivity was observed. For example, allylresorcinol was not epoxidized with rates higher than that of allylbenzene. Presumably, the substrate is not bound in the cleft of 31b because the latter is occluded by methoxy groups. It is possible that the reaction occurs on the outside of the metalloclip, which cannot discriminate between guest molecules. 

H. C. Sacco, Y. lamamoto, J. R. L. Smith, Alkene epoxidation with iodosylbenzene catalysed by polyionic manganese porphyrins electrostatically bound to counter-charged supports, /. Chem. Soc., Perkin Trans. 2 (2001) 181. 

In pursuit of biomimetic catalysts, metaUoporphyrins have been extensively studied in attempts to mimic the active site of cytochrome P450, which is an enzyme that catalyzes oxidation reactions in organisms. In recent decades, catalysis of alkene epoxidation with metaUoporphyrins has received considerable attention. It has been found that iron [1-3], manganese [4,5], chromium [6], and cobalt porphyrins can be used as model compounds for the active site of cytochrome P450, and oxidants such as iodosylbenzene, sodium hypochlorite [7,8], hydrogen peroxide [9], and peracetic acid [10] have been shown to work for these systems at ambient temperature and pressure. While researchers have learned a great deal about these catalysts, several practical issues limit their applicability, especially deactivation. 

FIGURE 19.4 Mechanism of styrene epoxidation with iodosylbenzene catalyzed by Mn-porphyrins proposed based on transition state structures identified. 

Asymmetric epoxidation. With a chiral (salen)Mn(III) complex to mediate the epoxidation of alkenes, iodosylbenzene supplies the active oxygen atom. 

Asymmetric Epoxidation of Viny Itrimethy Isilane. Vinyltri-methylsilane is converted to a predominant enantiomer of undetermined configuration by the aa S/S-TAPP aa/3/3-tetrakis(amino-phenyl)porphyrin -catalyzed epoxidation with iodosylbenzene (eq 31). Q ,/ -Epoxysilanes have been shown to have excellent synthetic utility. ... 

The mechanism of olefin epoxidation with iodosylbenzene in the presence of Cr(III) Schiff base complexes has been studied.The same reaction is catalysed by V0(acac)2 probably yij free radicals.Trans-stilbene is epoxidised by NalOi, in the presence of RuClg and substituted phenanthroline ligands. Vanadium(V) supported on a functionalised polystyrene resin is a good catalyst for the epoxidation of allylic alcohols by ButQOH a similar Mo(VI) catalyst is more suitable for cyclohexene epoxidation. ... 

The observation that addition of imidazoles and carboxylic acids significantly improved the epoxidation reaction resulted in the development of Mn-porphyrin complexes containing these groups covalently linked to the porphyrin platform as attached pendant arms (11) [63]. When these catalysts were employed in the epoxidation of simple olefins with hydrogen peroxide, enhanced oxidation rates were obtained in combination with perfect product selectivity (Table 6.6, Entry 3). In contrast with epoxidations catalyzed by other metals, the Mn-porphyrin system yields products with scrambled stereochemistry the epoxidation of cis-stilbene with Mn(TPP)Cl (TPP = tetraphenylporphyrin) and iodosylbenzene, for example, generated cis- and trans-stilbene oxide in a ratio of 35 65. The low stereospecificity was improved by use of heterocyclic additives such as pyridines or imidazoles. The epoxidation system, with hydrogen peroxide as terminal oxidant, was reported to be stereospecific for ris-olefins, whereas trans-olefins are poor substrates with these catalysts. 

The mesoporous character of MCM-41 overcomes the size limitations imposed by the use of zeolites and it is possible to prepare the complex by refluxing the chiral ligand in the presence of Mn +-exchanged Al-MCM-41 [34-36]. However, this method only gives 10% of Mn in the form of the complex, as shown by elemental analysis, and good results are only possible due to the very low catalytic activity of the uncomplexed Mn sites. The immobihzed catalyst was used in the epoxidation of (Z)-stilbene with iodosylbenzene and this led to a mixture of cis (meso) and trans (chiral) epoxides. Enantioselectivity in the trans epoxides was up to 70%, which is close to the value obtained in solution (78% ee). However, this value was much lower when (E)-stilbene was used (25% ee). As occurred with other immobilized catalysts, reuse of the catalyst led to a significant loss in activity and, to a greater extent, in enantioselectivity. 

Dioxo-ruthenium porphyrin (19) undergoes epoxidation.69 Alternatively, the complex (19) serves as the catalyst for epoxidation in the presence of pyridine A-oxide derivatives.61 It has been proposed that, under these conditions, a nms-A-oxide-coordinated (TMP)Ru(O) intermediate (20) is generated, and it rapidly epoxidizes olefins prior to its conversion to (19) (Scheme 8).61 In accordance with this proposal, the enantioselectivity of chiral dioxo ruthenium-catalyzed epoxidation is dependent on the oxidant used.55,61 In the iron porphyrin-catalyzed oxidation, an iron porphyrin-iodosylbenzene adduct has also been suggested as the active species.70... 

The epoxidation of alkenes using iodosylbenzene, with tetra-n-butylammonium bromide and a manganese or cobalt polytungstate as co-catalysts [24], appears to have little advantage as a synthetic procedure over other methods. n-Hexene produces the oxirane (58%), when catalysed by the manganese salt, whereas norbornene is more readily converted (96%) into the oxirane with the cobalt salt. 

Iodosylbenzene is sufficiendy reactive on its own to epoxidize electron-deficient olefins such as tetracyanoethylene (43). It is possible that coordinated monomeric iodosylbenzene is substantially more reactive than polymeric iodosylbenzene and that complexation of a monomeric form is sufficient to provide the requisite reactivity with normal olefins. 

Chromium complexes in general are poor catalysts for the epoxidation of alkenes with TBHP due to the decomposition of the oxygen donor with formation of molecnlar oxygen . Epoxidation reactions with this metal are known with other oxygen transfer agents than peroxides (e.g. iodosylbenzene) and will not be discnssed here. 

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