Schiff bases, manganese catalysts

Sulfamate indan-2-yl ester 145 is oxidized by iodobenzene diacetate to give condensed 1,2,3-oxathiazole di-A-oxides 146 (Equation 35). Various rhodium <2001JA6935, 2004HCA1607>, manganese(m) Schiff base <2005TL5403>, and ruthenium porphyrin <2002AGE3465> catalysts can be used for this transformation. Enantioselective intramolecular amidation is achieved with good yields. 

A. Martinez, C. Hemmert, B. Mcunicr, A macrocyclic chiral manganese(III) Schiff base complex as an efficient catalyst for the asymmetric epoxidation of olefins, /. Catal. 235 (2005) 250. 

Silva AR, Budarin V, Clark JH, Castro B de, Freire C. Chiral manganese(IIl) schiff base complexes anchored onto activated carbon as enantioselective heterogeneous catalysts for alkene epoxidation. Carbon 2005 43(10) 2096-2105. 

Figure 9.8 Catalytic cycle for the epoxidation of unfunctionalized alkenes with a chiral Schiff base complex of manganese as the catalyst.

A novel polynuclear manganese Schiff base complex was prepared and its catalytic activity towards the decomposition of hydrogen peroxide was studied. It is observed that the activity of the catalyst depends on the reaction temperature and the nature of the reaction medium. There is no appreciable reduction in activity was noticed after several runs which suggests that the complex is very stable. From this study, we assumed that the catalyst is a good model for effective hydrogen peroxide decomposition in aqueous medium. 

A new family of hybrid organic-inorganic catalysts with dispersed active sites inside ordered mesoporous materials has been prepared by anchorage of transition-metal ligands of Schiff base-type and chiral amino alcohols like (li ,2S)-ephedrine on micelle-templated silicas [180]. Metalation of the grafted ligands with manganese was followed by UV-VIS spectroscopy. 

Epoxidation of alkenes with iodosylbenzene can be effectively catalyzed by the analogous salen or chiral Schiff base complexes of manganese(in), ruthenium(II), or ruthenium(III). For example, the oxidation of indene with iodosylbenzene in the presence of (/ ,5)-Mn-salen complexes as catalysts affords the respective (15,2/ )-epoxyindane in good yield with 91-96% ee [704]. Additional examples include epoxidation of alkenes with iodosylbenzene catalyzed by various metalloporphyrins [705-709], corrole metal complexes, ruthenium-pyridinedicarboxylate complexes of terpyridine and chiral bis(oxazoUnyl)pyridine [710,711]. 

The main drawback in Sharpless epoxidation is that the substrate must bear a functional group to achieve the precoordination required for high enantioselec-tivity (as in the case of allyl alcohol). This restriction is not applicable to the epoxidation of alkyl- and aryl-substituted olefins with manganese complexes of chiral Schiffs bases as catalysts. Very high enantioselectivities can be obtained in these reactions (Jacobsen, 1993). The most widely used catalysts that give high enantioselectivity are those derived from the Schiff bases of chiral diamines such as [SiS] and [RR] 1,2-diphenylethylenediamine and [SS] and [RR] cyclohexyl-1,2-diamine. An example is the synthesis of cromakalim. 

Electrocatalytic oxidations (mainly epox-idation) of alkenes by manganese porphyrins [77, 78] and a Schiff-base [79] and iron and cobalt porphyrins [78] have been achieved. Hydrogen peroxide or the superoxide ion (O ) was generated electrochem-ically by reduction of dioxygen in solvents containing an acid or acid anhydride, the metal compounds as catalysts, and olefins as substrates, in the presence or absence of an axial base. The reaction was believed to take place through the formation of a high valent metal 0x0 porphyrin, produced... 

C-H oxidation (150). The Jacobsen s ligand has been used for the modification of the manganese exchanged Al-MCM-41, that is the immobilized catalyst has been investigated in epoxidation of styrene (151). Chiral manganese-Schiff base complexes were immobilized on a glassy carbon electrode surface (152). Enan-tioselective epoxidation reactions were also catalyzed with Mn(III) complexes of chiral porphirines (97,153). 

In this context it is worth noting that neither the titanium(IV) tartrate catalyst nor other metal catalyst-alkyl hydroperoxide reagents are effective for the asymmetric epoxidation of unfunctionalized olefins. The only system that affords high enantioselectivities with unfunctionalized olefins is the manganese(III) chiral Schiff s base complex/NaOCl combination developed by Jacobsen [42]. There is still a definite need, therefore, for the development of an efficient chiral catalyst for asymmetric epoxidation of unfunctionalized olefins with alkyl hydroperoxides or hydrogen peroxide. 

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