Olefinic epoxides

Sulfitation and Bisulfitation of Unsaturated Hydrocarbons. Sulfites and bisulfites react with compounds such as olefins, epoxides, aldehydes, ketones, alkynes, a2iridines, and episulftdes to give aHphatic sulfonates or hydroxysulfonates. These compounds can be used as intermediates in the synthesis of a variety of organic compounds. 

The primary determinant of catalyst surface area is the support surface area, except in the case of certain catalysts where extremely fine dispersions of active material are obtained. As a rule, catalysts intended for catalytic conversions utilizing hydrogen, eg, hydrogenation, hydrodesulfurization, and hydrodenitrogenation, can utilize high surface area supports, whereas those intended for selective oxidation, eg, olefin epoxidation, require low surface area supports to avoid troublesome side reactions. 

The phenomenon that early transition metals in combination with alkyl hydroperoxides could participate in olefin epoxidation was discovered in the early 1970s [30, 31]. While m-CPBA was known to oxidize more reactive isolated olefins, it was discovered that allylic alcohols were oxidized to the corresponding epoxides at the same rate or even faster than a simple double bond when Vv or MoVI catalysts were employed in the reaction [Eq. (2)] [30]. 

A breakthrough in the area of asymmetric epoxidation came at the beginning of the 1990s, when the groups of Jacobsen and Katsuki more or less simultaneously discovered that chiral Mn-salen complexes (15) catalyzed the enantioselective formation of epoxides [71, 72, 73], The discovery that simple achiral Mn-salen complexes could be used as catalysts for olefin epoxidation had already been made... 

In conclusion, the above summary of oxidation methods shows that there is still room for further improvements in the field of selective olefin epoxidation. The development of active and selective catalysts capable of oxidizing a broad range of olefin substrates with aqueous hydrogen peroxide as terminal oxidant in inexpensive and environmentally benign solvents remains a continuing challenge. 

The catalytic activitira of synfliesized catalysts are given in Table 1. The TS-1 catalyst exhibited the highest epoxide yield and the best catalytic performance for the epoxidation of 1-hexene. The convasion of cyclohexene, however, is the lowest over TS-1. In case of TS-1/MCM-41-A and TS-1/MCM-41-B, the selectivity to epoxide is much hi er than that of Ti-MCM-41. Moreover, the conversion of 1-hexene as well as cyclohexene is found larger on the TS-l/MCM-41-Aand TS-1/MCM-41-B than on other catalysts. While the epoxide yield from 1-hexene is nearly equivalent to that of TS-1, the yield from cyclohexene is much larger than those of the otiier two catalysts. Th e results of olefins epoxidation demonstrate that the TS-l/MCM-41-Aand TS-1/MCM-41-B possess the surface properties of TS-1 and mesoporosity of a typical mesoporous material, which were evidently brou in by the DGC process. 

Experimental results of olefins epoxidation with H2O2 over Tr-conlaing catalysts. 

Abstract In this review, recent developments of iron-catalyzed oxidations of olefins (epoxidation), alkanes, arenes, and alcohols are summarized. Special focus is given on the ligand systems and the catalytic performance of the iron complexes. In addition, the mechanistic involvement of high-valent iron-oxo species is discussed. 

Stack and coworkers immobilized phenantrohne derivative 16 on micelle-templated silica SBA-15 (Scheme 8) [55,56]. The system showed more selective and efficient catalytic activity for olefin epoxidations with peracetic acid than the analogous homogeneous catalyst. 

Diketonate cobalt(III) complexes with alkyl peroxo adducts have been prepared recently and characterized structurally, and their value in hydrocarbon oxidation and olefin epoxidation examined.980 Compounds Co(acac) 2(L) (O O / - B u) with L = py, 4-Mepy and 1-Meim, as well as the analog of the first with dibenzoylmethane as the diketone, were prepared. A distorted octahedral geometry with the monodentates cis is consistently observed, and the Co—O bond distance for the peroxo ligand lies between 1.860(3) A and 1.879(2) A. 

Preparation and Activity of a V-Ti/Silica Catalyst for Olefin Epoxidation... 

A heterogeneous olefin epoxidation catalyst containing both V and Ti in the active site was prepared by sequential non-hydrolytic grafting. The silica was exposed first to VO(OiPr)3 vapor followed by Ti(0 Pr)4 vapor. Formation of propene is evidence for the creation of Ti-O-V linkages on the surface. Upon metathesis of the 2-propoxide ligands with BuOOH, the catalyst becomes active for the gas phase epoxidation of cyclohexene. The kinetics of epoxidation are biphasic, indicating the presence of two reactive sites whose activity differs by approximately one order of magnitude. 

The presence of V does not diminish the activity of a grafted Ti-Si02 catalyst for olefin epoxidation. However, activity towards simple olefins such as cyclohexene is not enhanced. Since homogeneous V catalysts are known to catalyze the epoxidation of functionalized olefins (e.g., allylic alcohols), the ability of a mixed V-Ti/Si02 catalyst to achieve such transformations will be the next focus of our investigations. 

By complexation of MnNaY with 1,4,7-trimethyltriazacyclononane, a new heterogeneous catalyst was obtained for olefin epoxidation with H202. Excellent epoxide selectivities were obtained, with limited epoxide solvolysis. The oxygenation appears to go through a radical intermediate. The manganese trizacyclononane epoxidation catalyst was also heterogenized via surface gly-cidylation.103... 

Xu, L., Sithambaram, S., Zhang, Y., Chen, C., Jin, L., Joesten, R. and Suib, S.L. (2009) Novel urchin-like CuO synthesized by a facile reflux method with efficient olefin epoxidation catalytic performance. Chemistry of Materials, 21, 1253-1259. Calvert, C., Joesten, R., Ngala, K., Villegas, J., Morey, A., Shen, X. and Suib,S.L. 

Vinyl epoxides are highly useful synthetic intermediates. The epoxidation of dienes using Mn-salen type catalysts typically occurs at the civ-olefin. Epoxidations of dienes with sugar-derived dioxiranes have previously been reported to react at the trans-olefin of a diene. A new oxazolidinone-sugar dioxirane, 9, has been shown to epoxidize the civ-olefin of a diene <06AG(I)4475>. A variety of substitution on the diene is tolerated in the epoxidation, including aryl, alkyl and even an additional olefin. All of these substitutions provided moderate yields of the mono-epoxide with good enantioselectivity. 

For the lability of alkoxy-type radicals, see Ando, W. (ed.). (1992). Organic Peroxides. Wiley, New York. In the same way, olefin epoxidation with peracids can be simply viewed as an electron transfer, followed by mesolytic cleavage of the peracid anion radical to carboxylate and hydroxyl radical, followed by homolytic coupling and proton loss. See also Nugent, W.A., Bertini, F. and Kochi, J.K. (1974). J. Am. Chem. Soc. 96,4945... 

Olefin epoxidation by alkyl hydroperoxides catalyzed by transition metal compounds occupies an important place among modern catalytic oxidation reactions. This process occurs according to the following stoichiometric equation ... 

The reaction of olefin epoxidation by peracids was discovered by Prilezhaev [235]. The first observation concerning catalytic olefin epoxidation was made in 1950 by Hawkins [236]. He discovered oxide formation from cyclohexene and 1-octane during the decomposition of cumyl hydroperoxide in the medium of these hydrocarbons in the presence of vanadium pentaoxide. From 1963 to 1965, the Halcon Co. developed and patented the process of preparation of propylene oxide and styrene from propylene and ethylbenzene in which the key stage is the catalytic epoxidation of propylene by ethylbenzene hydroperoxide [237,238]. In 1965, Indictor and Brill [239] published studies on the epoxidation of several olefins by 1,1-dimethylethyl hydroperoxide catalyzed by acetylacetonates of several metals. They observed the high yield of oxide (close to 100% with respect to hydroperoxide) for catalysis by molybdenum, vanadium, and chromium acetylacetonates. The low yield of oxide (15-28%) was observed in the case of catalysis by manganese, cobalt, iron, and copper acetylacetonates. The further studies showed that molybdenum, vanadium, and... 

From the energetics point of view, the epoxidation act should occur more easily (with a lower activation energy) in the coordination sphere of the metal when the cleavage of one bond is simultaneously compensated by the formation of another bond. For example, Gould proposed the following (schematic) mechanism for olefin epoxidation on molybdenum complexes [240] ... 

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