C/S-CYCLOOCTENE OXIDE

Table 7.4 c/s-Cyclooctene oxidation performance using homogeneous and heterogeneous Mn dimer catalysts at 273 K for 3 h [43]. 

In 2006, CoUman and Brauman employed ArIO in investigations of kinetics of the [(TPFPP)MnQ]-catalyzed epoxidation of c/s-cyclooctene, styrene, and 1-decene [57]. Their results established that the iodosylarene and metal complex rapidly react to form an active oxidant, which then reversibly forms an adduct with the substrate and then produces the epoxide product. The overall reaction follows saturation kinetics and can be fitted with a MichaeUs—Menten model. The identity of the active oxidant, however, could not be unambiguously established. 

The two-phase permanganate oxidation of olefins generally affords products of oxidative cleavage. Weber and Shepherd found that when benzyltriethylammonium chloride was used as catalyst and the temperature was maintained near 0°C, internal olefins were oxidized by basic permanganate in dichloromethane to the corresponding czs-glycols in moderate yields (Eq. 11.3) [6]. Cyclohexene, c/s-cyclooctene and trans-cyclododecene were dihydroxylated by this method in 15%, 50%, and 50% yields... 

The new technique is convenient for synthesis of pure (rani-cyclooctene. The oxide of m-cyclooctene (4) is converted into (ra .s-cyclooctene (7) in > 90% yield, > 99.5% isomeric purity. Rigorously aprotic conditions are required for stereoselectivity. In the same way (ran. -1-methylcyclooctene, c ,(ranr-1,4-cyclooctadiene, and cisjrans-1.5-cyclooctadiene have been prepared from the corresponding epoxides. 

Very recently, deprotonation-electrophile trapping of simple meso-epoxides was applied to medium-sized meso-cycloalkene oxides [77]. When cyclooctene oxide 62 is treated with s-BuLi in the presence of a diamine at -90°C, the Hthiated epoxide is stable enough to be trapped with a wide range of electrophiles, allowing the creation of carbon-heteroatom or carbon-carbon bonds [Eq. (33)]. The deprotonation is a symmetry-breaking step, and enantioselective deprotonation was successfully achieved in the presence of (-)-sparteine, leading to a range of enantio enriched functionalised epoxides 115 (in up to 86% ee). 

A soln. of cyclooctene oxide in benzene passed at 180 with the aid of Ng through a column packed with Li-orthophosphate pellets 3-hydroxycyclooctene. Y 70%. - Li-diethylamide causes mostly rearrangement to 2-hydroxybicyclo[3.3.0]-octane. M. N. Sheng, Synthesis 1972, 194 allyl alcohol from propylene oxide s. A. G. Polkovnikova, N. S. Usacheva, and A. E. Folomeeva, Khim. Prom. 49, 325 (1973) C. A. 79, 31412 2-ethylenealcohols preferably with Li-di-n-propylamide or Li-di-n-butylamide s. C. L. Kissel and B. Rickborn, J. Org. Chem. 37, 2060 (1972) by thermal rearrangement without added acids or bases s. R. J. Anderson et al., Am. Soc. 94, 5379 (1972) basic rearrangements of oxido compds., review s. V. N. Yandovskii and B. A. Ershov, Russ. Chem. Rev. 41, 403 (1972) (Eng. transl.). 

Both 0-atoms of Ru(TMP)(0)2 can be transferred to an olefin in a stoichiometric reaction to generate 2 moles of epoxide, and the species also catalyzes O -oxidation of olefins at ambient conditions in benzene with high selectivity and > 90% yields with norbomene the order of olefin reactivity is norbomene > c/s-p-methylstyrene > cyclooctene > (ra s-p-methylstyrenc, while epoxidation of cis- and /ra s-P-methylstyrene proceeds with retention of configuration . The suggested catalytic cycle shown in Figure 6 implies the key disproportionation of a Ru(IV)=0 intermediate to the Ru(VI)(0)2 and Ru(II) species (see also Section 2, eq. 16, and Section 3.1, eq. 25) ,... 

The lithium diethylamide-promoted isomerization of cis- and traws-cyclooctene oxide affords different products or the same products in different proportions. This lack of convergence rules out carbene 227 as a common intermediate (Scheme 1-173). Moreover, the c/s-oxirane reacts with isopropyllithium in the presence of (-)-sparteine enantioselectively. ... 

It is generally agreed that alkenyl hydroperoxides are primary products in the liquid-phase oxidation of olefins. Kamneva and Panfilova (8) believe the dimeric and trimeric dialkyl peroxides they obtained from the oxidation of cyclohexene at 35° to 40° to be secondary products resulting from cyclohexene hydroperoxide. But Van Sickle and co-workers (20) report that, The abstraction/addition ratio is nearly independent of temperature in oxidation of isobutylene and cycloheptene and of solvent changes in oxidations of cyclopentene, tetramethylethylene, and cyclooctene. They interpret these results to support a branching mechanism which gives rise to alkenyl hydroperoxide and polymeric dialkyl peroxide, both as primary oxidation products. This interpretation has been well accepted (7, 13). Brill s (4) and our results show that acyclic alkenyl hydroperoxides decompose extensively at temperatures above 100°C. to complicate the reaction kinetics and mechanistic interpretations. A simplified reaction scheme is outlined below. 

Bedioui, R, S. Gutierrez Granados, L. Gaillon, C. Bied-Charreton, and J. Devynck (1991). Electroassisted oxidation of ds -cyclooctene and adamantane by molecular oxygen catalyzed by polypyrrole manganese porphyrin films. Stud. Surf. Sci. Catal. 66, 221-228. 

Suberic add octanedioic add, HOOC-(CH2) -COOH, a higher saturated dicarboxylic add. m.p. 142°C, b.p. 300"C (d.). S.a. is formed (together with its homologs azelaic and sebacic acids) by oxidation of cork or ricinus oil with nitric acid. It is obtained in higher yields from cyclooctene (technical syn-thesisX... 

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