Epoxides halohydrins

The reaction of chloro- or bromohydrins with bases provides an economical route for the preparation of epoxides. Halohydrins are readily accessible by treatment of an alkene with either hypochlorous acid (Clj -1- H2O —> HOCl), hypochlorite bleach solution (NaOCl), or hypobromous acid (NBS -1- HjO HOBr). These reactions involve the... 

The activation of a diol function could be performed in many different ways. As will be discussed later, vicinal diols can be easily transformed into epoxides, halohydrins and cyclic sulfates, all of them reacting readily and with high stereocontrol with a range of nucleophiles. An intermediate typically generated during the formation of cyclic sulfates [113] is the corresponding cyclic sulfite (Scheme 37). Several nucleophiles, e.g. N3, Cl and Br react readily with activated cychc sulfites to afford in good yield and with clean inversion of stereochemistry, the substitution products. 

Cleavage of terminal epoxides halohydrins. The cleavage of a terminal epoxide (1) can result in two halohydrins. By proper choice of a metal halide either one of the halohydrins can be obtained with about 95% regioselectivity. 

Dehydro- halogenation Halohydrin Epoxide Synthesis of epoxides resolution of halohydrins and epoxides Halohydrin dehalogenase... 

Base promoted cyclization of vicinal halohydrms (Section 16 10) This reaction is an intramolecu lar version of the Williamson ether synthesis The alcohol function of a vicinal halohydrin is con verted to its conjugate base which then displa ces halide from the adjacent carbon to give an epoxide... 

The high degree of stereoselectivity associated with most syntheses and reactions of oxiranes accounts for the enormous utility of these systems in steroid syntheses. Individual selectivity at various positions in the steroid nucleus necessitates the discussion of a collection of uniquely specific reactions used in the synthesis of steroidal epoxides. The most convenient and generally applicable methods involve the peracid, the alkaline hydrogen peroxide and the halohydrin reactions. Several additional but more limited techniques are also available. 

Halohydrins are useful intermediates especially in the synthesis of epoxides The main reaction is usually accompanied by the formation of a dihalide... 

The following section describes the preparation of epoxides by the base-promoted ring closure of vicinal halohydrins. Because vicinal halohydrins are customarily prepared from alkenes (Section 6.17), both methods—epoxidation using peroxy acids and ring closure of halohydrins—are based on alkenes as the starting materials for preparing epoxides. 

The formation of vicinal halohydrins from alkenes was described in Section 6.17. Halohydrins are readily converted to epoxides on treatment with base ... 

Another method for the synthesis of epoxides is through the use of halo-hydrins, prepared by electrophilic addition of HO-X to alkenes (Section 7.3). When a halohydrin is treated with base, HX is eliminated and an epoxide is produced. 

Epoxides can also be opened by reaction with acids other than H30+. If anhydrous HX is used, for instance, an epoxide is converted into a trans halohydrin. 

The reversibility of halohydrin dehalogenase-catalyzed reactions has been used for the regioselective epoxide-opening with nonnatural nucleophiles (an example is given in Scheme 10.34) [133]. The stereoselectivity of the enzyme results in the resolution of the racemic substrate. At the same time, the regioselectivity imposed by the active site geometry yields the anti-Markovnikov product. [128]... 

Ring opening of epoxides with nucleophiles other than water (Cl, BrT I, NOz , CN ) can also be catalyzed by halohydrin dehalogenase enzymes (EC 3.8.1.5, also named haloalkane dehalogenase or haloalcohd dehalogenase) (Figure 6.74) [197]. 

When gem-disubstituted epoxides (122) are treated with Grignard reagents (and sometimes other epoxides), the product may be 123, that is, the new alkyl group may appear on the same carbon as the OH. In such cases, the epoxide is isomerized to an aldehyde or a ketone before reacting with the Grignard reagent. Halohydrins are often side products. 

Urea hydrogen peroxide adduct (UHP) was employed in metal-catalysed asymmetric epoxidation [98] and Baeyer-Villiger oxidation [99,100]. Since the presence of urea does not change the course of the reaction, this will not be described here. Conversion of epoxides to halohydrins with elemental... 

The activities of both haloalkanol dehalogenase (halohydrin hydrogen lyase) that catalyzes the formation of epoxides from alkanes with vicinal hydroxyl and halogen groups, and epoxide hydrolase that brings about hydrolysis of epoxyalkanes to diols are involved in a number of degradations that involve their sequential operation. 

Bartnicki EW, CE Castro (1969) Biodehalogenation. The pathway for transhalogenation and the stereochemistry of epoxide formation from halohydrins. Biochemistry 8 4677-4680. 

Castro CE, EW Bartnicki (1968) Biodehalogenation. Epoxidation of halohydrins, epoxide opening, and transhalogenation by a Elavobacterium sp. Biochemistry 1 3213-3218. 

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