Alkenes double bond migration

In isomerization reactions, an alkene is deprotonated to form an allyl anion, which is reprotonated to give the more stable alkene (double-bond migration). The most simple example is the isomerization of 1-butene producing a mixture of cis- and trans-2-butene (Scheme 3). Because the stability of the cis-allyl anion formed as an intermediate is greater than for the trans form, a high cis/trans ratio is observed for base-catalyzed reactions whereas for acid-catalyzed reactions the ratio is close to unity. Thus, the cis/trans ratio of the products has frequently been used as an indication of base-catalyzed reaction mechanisms. The carbanions formed in the course of such superbase reactions are not freely mobile in solution,... 

The Michael-induced RBR exploits the electrophilic nature of vinyl-substituted sulfones. Upon nucleophilic attack, the alkene double bond migrates to form an episulfone intermediate by displacement of an a-halide fScheme R.12T The product alkene, resulting from subsequent SO2 extrusion, is transposed by one position from the original alkene. The a-halide may... 

Alkali metal doped or supported on metal oxides show high activities for alkene double bond migration. Although the states of alkali elements are not known, the reaction intermediates are believed to be anionic, and consequently, it is assumed that the basic sites are operating in the reaction. The most active catalyst among alkali metals dispersed on different metal oxides is sodium dispersed on alumina. The sodium dispersed on alumina shows such a high activity as to proceed double bond migration even at 213 K. ... 

Hydroperoxides have been obtained from the autoxidation of alkanes, aralkanes, alkenes, ketones, enols, hydrazones, aromatic amines, amides, ethers, acetals, alcohols, and organomineral compounds, eg, Grignard reagents (10,45). In autoxidations involving hydrazones, double-bond migration occurs with the formation of hydroperoxy—azo compounds via free-radical chain processes (10,59) (eq. 20). 

The ene reaction is a concerted reaction in which addition of an alkene to an electrophilic olefin occurs with migration of a hydrogen and the alkene double bond. For example ... 

Ion 21 can either lose a proton or combine with chloride ion. If it loses a proton, the product is an unsaturated ketone the mechanism is similar to the tetrahedral mechanism of Chapter 10, but with the charges reversed. If it combines with chloride, the product is a 3-halo ketone, which can be isolated, so that the result is addition to the double bond (see 15-45). On the other hand, the p-halo ketone may, under the conditions of the reaction, lose HCl to give the unsaturated ketone, this time by an addition-elimination mechanism. In the case of unsymmetrical alkenes, the attacking ion prefers the position at which there are more hydrogens, following Markovnikov s rule (p. 984). Anhydrides and carboxylic acids (the latter with a proton acid such as anhydrous HF, H2SO4, or polyphosphoric acid as a catalyst) are sometimes used instead of acyl halides. With some substrates and catalysts double-bond migrations are occasionally encountered so that, for example, when 1 -methylcyclohexene was acylated with acetic anhydride and zinc chloride, the major product was 6-acetyl-1-methylcyclohexene. ... 

The hydrogenation and isomerization of alkenes can usually be described by the classical Horiuti-Polanyi mechanism. According to that mechanism, in a deuterium atmosphere, double bond migration incorporates deuterium into the allylic position. 

Some hydrometalation reactions have been shown to be catalyzed by zirconocene. For instance, CpiZrCf-catalyzed hydroaluminations of alkenes [238] and alkynes [239] with BU3AI have been observed (Scheme 8-34). With alkyl-substituted internal alkynes the process is complicated by double bond migration, and with terminal alkynes double hydrometalation is observed. The reaction with "PrjAl and Cp2ZrCl2 gives simultaneously hydrometalation and C-H activation. Cp2ZrCl2/ BuIi-cat-alyzed hydrosilation of acyclic alkenes [64, 240] was also reported to involve hydrogen transfer via hydrozirconation. 

Since edges (and presumably ledges) are now associated with double bond migration,98 and since apparent trans addition is a function of the double bond migration ability of various catalysts, perhaps such locations can produce both processes. The fact that tetrasubstituted alkenes hydrogenate much more slowly than tri-, di-, or monosubsituted alkenes would allow greater... 

A range of other terminal alkenes has been hydrogenated with ruthenium-diphosphine catalysts. The first set of substrates (Fig. 30.7 Table 30.5) was hydrogenated with Ru-BINAP in dichloromethane (DCM) at 30°C. Products of double bond migration were also detected [5]. 

With more substituted alkenes, reaction under these conditions is often accompanied by double-bond migrations which eventually lead to the formation of an alky ltrichloro silane with a primary alkyl group.51 52... 

The formation of 1,2,3-trioxolanes from an alkene and ozone is the first step in the ozonolysis reaction, which is widely used in synthesis to convert alkenes to aldehydes or carboxylic acids. No instances of double bond migration during ozonolysis are known (since the first step is a cyclo-... 

For reviews of double-bond migrations, see Pines Stalick Base-Catalyzed Reactions of Hydrocarbons and Related Compounds Academic Press New York. 1977, pp, 25-123 DeWolfe, in Bamford Tipper Comprehensive Chemical Kinetics, vol. 9 Elsevier, New York, 1973, pp. 437-449 Yanovskaya Shakhidayatov Russ. Chem. Rev. 1970,39, 859-874 Hubert Reimlinger Synthesis 1969, 97-112,1970, 405-430 Mackenzie, in The Chemistry of Alkenes. vol. 1, Patai, Ed., pp. 416-436, vol. 2, Zabicky, Ed., pp. 132-148 Wiley New York, 1964, 1970 Broaddus, Acc. Chem. Res. 1968, I, 231-238 Cram, Ref. 25, pp. 175-210. 

Selective double-bond migration of linear and cyclic alkenes without skeletal rearrangement is achieved by treatment with basic reagents ([Eq. (1.29)] see also Chapter 4) ... 

In contrast with these results, catalytic cracking yields a much higher percentage of branched hydrocarbons. For example, the catalytic cracking of cetane yields 50-60 mol of isobutane and isobutylene per 100 mol of paraffin cracked. Alkenes crack more easily in catalytic cracking than do saturated hydrocarbons. Saturated hydrocarbons tend to crack near the center of the chain. Rapid carbon-carbon double-bond migration, hydrogen transfer to trisubstituted olefinic bonds, and extensive isomerization are characteristic.52 These features are in accord with a carbo-cationic mechanism initiated by hydride abstraction.43,55-62 Hydride is abstracted by the acidic centers of the silica-alumina catalysts or by already formed carbocations ... 

Migration of the double bond of terminal alkenes to internal position is favored by the equilibria. Thus 1-butene in the presence of activated clay, silica gel, alumina, or phosphoric acid on pumice may yield equilibrium product mixtures comprised of about 20% 1-butene and 80% 2-butenes.91 The main transformation of branched 1-alkenes under mild conditions is also double-bond migration. For example, 2,4,4-trimethyl-1-pentene is isomerized to the equilibrium mixture92 with 20% 2,4,4-trimethyl-2-pentene when treated with silica gel at 25°C. 

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