Isomerization migration

Alkene isomerization/migration is a potential side-reaction in olefin metathesis processes that can significantly decrease the yield of a desired product, particularly in reactions that employ electron-rich allylic or homoallylic... 

Thermogravimetric curves for the polyacetylene, there are two exothermic peaks at 145 and 325°C [16]. The first of these corresponds to an irreversible cis-trans isomerization. Migration of hydrogen occurs at 325°C, open chain and cross-linking without the formation of polyacetylene volatile products. The color of the polymer becomes brown. A large number of defects appears. In the infrared spectrum there are absorption bands characteristic of the CH, CH3, -C=C- and -C2H5- groups [16]. 

Alkene isomerization/migration is an undesired side reaction in olefin metathesis. This isomerization has been attributed to ruthenium hydride species formed upon catalyst decomposition [63, 64]. Several computational investigations of ruthenium hydride-catalyzed olefin isomerization have been reported, in which the isomerization was found to occur via olefin insertion into the ruthenium hydride, rotation about the Ru-C a bond, and P-hydride elimination (Scheme 7.15a) [65, 66]. These processes typically require only relatively low activation barriers. Once the ruthenium hydride is formed, olefin isomerization... 

Scheme 12.30 Ru-hydride decomposition product 100, which can promote the isomerization/migration of olefins.

NMR analysis showed that the tritium was distributed along the entire carbon chain as indicated in the strucmre. This result is likely due to a combination of double bond isomerization, migration and saturation processes. Such greater-than-normal incorporation of label can be beneficial in enabling improved sensitivities of detection in the use of the labeled compounds, but only if the regioselectivity of labeling is not detrimental. 

What happens when isomerization is performed is that the double bond of the allylbenzene safrole migrates to the more energetically favorable position between the alpha and beta carbons of the propyl side chain. Thus isosafrole, a propenylbenzene, is born. 

Diacetoxylation of various conjugated dienes including cyclic dienes has been extensively studied. 1,3-Cyclohexadiene was converted into a mixture of isomeric l,4-diacetoxy-2-cyclohexenes of unknown stereochemistry[303]. The stereoselective Pd-catalyzed 1,4-diacetoxylation of dienes is carried out in AcOH in the presence of LiOAc and /or LiCI and beiizoquinone[304.305]. In the presence of acetate ion and in the absence of chloride ion, /rau.v-diacetox-ylation occurs, whereas addition of a catalytic amount of LiCl changes the stereochemistry to cis addition. The coordination of a chloride ion to Pd makes the cis migration of the acetate from Pd impossible. From 1,3-cyclohexadiene, trans- and ci j-l,4-diacetoxy-2-cyclohexenes (346 and 347) can be prepared stereoselectively. For the 6-substituted 1,3-cycloheptadiene 348, a high diaster-eoselectivity is observed. The stereoselective cij-diacetoxylation of 5-carbo-methoxy-1,3-cyclohexadiene (349) has been applied to the synthesis of dl-shikimic acid (350). 

The aldehyde or ketone is called the keto form and the keto enol equilibration referred to as keto-enol isomerism or keto-enol tautomerism Tautomers are constitu tional isomers that equilibrate by migration of an atom or group and their equilibration IS called tautomerism The mechanism of keto-enol isomerism involves the sequence of proton transfers shown m Figure 9 6... 

Step 2 Enzyme catalyzed proton transfer steps cause migration of the double bond converting the mine formed m step 1 to an isomeric mine... 

Migration of the Methyl Groups. Reactions that involve migration of the methyl groups include isomerization, disproportionation, and... 

Transalkylation is also catalyzed by acids, but requires more severe conditions than isomerization. As shown below, the methyl migration is intermolecular and ultimately produces a mixture of aromatic compounds ranging from benzene to hexamethylbenzene. The overall equiHbrium constants for all possible methylbenzenes have been deterrnined experimentally and calculated theoretically (Fig. 2 and Table 3). 

Bromination can be conveniently effected by transfer of bromine from one nucleus to another. As the Friedel-Crafts isomerization of bromoaromatic compounds generally takes place through an intermolecular mechanism, the migrating bromine atom serves as a source of positive bromine, thus effecting ring brominations (161,162). 2,4,6-Tribromophenol, for example, has been prepared by bromination of phenol with dibromobenzene. 

From a general point of view, the tautomeric studies can be divided into 12 areas (Figure 20) depending on the migrating entity (proton or other groups, alkyl, acyl, metals. ..), the physical state of the study (solid, solution or gas phase) and the thermodynamic (equilibrium constants) or the kinetic (isomerization rates) approach. 

A well-known example of non-prototropic tautomerism is that of azolides (acylotropy). The acyl group migrates between the different heteroatoms and the most stable isomer (annular or functional) is obtained after equilibration. In indazoles both isomers are formed, but 2-acyl derivatives readily isomerize to the 1-substituted isomer. The first order kinetics of this isomerization have been studied by NMR spectroscopy (74TL4421). The same publication described an experiment (Scheme 8) that demonstrated the intermolecular character of the process, which has been called a dissociation-recombination process. 

Diazo compounds react with alkenes to afford A -pyrazolines, which in turn izomerize to A -pyrazolines if there is a hydrogen atom a to the N=N bond (Scheme 54). In those cases where two possible ways of isomerization exist, the more acidic hydrogen migrates preferentially. The alkene configuration is conserved on the A -pyrazoline (stereospecificity) but the regioselectivity depends on the substituents of both the alkene and the diazo compound. 

The isomerization of oxaziridines (1) to acid amides with migration of a substituent from C to N is a general reaction and is always observed when no other reactions predominate under the relatively harsh conditions (heating to above 150 °C or photolysis). Even then one can make acid amide formation the main reaction by working at 300 °C (57JA5739) and by dilution techniques. For example, caprolactam (63) is formed in 88% yield by flash pyrolysis of oxaziridine (52) at about 300 °C, whereas decomposition of (52) at lower temperatures gives almost no (63) (77JPR274). 

The double bond migration in steroid hydrocarbons catalyzed by acids or noble metals (see, for example, ref. 185) will not be discussed here. A general review of nonsteroid olefin isomerization has recently been published. Iron carbonyl has been used to isomerize steroidal dienes. 

To the structural generalizations on carborancs (p. 183) can be added the rule that, in metallocarboranes, the M atom tends to adopt a vertex with high coordination number. M occupancy of a low CN vertex is not precluded, particularly in kineiically controlled syntheses, but isomerization to more stable configurations usually results in the migration of M to high CN vertices. 

In 57 a bromine migration possibly competes with the generation of 4-ethoxy-2,3-pyridyne (58), induced by the abstraction of a hydrogen ion from C-2 of 57 (cf. the isomerization of 1,2,4-tribromobenzene to... 

Apart from the IH and 2H tautomers 2a and 2b, isomeric forms in which the migrating proton takes up its position on one of the carbon atoms in the ring are formally possible. For the case of unsubstituted pyrazole 2, R = r2 = r3 = tjjg tautomeric equilibrium should be represented by the scheme involving 4H 2e and a pair of degenerate 5H species 2c and 2d (Scheme 2). 

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