Big Chemical Encyclopedia

Chemical substances, components, reactions, process design ...

Articles Figures Tables About

Allyl systems isomerization

Alkyl derivatives of 1,3-butadiene usually undergo photosensitized Z-E isomerism when photosensitizers that can supply at least 60 kcal/mol are used. Two conformers of the diene, the s-Z and s-E, exist in equilibrium, so there are two nonidentical ground states from which excitation can occur. Two triplet excited states that do not readily interconvert are derived from the s-E and s-Z conformers. Theoretical calculations suggest that at their energy minimum the excited states of conjugated dienes can be described as an alkyl radical and an orthogonal allyl system called an allylmethylene diradical ... [Pg.772]

Homoallylic systems may isomerize under hydrogenation conditions to allylic systems, causing hydrogenolysis to occur when it would not have been expected (39b,45a-45c). In these cases, if hydrogenolysis is unwanted, it is best to avoid those catalysts and conditions that favor isomerization. Double-bond migration to an allylic position may occur even if the double bond is required to leave a tetrasubstituted position (26a). [Pg.168]

Thus the rotation of the allylic system out of the plane (required before ring closure can occur) results in the reduction of the available allylic resonance energy by about 5 kcal mole". This particular steric requirement does not apply to the isomerizations to the dienes, and these have much the same values as for vinylcyclopropane itself, viz. ... [Pg.159]

It has been shown" that isomerization of the exocyclic allylic system of the five-membered ring D of kaurenols depends on the orientation of the C(15) hydroxyl group. The total synthesis of methyl atis-16-en-19-oate, a tetracyclic diterpenoid possessing a bicyclo[2.2.2]octane skeleton, has been accomplished" using a homoallyl-homoallyl radical rearrangement process of methyl 12-hydroxykaur-16-en-19-oate monothioimid-azolide (280) as the pivotal step. Two plausible mechanisms have been presented" ... [Pg.572]

If the allylic system is substituted, several isomeric products can be formed. Assuming a chair-like transition state, the stereochemical outcome of a metallo-Claisen rearrangement is controlled by the geometries of the vinyl and allyl moieties, so that, if the vinyl part 68 is stereochemically pure, three different products, syn/anti-73 or 74, can be formed, depending on the exact nature of the active allylic part 72 (Scheme 6)38. [Pg.615]

Allylic amide isomerization, 117 Allylic amine isomerization ab initio calculations, 110 catalytic cycle, 104 cobalt-catalyzed, 98 double-bond migration, 104 isotope-labeling experiments, 103 kinetics, 103 mechanism, 103 model system, 110 NMR study, 104 rhodium-catalyzed, 9, 98 Allylnickel halides, 170 Allylpalladium intermediates, 193 Allylsilane protodesilylation, 305 Aluminum, chiral catalysts, 216, 234, 310 Amide dimers, NMR spectra, 282, 284 Amines ... [Pg.192]

A second difficulty arises from consideration of allylic systems. Because the resulting cationic center is stabilized by interaction with the -it electrons, allylic halides ionize readily to produce the delocalized allylic ion, 2. The free ipn theoiy predicts that isomeric allyli halides that give the samp intermediate,-upon ionization should yield a product distribution independent of the isomeric origin of thp ion Scheme 2 illustrates the argument. The prediction is sometimes, but... [Pg.216]

In allylic systems, favorable overlap of the p orbitals of the n system should require a coplanar arrangement of the three sp2 carbons and their five substituent atoms evidence that such a structure is indeed preferred comes, for example, from proton magnetic resonance observations that demonstrate barriers to bond rotation in the isomeric dimethylallyl ions 21, 22, and 23. These ions form stereo-specifically from the three dimethylcyclopropyl chlorides (Section 12.2), and barriers to rotation about the partial double bonds are sufficiently high to prevent interconversion at low temperature. At — 10°C, 21, the least stable isomer,... [Pg.235]

Although various transition-metal complexes have reportedly been active catalysts for the migration of inner double bonds to terminal ones in functionalized allylic systems (Eq. 3.2) [5], prochiral allylic compounds with a multisubstituted olefin (Rl, R2 H in eq 2) are not always susceptible to catalysis or they show only a low reactivity [Id]. Choosing allylamines 1 and 2 as the substrates for enantioselective isomerization has its merits (1) optically pure citronellal, which is an important starting material for optically active terpenoids such as (-)-menthol, cannot be obtained directly from natural sources [6], and (2) both ( )-allylamine 1 and (Z)-allylamine 2 can be prepared in reasonable yields from myrcene or isoprene, respectively, The ( )-allylamine 1 is obtained from the reaction of myrcene and diethylamine in the presence of lithium diethylamide under Ar in an almost quantitative yield (Eq. 3.3) [7], The (Z)-allylamine 2 can also be prepared with high selectivity (-90%) by Li-catalyzed telomerization of isoprene using diethylamine as a telomer (Eq. 3.4) [8], Thus, natural or petroleum resources can be selected. [Pg.146]

Isomerization of a it-allyl species can arise from a bimolecular reaction as shown in Scheme 8E.5 [44], In the case of unsymmetrically substituted allyl systems, this process constitutes... [Pg.596]

Heterogeneous copper catalysts prepared with the chemisorption-hydrolysis technique are effective systems for hydrogen transfer reactions, namely carbonyl reduction, alcohol dehydrogenation and racemization, and allylic alcohol isomerization. Practical concerns argue for the use of these catalysts for synthetic purposes because of their remarkable performance in terms of selectivity and productivity, which are basic features for the application of heterogeneous catalysts to fine chemicals synthesis. Moreover, in all these reactions the use of these materials allows a simple, safe, and clean protocol. [Pg.333]

If we make the two ends of the allyl system more similar, say one end primary and one end secondary, things are more equal. We could consider the two isomeric butenyl chlorides. [Pg.605]

Beside the Grignard and other C-C bond-forming reactions, a number of functional group transformations may also serve as an entry into allylic systems. Some of them, namely the reduction of a, -unsaturated carbonyl compounds (products of crotonic condensation), halogenation of alkenes at the allylic position with Af-bromosuccinimide (NBS) and epoxide isomerization, are shown in Scheme 2.56. [Pg.108]

This catalytic system is also applicable to isomerization of allylic alcohols. Under reaction conditions which are the same as, or milder than, those for the rearrangement of homoallylic alcohols, the allylic alcohols isomerized rapidly [12bj. [Pg.314]

The reactions and product distributions thus far reported have been exclusively concerned with hexene. It was of interest to see whether the high specificity of positional substitution could be maintained with the other hexene isomers. By positional substitution specificity is meant ester attachment on ether of the carbons involved in the original carbon-carbon double bond. Table VII shows the results of these studies. The internal olefins reacted more slowly than the a-olefin, and with both palladium chloride-cupric chloride and 7r-hexenylpalladium chloride-cupric chloride systems high substitutional specificity (> 95% ) was also maintained with 2-hexene (Table VII). However, with 3-hexene the specificity is considerably lower (80%). Whether this is caused by 3-hexene isomerization prior to vinylation or by allylic ester isomerization is not known. A surprisingly high ratio of 2-substitution to 3-substitution is found ( 7 1) in the products from 2-hexene. An effect this large... [Pg.114]

Changes in stereochemistry of the type under consideration might be expected to have a parallel in reactions involving allylic systems. The products of deamination of the isomeric butenyl- and pentenyl-amines in acetic acid and in aqueous solution, shown in Table 5, offer some... [Pg.365]

Other double-bond isomerizations (e.g., those that occur in the course of Pd-catalyzed hydrogenolyses or hydrogenations) proceed by insertion of the alkene into a M-H bond followed by /3-hydride elimination. Wilkinson s catalyst, though, lacks a Rh-H bond into which an alkene can insert. The reaction may proceed by oxidative addition to an allylic C-H bond, then reductive elimination at the other end of the allylic system. [Pg.323]

As shown in Scheme 2, ti-o-ji isomerization can result in syn-anti interconversion by rotation around the o-(C-C) bond in the r -intermediate syn and anti refer to the positions syn and anti to the substituent at C2). The syn position is sterically favored and, consequently, in 1 -monosubstituted allyl systems the syn-isomer is more stable than the anfi-isomer.In general, the thermodynamic equilibrium lies far on the side of the syn-isomer and only if a substituent is sufficiently small (e.g., R=Me) is the anfi-isomer present in notable amounts. However, certain ligands, that exert strong steric hindrance in the coordination plane toward the [Pg.792]


See other pages where Allyl systems isomerization is mentioned: [Pg.774]    [Pg.232]    [Pg.105]    [Pg.369]    [Pg.39]    [Pg.158]    [Pg.302]    [Pg.252]    [Pg.89]    [Pg.155]    [Pg.141]    [Pg.149]    [Pg.234]    [Pg.641]    [Pg.652]    [Pg.282]    [Pg.368]    [Pg.246]    [Pg.984]    [Pg.1002]    [Pg.229]    [Pg.145]    [Pg.158]    [Pg.39]    [Pg.234]    [Pg.771]    [Pg.771]    [Pg.792]    [Pg.793]   


SEARCH



Allyl isomerization

Allyl system

Allylic isomerization

Isomerism systems

© 2024 chempedia.info