Hydride abstraction mechanism

That reaction rates are barely affected by the nuclear substitution ill-accords with the hydride abstraction mechanism. However, nuclear substitution affects both the ionisation of the alcohol as well as the oxidation step. The value of k IkT agrees well with that of 55.5 calculated from kujk,) by means of the Swain relationship, i.e. kujkpy- = k lkr. 

Hirschler and Hudson (36/6), however, favor the opinion that Bronsted sites are exclusively responsible for the activity of silica-alumina. In studying the adsorption of perylene and of triphenylmethane, they concluded that carbonium ions are not formed by a hydride abstraction mechanism as claimed by Leftin (362). Instead, triphenylmethane is oxidized by chemisorbed oxygen to triphenylcarbinol in a photo-catalyzed reaction, followed by reaction with a Bronsted acid giving water and a triphenylmethyl carbonium ion. After treatment with anhydrous ammonia, the organic compound was recovered by extraction as triphenylcarbinol. About thirteen molecules of ammonia per assumed Lewis site were required to poison the chemisorption of trityl ions. The authors explain the selective inhibition of certain catalyzed reactions by alkali by assuming that only certain of the acidic protons will ion-exchange with alkali ions. 

One of the main difficulties in understanding the carbocationic nature of acid-catalyzed transformations of alkanes via the hydride abstraction mechanism was that no stoichiometric amount of hydrogen gas evolution was ever observed from the reaction mixture, although even in the early work of Nenitzescu et al. H2 gas was detected in measurable amounts. For this reason, an alternative mechanism was proposed The direct hydride abstraction by the Lewis acid [Eq, (6,10)],... 

P-Hydrogen eliminations and p-aryl eliminations from alkoxo and amido complexes are also known. Such eliminations have been shown to occur by migratory de-insertion pathways, as well as alternative p-hydride abstraction mechanisms. P-Hydrogen eliminations from metal-silyl complexes are rare because the silicon-carbon double bond in the product is weak. For similar reasons, p-hydrogen eliminations from metal-thiolate complexes are rare. 

The extremely electrophilic tetrafluoropyridylnitrene inserts into C-H bonds much more readily than does phenylnitrene, and again evidence for the triplet nitrene was presented. In other experiments the same workers discounted the possibility of a hydride abstraction mechanism. Intramolecular C-H insertions are known to proceed in high yield through the triplet nitrene (see Section III.l) ... 

Further research into the reaction mechanism revealed that the reaction rate was correlated with the electron structure of the sulfoxide the more electropositive sulfoxides were the better oxygen donors. Excellent correlation of the reaction rates with the heterolytic benzylic carbon-hydrogen bond dissociation energies indicated a hydride abstraction mechanism in the rate-determining step to yield a carbocation intermediate. The formation of 9-phenylfluorene as by-product in the oxidation of triphenylmethane supports this suggestion. Further kinetic experiments and NMR showed the formation of a polyoxometalate-sulfoxide complex before the oxidation reaction, this complex being the active oxidant in these systems. Subsequently, in a similar reaction system, sulfoxides were used to facilitate the aerobic oxidation of alcohols [29]. In this manner, benzylic, allyUc, and aliphatic alcohols were all oxidized to aldehydes and ketones in a reaction catalyzed by Ke jn-type... 

Ph3C BF4, CH2CI2, 5-30 min, 80-95% yield. " The mechanism of this cleavage has been determined to involve complex formation by the trityl cation with the sulfur, followed by hydrolysis, rather than by hydride abstraction. ... 

A few results have been reported on the oxidation of cyclohexanol by acidic permanganate In the absence of added fluoride ions the reaction is first-order in both alcohol and oxidant , the apparent first-order rate coefficient (for excess alcohol) at 25 °C following an acidity dependence k = 3.5-1-16.0 [H30 ]sec fcg/A , depends on acidity (3.2 in dilute acid, 2.4 in 1 M acid) and D2o/ H20 is f-74. Addition of fluoride permitted observation of the reaction for longer periods (before precipitation) and under these conditions methanol is attacked at about the same rates as di-isopropyl ether, although dioxan is oxidised over twenty times more slowly. The lack of specificity and the isotope effect indicates that a hydride-ion abstraction mechanism operates under these conditions. (The reactivity of di-isopropyl ether towards two-equivalent oxidants is illustrated by its reaction with Hg(II).) Similar results were obtained with buffered permanganate. 

Hannon and Traylor158 used a specifically labelled organotin hydride, l/iiw-3-deutero-2-trimethylstannylbutane, to determine the mechanism and stereochemistry of the hydride abstraction from an organostannane by a carbocation (equation 101). 

The four hitherto known routes of the C-H insertion are shown in Scheme 1. In general, the insertion by singlet carbenes proceeds via route a in one step, whereas the reaction by triplet carbenes proceeds sequentially via route b, i.e., hydrogen abstraction followed by recombination of the radical pairs.4 Other stepwise mechanisms are hydride abstraction (route c) and proton abstraction (route d), both being followed by the recombination of ion pairs. However, extended study on routes c and d for synthetic purposes had not been done before we started, except for a few earlier studies on carbanion-promoted P C-H insertion reactions.5,6 Recent advances in transition metal-catalyzed... 

E.Z-Selectivity in the insertion by unsymmetrical carbenoid 24, is specifically indicative of the transition state of the stepwise mechanism. Based on the evidence that carbenoid 24, which is generated from 42 or 43 (E Z = 84 16), exists nearly exclusively in the -configuration under the equilibrium even at —95°C,29 the observed stereoselectivity for E-isomers in the insertion products verifies that hydride abstraction takes place via an Sn2-like transition state 52 with inversion of configuration at the carbenoid carbon, followed by the recombination of menthone 40 and carbanion 53 (Scheme 19). 

The bathochromic shifts with increasing chain concentration are compatible with the mechanism proposed above, since an increase in the concentration of unsaturated chains will favour hydride abstraction and will therefore give allylic ions with higher degrees of conjugation, which will absorb at wavelengths greater than 450 mp. The only serious chemical (as opposed to mechanistic) uncertainty in this scheme is whether route III—> IB or III — IC, or both, or perhaps some other process, adequately represent the removal of the ions by addition of monomer. Some reaction path of this kind seems to exist since there is no evidence that either route II —> III or route II — VI is reversible. 

The mechanism of alkyl hydrogen exchange was not clarified, but a possible mechanism was postulated. Partial hydride abstraction by a Lewis acid site may have occured forming a carbocation-like species followed by exchange of a proton at a R-carbon. Such a mechanism predicts exchange to occur preferentially at methyl groups adjacent to the most stable carbocations (benzylic > 3° > 2° > 1°). This is consistent with the observed relative rates of epimerization of steranes during thermal maturation of sediments (83). 

The different synthetic applications of acceptor-substituted carbene complexes will be discussed in the following sections. The reactions have been ordered according to their mechanism. Because electrophilic carbene complexes can undergo several different types of reaction, elaborate substrates might be transformed with little chemoselectivity. For instance, the phenylalanine-derived diazoamide shown in Figure 4.5 undergoes simultaneous intramolecular C-H insertion into both benzylic positions, intramolecular cyclopropanation of one phenyl group, and hydride abstraction when treated with rhodium(II) acetate. 

If chiral catalysts are used to generate the intermediate oxonium ylides, non-racemic C-O bond insertion products can be obtained [1265,1266]. Reactions of electrophilic carbene complexes with ethers can also lead to the formation of radical-derived products [1135,1259], an observation consistent with a homolysis-recombination mechanism for 1,2-alkyl shifts. Carbene C-H insertion and hydride abstraction can efficiently compete with oxonium ylide formation. Unlike free car-benes [1267,1268] acceptor-substituted carbene complexes react intermolecularly with aliphatic ethers, mainly yielding products resulting from C-H insertion into the oxygen-bound methylene groups [1071,1093]. 

The preferred mechanism (66) for the isomerization involves 7r-complex-ing followed by hydride abstraction to give a 7r-allylrhodium hydride intermediate, e.g.,... 

Mechanism B-. The redox reaction is intimately connected to a chemical reaction, for instance a hydrogen or hydride abstraction. 

The results implicate the mechanism shown in Scheme 6. Thus initial migratory insertion of CO into the Zr-C bond is followed by intramolecular insertion of the oxycarbene into the Zr-H bond to produce what could be considered an aldehyde adduct of bis(pentamethylcyclopentadienyl)zirconium(II). The final step involves simple /J-hydride abstraction to give the enolate hydride, 24. 

Sommer (130, 130a) and Hall (131) have independently described the low-temperature H/D exchange of isobutane on zeolites. The traditional mechanism involves a five-coordinate carbonium ion intermediate yet no exchange occurred for the methine position, and this is inconsistent with a carbonium ion. This surprising result was explained by Sommer with a reaction sequence beginning with hydride abstraction by an unknown route... 

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