Selective oxidation mechanistic studies

Bagnasco, G., Peluso, G., and Russo, G., Ammonia oxidation over CuO/Ti02 selectivity and mechanistic study, paper presented at the 3rd World Congress on Oxidation Catalysis, 1997, pp. 643-652. 

AMMONIA OXIDATION OVER Cu0/Ti02 CATALYST SELECTIVITY AND MECHANISTIC STUDY... 

The oxidation of benzylic alcohols was quantitative within hours and selective to the corresponding benzaldehydes, but the oxidation of allylic alcohols was less selective. The oxidation of aliphatic alcohols was slower but selective. In mechanistic studies considering oxidation of benzylic alcohols, similar to the oxidation of alkylarenes, a polyoxometalate-sulfoxide complex appears to be the active oxidant. Further isotope-labeling experiments, kinetic isotope effects, and especially Hammett plots showed that oxidation occurs by oxygen transfer from the activated sulfoxide and elimination of water from the alcohol. However, the exact nature of the reaction pathway is dependent on the identity of substituents on the phenyl ring. 

FIGURE 6.42 Oxidation of 3-oxa-chromanol 58 in the presence of 1 equivalent of water mechanistic study hy means of selectively deuterated starting material. The initially formed ortho-quinone dimethide 63 rearranges into styrene derivative 64, which then reacts with water to provide acetophenone 61. 

The attractive (80) features of MOFs and similar materials noted above for catalytic applications have led to a few reports of catalysis by these systems (81-89), but to date the great majority of MOF applications have addressed selective sorption and separation of gases (54-57,59,80,90-94). Most of the MOF catalytic applications have involved hydrolytic processes and several have involved enantioselec-tive processes. Prior to our work, there were only two or three reports of selective oxidation processes catalyzed by MOFs. Nguyen and Hupp reported an MOF with chiral covalently incorporated (salen)Mn units that catalyzes asymmetric epoxidation by iodosylarenes (95), and in a very recent study, Corma and co-workers reported aerobic alcohol oxidation, but no mechanistic studies or discussion was provided (89). 

Indolizines were arylated under similar conditions selectively in the 3-position (6.90.). A detailed mechanistic study of the transformation revealed that in this reaction the arylpalladium species, formed in the first step of the catalytic cycle, is attached to the indolizine core in an electrophilic substitution step, which is followed by reductive elimination. The presence of alternate routes such as Heck-type insertion, oxidative addition of the C-H bond, or transmetalation were excluded on the basis of experimental evidence.121... 

Most mechanistic studies have focused on elucidation of the role of alkali promoters. The addition of Li+ to MgO has been shown to decrease the surface area and to increase both methane conversion and selective C2 production.338,339 As was mentioned, however, besides this surface-catalyzed process, a homogeneous route also exists to the formation of methyl radicals.340-342 The surface active species on lithium-doped catalysts is assumed to be the lithium cation stabilized by an anion vacancy. The methyl radicals are considered to be produced by the interaction of methane with O- of the [Li+0-] center330,343 [Eq. (3.32)]. This is supported by the direct correlations between the concentration of [Li+0 ] and the concentration of CH3 and the methane conversion, respectively. The active sites then are regenerated by dehydration [Eq. (3.33)] and subsequent oxidation with molecular oxygen [Eq. (3.34)] ... 

The rearrangement of light and deuterium-labelled cis- and trans-2-methyl-3-phenyloxiranes (1, 2 and 1, 2 ) was studied on ZnO, Al-O-j and WO, and in the presence of BF,. Both in the gas phase (473-673 K) and in the liquid phase (298-413 K), l-phenyl-2-propanone (3) and 2-phenylpropanal (4) were formed with high selectivities (0-90% and 11-80%, respectively). Ring-opening was found to occur by selective fission of the benzyl C-0 bond. Mechanistic studies revealed the formation of an open carbenium ion or a double-bonded surface intermediate. The acidic (electrophilic) and basic characters of the oxides determine the product distributions by affecting the relative importance of the competing mechanisms. 

As early as in 1956, Braude et al.92 suggested that the selective oxidation of unsaturated alcohols with the quinone o-chloranil (82), can be explained by the intermediacy of a resonance-stabilized cation resulting from a hydride abstraction. Later, detailed mechanistic studies confirmed this hypothesis94c,95e in oxidations performed with the more common quinone DDQ. 

Pyridylarenes undergo Cu(II)-catalysed diverse oxidative C-H functionalization reactions. The tolerance of alkene, alkoxy, and aldehyde functionality is a synthetically useful feature of this reaction. A radical-cation pathway (Scheme 4) has been postulated to explain the data from mechanistic studies. A single electron transfer (SET) from the aryl ring to the coordinated Cu(II) leading to the cation-radical intermediate is the rate-limiting step. The lack of reactivity of biphenyl led to the suggestion that the coordination of Cu(II) to the pyridine is necessary for the SET process. The observed ortho selectivity is explained by an intramolecular anion transfer from a nitrogen-bound Cu(I) complex.53... 

The first example of intermolecular Pd-catalysed aminoacetoxylation of alkenes, such as (52), with phthalimide as the nitrogen source and PhI(OAc)2 as the stoichiometric oxidant and source of acetate has been reported. The reaction is highly regio- and diastereo-selective mechanistic studies revealed that the reaction proceeds... 

The ability to incorporate deuterium or tritium selectively into appropriate positions on nucleotides has had a tremendous impact on mechanistic studies on sugar oxidation. In particular, Stubbe and coworkers have shown that when thymidine deuterated at the 4 position is incorporated into restriction fragments, sequence-selective isotope effects are observed for cleavage by Fe-BLM (12). These isotope effects are essentially equal for the radical and carbocation pathways (Scheme... 

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