Alcohol oxide catalysis

Silver carbonate, alone or on CeHte, has been used as a catalyst for the oxidation of methyl esters of D-fmctose (63), ethylene (64), propylene (65), trioses (66), and a-diols (67). The mechanism of the catalysis of alcohol oxidation by silver carbonate on CeHte has been studied (68). 

The complex Pd-(-)-sparteine was also used as catalyst in an important reaction. Two groups have simultaneously and independently reported a closely related aerobic oxidative kinetic resolution of secondary alcohols. The oxidation of secondary alcohols is one of the most common and well-studied reactions in chemistry. Although excellent catalytic enantioselective methods exist for a variety of oxidation processes, such as epoxidation, dihydroxy-lation, and aziridination, there are relatively few catalytic enantioselective examples of alcohol oxidation. The two research teams were interested in the metal-catalyzed aerobic oxidation of alcohols to aldehydes and ketones and became involved in extending the scopes of these oxidations to asymmetric catalysis. 

Barium oxide and sodium hydride are more potent catalysts than silver oxide. With barium oxide catalysis, reactions occur more rapidly but O-acetyl migration is promoted. With sodiun hydride, even sterically hindered groups may be quantitatively alkylated but unwanted C-alkylation Instead of, or in addition to, 0-alkylatlon is a possibility. Sodium hydroxide is a suitable catalyst for the alkylation of carboxylic acids and alcohols [497J. 

Yeast alcohol dehydrogenase, catalysis of oxidation by NAD of benzyl alcohol equilibrium interconversion of benzyl alcohol and benzaldehyde... 

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). 

Nanoparticles, which often show enhanced catalytic abilities [32, 33] unusual optical properties [34], and novel quantum size effects [35], have been widely used in fields such as catalysis [36, 37], sensing [38], optoelectronics [39], and microelectronics [40]. Nanoparticle catalysis is industrially and experimentally important because a large variety of C-C coupling [41] and alcohol oxidation [32] can be effectively catalyzed by nanoparticles. In this part, we will present a brief review on recent advances in supported nanoparticle heterogeneous catalysts on various mesoporous materials. Heterogeneous nanoparticle catalysts have several... 

The present paper illustrates the versatility of Mo and W exchanged LDHs in heterogeneous oxidation catalysis with three selected examples (a) the W-catalyzed epoxidation of allyl alcohol, (b) the Mo-catalyzed epoxidation of cyclohexene, (c) the bleaching of a typical model dye component with aqueous H202. 

Selective oxidation of alkanes and benzene derivatives to alcohols and phenols, respectively, are among the most difficult reactions in oxidation catalysis. Therefore, the stoichiometric hydroxylation of alkenes and aromatics performed by a-oxygen at room temperature has aroused great interest as a potential way for developing new steady state catalytic processes for the preparation of these valuable products, similar to the hydroxylation of benzene to phenol. 

Oxidation Catalysis Olefinic alcohol epoxidation with t-BuOOH VO(OiPr)3... 

Several studies have tackled the structure of the diketopiperazine 1 in the solid state by spectroscopic and computational methods [38, 41, 42]. De Vries et al. studied the conformation of the diketopiperazine 1 by NMR in a mixture of benzene and mandelonitrile, thus mimicking reaction conditions [43]. North et al. observed that the diketopiperazine 1 catalyzes the air oxidation of benzaldehyde to benzoic acid in the presence of light [44]. In the latter study oxidation catalysis was interpreted to arise via a His-aldehyde aminol intermediate, common to both hydrocyanation and oxidation catalysis. It seems that the preferred conformation of 1 in the solid state resembles that of 1 in homogeneous solution, i.e. the phenyl substituent of Phe is folded over the diketopiperazine ring (H, Scheme 6.4). Several transition state models have been proposed. To date, it seems that the proposal by Hua et al. [45], modified by North [2a] (J, Scheme 6.4) best combines all the experimentally determined features. In this model, catalysis is effected by a diketopiperazine dimer and depends on the proton-relay properties of histidine (imidazole). R -OH represents the alcohol functionality of either a product cyanohydrin molecule or other hydroxylic components/additives. The close proximity of both R1-OH and the substrate aldehyde R2-CHO accounts for the stereochemical induction exerted by RfOH, and thus effects the asymmetric autocatalysis mentioned earlier. 

It should be noted that the related imine-oxaziridine couple E-F finds application in asymmetric sulfoxidation, which is discussed in Section 10.3. Similarly, chiral oxoammonium ions G enable catalytic stereoselective oxidation of alcohols and thus, e.g., kinetic resolution of racemates. Processes of this type are discussed in Section 10.4. Whereas perhydrates, e.g. of fluorinated ketones, have several applications in oxidation catalysis [5], e.g. for the preparation of epoxides from olefins, it seems that no application of chiral perhydrates in asymmetric synthesis has yet been found. Metal-free oxidation catalysis - achiral or chiral - has, nevertheless, become a very potent method in organic synthesis, and the field is developing rapidly [6]. 

Re has recently come to the forefront in liquid phase oxidation catalysis, mainly as a result of the discovery of the catalytic properties of the alkyl compound CH3Re03 [methyltrioxorhenium (MTO)]. MTO forms mono-and diperoxo adducts with H2O2 these species are capable of transferring an oxygen atom to almost any nucleophile, including olefins, allylic alcohols, sulfur compounds, amides, and halide ions (9). Moreover, MTO catalysis can be accelerated by coordination of N ligands such as pyridine (379-381). An additional effect of such bases is that they buffer the strong Lewis acidity of MTO in aqueous solutions and therefore protect epoxides, for example. 

FIGURE 19 Changes during alcohol oxidation on supported molybdena catalysts (A) methanol oxidation (Reprinted from Journal of Catalysis 150, 407 (1994), M.A. Banares, H. Hu, I.E. Wachs, Molybdena on Silica Catalysts - Role of Preparation Methods on the Structure Selectivity Properties for the Oxidation of Methanol, copyright (1994) with permission from Elsevier). (B) ethanol oxidation (Reprinted with permission from Journal of Physical Chemistry, 99,14468 (1995) by W. Zhang, A. Desikan, S.T. Oyama, Effect of Support in Ethanol Oxidation on Molybdenum Oxide, copyright 1995, American Chemical Society). 

In the so called pinacol(ine)(one)-rearrangement water is eliminated from 1,2-diols 57). If it is run under acid-catalysis, it will undoubtedly proceed via a more or less free solvated carbocation, in which a migration ( Wagner-Meerwein-rearrange-ment ) of the substituent occurs from relative position 2 to 3. Therefore, it should be classified as a [l,2,3]-elimination (Scheme 5). The same is true for the Tiffenau-reaction (Scheme 6), which also succeeds in the poly- and acyclic families. By deamination of cyclic -amino-alcohols [oxidative [l,2,3]-elimination of (formally) ammonia via a possibly not fully free carbocation] the same ring enlarged ketones... 

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