Reaction mechanism Wacker oxidation

Under the conditions of the Wacker oxidation, 4-trimethylsilyl-3-alkyn-l-ols give 7 -lactones. Similarly, A-carbamoyl or A-acetyl 4-trimethylsilyl-3-alkynamines cyclize to y -lactams. Formulate a mechanism for these reactions. (Hint In DzO,... 

Wacker (1) A general process for oxidizing aliphatic hydrocarbons to aldehydes or ketones by the use of oxygen, catalyzed by an aqueous solution of mixed palladium and copper chlorides. Ethylene is thus oxidized to acetaldehyde. If the reaction is conducted in acetic acid, the product is vinyl acetate. The process can be operated with the catalyst in solution, or with the catalyst deposited on a support such as activated caibon. There has been a considerable amount of fundamental research on the reaction mechanism, which is believed to proceed by alternate oxidation and reduction of the palladium ... 

Intramolecular coordination is apparently responsible for most examples of regioselective Wacker oxidations of internal olefins, but electronic effects are also operating [28], specifically in acceptor-substituted olefins. Steric effects are currently not well explored [8], Recent theoretical studies on the mechanism of the Wacker and related reactions are available elsewhere [29, 30],... 

The mechanism of the Wacker oxidation has been much investigated. The following reactions are involved ... 

The point has been made that the conditions of p-chloroethanol formation are not the same as used for the Wacker oxidation. Cu Pd chlorine-bridged dimers are likely reactants under higher [Cl ] reaction conditions, which may lead to a different reaction mechanism. However, a second stereochemical study also obtained results consistent with trans hydroxypaUadation. When cfr-l,2-dideuteroethene is oxidized in water with PdCl2 under a CO atmosphere, the product is tran5 -2,3-dideutero-jS-propiolactone (Scheme 37). The reaction conditions were, once again, not identical with standard Wacker process conditions, since the solvent was acetonitrile water, the temperature was —25°C, the bis-ethene PdCl2 complex was used, and there was no excess Cl present. Nevertheless, it is clear that, under many reaction conditions, a trans addition of water onto ethene coordinated to Pd is the favored reaction stereochemistry. 

Among the several types of homogeneously catalyzed reactions, oxidation is perhaps the most relevant and applicable to chemical industry. The well-known Wacker oxidation of ethylene to ethylene oxide is the classic example, although this is not a true catalytic process since the palladium (II) ion becomes reduced to metallic palladium unless an oxygen carrier is present. Related to this is the commercial reaction of ethylene and acetic acid to form vinyl acetate, although the mechanism of this reaction does not seem to have yet been discussed publicly. Attempts to achieve selective oxidation of olefins or hydrocarbons heterogeneously do not seem very successful. 

The reaction according to eq. (4) seems to proceed via a mechanism which is common for the homogeneous Pd-catalyzed reactions that are often referred to as Wacker oxidations (cf. Section 2.4.1, [4, 8, 9]). In fact, there are several liquid-phase olefin oxidations that are catalyzed by Pd complexes, and the nature of the reaction products depends on the solvent used (Scheme 3). 

Hegedus proposed that the mechanism of this transformation proceeds through a Wacker-type reaction mechanism that is promoted by Pd(II). As shown below, coordination of the olefin to Pd(II) results in precipitate 121, which upon treatment with Et,N undergoes intramolecular trany-aminopalladation to afford intermediate 122. As expected, the nitrogen atom attack occurs in a 5-exo-trig fashion to afford 123. [l-Hydride elimination of 123 gives rise to exocyclic olefin 124, which rearranges to indole 120. The final step of this mechanism leads to the formation of catalytically inactive Pd(0). However, addition of oxidants such as benzoquinone allows for catalytic turnover. 

Many types of palladium-catalyzed oxidative fimctionalizations of olefins related to the Wacker process have been developed, and these reactions are presented later in this chapter. To imderstand the relationship between these reactions and the basic Wacker oxidation of ethylene to form acetaldehye, the mechanism of the Wacker process is discussed before the related oxidation processes. 

The mechanism of the Wacker oxidation has been the subject of many mechanistic studies and much discussion for nearly 50 years. At this point, the identity of the elementary steps of this process appears to depend on the reaction conditions. The majority of the mechanistic discussion has focused on whether the C-O bond is formed by nucleophilic attack of water on a coordinated olefin or by insertion of an olefin into a metal-hydroxo complex. These elementary reactions were discussed in Qiapters 11 and 9, respectively. It appears that the mechanism involving nucleophilic attack occurs under conditions of high chloride concentration, and the mechanism involving olefin insertion occurs imder conditions of low chloride concentration. ... 

The last catalytic reaction we examine in this overview is the Wacker oxidation of ethylene to acetaldehyde with O2, now used to make about 4 million tons a year of aldehydes from alkenes. This reaction shows several new features of great interest. Although the work started with a commonplace observation— the stoichiometric oxidation of alkenes by Pd(II) salts with formation of Pd(0)— the authors were able to make the system catalytic by finding a clean way to reoxidize the Pd(0) to Pd(II) with air. The mechanism was obscure for years because the kinetics gave an incomplete picture and it was only with sophisticated labeling studies that the currently accepted mechanism was discovered. 

There are other Pd-catalyzed or -promoted oxidation reactions of various hydrocarbons under similar reaction conditions. These reactions also involve C—H activation, which may proceed via 1,2-elimination. However, the overall mechanism may be different from that of the Wacker oxidation. For example, oxidation of benzene to phenol with O2 and Pd(OAc)2 may appear to be an arene version of the Wacker oxidation. However, as discussed later in this section, it must proceed via phenylpalladium acetate. For /3-elimination leading to C—H activation, two limiting mechanisms, one ionic and the other concerted, may be considered (Scheme 1). The concerted path (path b) is particularly attractive, as it also readily provides a plausible mechanism for widely observed benzylic, ally lie, and propargyhc C— H activation via 1,2-elimination as well as for alkynyl C—H activation (Scheme 2). 

Supercritical CO2 is a non-polar, aprotic solvent and promotes radical mechanisms in oxidation reactions, similar to liquid-phase oxidation. Thus, wall effects might occur as known, e.g. from olefin epoxidation with 02 or H202 which may decrease epoxide selectivities. The literature covers the synthesis of fine chemicals by oxidation either without catalysts (alkene epoxidation, cycloalkane oxidation, " Baeyer-Villiger oxidation of aldehydes and ketones to esters ), or with homogeneous metal complex catalysts (epoxidation with porphyrins, salenes or carbonyls ). Also, the homogeneously catalysed oxidation of typical bulk chemicals like cyclohexane (with acetaldehyde as the sacrificial agent ), toluene (with O2, Co +/NaBr ) or the Wacker oxidation of 1-octene or styrene has been demonstrated. 

Mechanisms of oxidation are extremely diverse and may be of several free radical or charge transfer types as well as organometallic or Wacker-type reaction. Most of the last type depend on the reaction of a substrate with an oxidized form of the catalyst. An alternative would be to form a complex with the reduced form of the catalyst and then oxidize it, e.g.,... 

What is the oxidation product of ethylene by O2 (Wacker process) in acetic acid (Moiseev reaction) Write the reaction mechanism. 

Water is so extensively used in catalytic oxidation reactions that usually this fact is regarded as a natural feature and remains unnoticed. Wacker oxidation of olefins by palladium complexes involves water as a nucleophilic reagent, and thus the whole Wacker-type chemistry, which has developed into a powerful and versatile method of organic synthesis, is derived from aqueous catalysis [178]. The role of the nature of the co-oxidant and the mechanism of deactivation of the palladium catalyst due to aggregation and growth of inactive metal particles were recently investigated, and such study may have relevance for other processes catalyzed by phosphine-less palladium catalysts [179]. 

Kinetic and isotope-labeling studies are fully consistent with the mechanism shown for Wacker oxidation in Figure 8.1. The conversion of 8.4 to 8.5 is the rate-determining step. The conversion of 83 to 8.4 has been a matter of some controversy. In principle, both intermolecular reaction between 8.3 and external water and intramolecular reaction between coordinated ethylene and coordinated water could lead to the formation of 8.4. 

---