Subject Wacker process

Oxidation Catalysis by Copper Peroxo and Superoxo Complexes. Copper ions and compounds participate in or catalyze a variety of oxidation reactions that consume 02. This is one of the several key biochemical roles of copper and much of the recent work on the subject has been done in efforts to model the biological systems. In some (non-biological) cases, e.g., the Wacker process, copper(II) itself may be the actual oxidant, but usually it serves as a carrier of oxygen. 

The Wacker process was a major landmark and a great push towards the development of homogeneous catalysis. The mechanism of acetaldehyde formation differs fundamentally from the other oxidation processes as O2 itself is not directly involved. As is clear from Figure 28 the actual oxidant is Pd(II) which is reduced to Pd(0). The intimate pathway of the reaction involves nucleophilic attack and was the subject of much debate. 

Much of what is currently known about substitution reactions of square planar complexes came from a lar e number of careful studies executed in the I960s and I970S.3 You should not conclude, however, that details of the mechanisms of these I eactions are of historical intei est only. Work in this area continues unabated as studies focus on chelation, steric effects, biological i eactions. and homogeneous catalysts. For example, the mechanism for the Wacker process (Chapter 15), which utilizes squai e planar [PdCl ] as a homogeneous catalyst for the industrial conversion of ethylene to acetaldehyde, is still a subject of investigation. The overall reaction for the process is ... 

This article will be concerned with the mechanisms of some of these reactions and with some of the general principles that underly this relatively new and rapidly developing field of chemistry. The subject in question has attracted much interest in recent years both because of the novelty of much of the chemistry it reveals and because of its potential practical applications, exemplified by at least two processes (the Oxo and Wacker processes) which have already achieved considerable industrial importance. The possible relevance of many of the catalytic reactions in this field as model systems for related heterogeneous and enzymic process also lends interest to the subject although attempts to exploit this theme have thus far met with only limited success. 

When 1,3-dienes containing a tethered alcohol are subjected to Wacker-type reactions, the initial intramolecular oxypalladation event creates a 7r-allylpalladium species, which can then undergo an additional bond-forming process to effect an overall 1,4-difunctionalization of the diene with either cis- or // -stereochemistry (Scheme 18).399 An array of substrate types has been shown to participate in this reaction to generate both five- and six-membered fused or ro-oxacycles.435-437 Employing chiral benzoquinone ligands, progress toward the development of an asymmetric variant of this reaction has also been recorded, albeit with only modest levels of enantioselectivity (up to 55% ee).438... 

The Wacker or Smidt process, used to synthesize acetaldehyde from ethylene, involves a catalytic cycle that uses PdCl4. A brief outline of a cycle proposed for this process is shown in Figure 14-17. The fourth step in this cycle is substantially more complex than that shown in the figure and has been the subject of much study. ... 

Although the Wacker-type oxidation of olefins has been applied since the early 1980s, processes involving higher olefins are stiU the subject of investigations due to their poor solubility in water. Particularly interesting in this context is the inverse phase-transfer catalysis using water-soluble host molectdes. Indeed, upon a careful choice of the substituent, these receptor molecules avoid the isomerization into internal olefins or make it possible to perform substrate selective oxidations that cannot be achieved a biphasic medium with conventional transition metal catalysts. 

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. ... 

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