Metal-catalyzed processes 1018 Subject

The purpose of this section is not to enquire into the mechanisms of these reactions, relevant though this might be to the subject of metal-catalyzed processes. It is rather to note those complexes which are reactive in the reactions listed above and to add this information to our small sum of knowledge concerning the stability of hydrocarbon metal complexes. 

Substituted alkynes play a pivotal role in modem organic synthesis. Although many methods are viable for their constmction, metal-catalyzed processes belong to the most efficient ones. The copper-mediated (Palladium free) alkynylation is known under the name Castro-Stephens reaction, j e palladium-catalyzed counterpart was discovered by Heck and Cassar (see Scheme 5-122), which is subject of the next paragraph. Nowadays the Sonogashira reaction, j ich uses copper co-catalysts, can be found as the method of choice. 

During the past few years, increasing numbers of reports have been published on the subject of domino reactions initiated by oxidation or reduction processes. This was in stark contrast to the period before our first comprehensive review of this topic was published in 1993 [1], when the use of this type of transformation was indeed rare. The benefits of employing oxidation or reduction processes in domino sequences are clear, as they offer easy access to reactive functionalities such as nucleophiles (e. g., alcohols and amines) or electrophiles (e. g., aldehydes or ketones), with their ability to participate in further reactions. For that reason, apart from combinations with photochemically induced, transition metal-catalyzed and enzymatically induced processes, all other possible constellations have been embedded in the concept of domino synthesis. 

The transformation shown in equation (54) retains many of the features of ordinary photochemical and transition-metal-catalyzed thermal reactions of organic compounds, but displays some unique characteristics as well. In cases where irradiation serves only to accelerate the rate of the expected thermal process, higher chemical yields of product can result, reaction rates are subject to greater control through regulation of light intensity, and thermally sensitive products are isolated more readily since elevated reaction temperatures can be avoided. Alternatively, the function of M may be to facilitate known photochemical reactions of O or perhaps introduce new reaction channels not observed upon irradiation of O alone. A detailed discussion of the mechanisms and synthetic applications of these processes has been presented.177... 

Metal-catalyzed oxidation of alcohols to aldehydes and ketones is a subject that has received significant recent attention [21,56,57]. One such method that utilizes NHC ligands is an Oppenauer-type oxidation with an Ir or Ru catalyst [58-62]. These alcohol oxidation reactions consist of an equilibrium process involving hydrogen transfer from the alcohol substrate to a ketone, such as acetone (Eq. 5), or an alkene. Because these reactions avoid the use of a strong oxidant, the potential oxidative instability of NHC ligands is less problematic. Consequently, these reactions represent an important target for future research into the utility of NHCs. 

Metal enolates have played a Umited role in the metal-catalyzed isomerization of al-kenes . As illustrated in a comprehensive review by Bouwman and coworkers, ruthenium complex Ru(acac)3 (51) has been used to isomerize a wide range of substituted double bonds, including aUylic alcohols (131), to the corresponding ketones (132) (equation 38) . The isomerization of aUylic alcohols affords products that have useful applications in natural product synthesis and in bulk chemical processes. An elegant review by Fogg and dos Santos shows how these complexes can be used in tandem catalysis, where an alkene is subjected to an initial isomerization followed by a hydroformylation reaction ... 

Free radical promoted hydrosilation of olefins typically gives poorer conversions than are produed by hydrosilation mediated by metal catalysts. However, they are not subject to isomerization of the olefin, a side reaction that can be a nuisance in metal-catalyzed hydrosilations. This is due to the extremely efficient hydrogen atom transfer reaction from Si-H to carbon radicals and the resulting very short lifetimes of the latter. The generally accepted mechanism for these processes is illustrated in Scheme 1. 

The review of the experimental results, which now follows, will concentrate on assessing the extents to which the transition metals catalyze the processes of olefin exchange and isomerization and the mechanisms of these processes in the light of the subject matter of this section. 

Eight-membered rings can be obtained by [4+4]-cycloadditions of 1,3-dienes [1] via diradicals or other intermediates. Synthesis of such compounds has been achieved by thermal, [2] photochemical, [3] and by metal-catalyzed [4] processes these reactions have been the subject of extensive mechanistic [5] and theoretical [5c] studies. Their strategic applications in natural product synthesis have been reviewed. [5d] The thermal version has generated little interest, except in orthoquino-dimethane dimerizations and in cycloreversions the Cope rearrangement of 1,2-divinyl-cyclobutanes [3] is more commonly used. [4+4]-Cycloadditions are also used with 1,3-dipoles or mesoionic heterocycles for the synthesis of six- and seven-membered rings. Sometimes also [6+4]-cycloadditions are... 

One of the major subjects of interest over the last decade in metal-catalyzed alkane oxidation reactions has been the understanding of the factors determining the C-H site selectivity of such processes [61], This knowledge is necessary to face the challenge of devising chemical tools for overcoming the innate reactivity of C-H bonds, introducing novel selectivities in these reactions. 

The cellulose fiber in paper is attacked and weakened by sulfur dioxide. Paper made before about 1750 is not significantly affected by sulfur dioxide (11). At about that time, the manufacture of paper changed to a chemical treatment process that broke down the wood fiber more rapidly. It is thought that this process introduces trace quantities of metals, which catalyze the conversion of sulfur dioxide to sulfuric add. Sulfuric acid causes the paper to become brittle and more subject to cracking and tearing. New papers have become available to minimize the interaction with SO2. 

Over the last decade, the chemistry of the carbon-carbon triple bond has experienced a vigorous resurgence [1]. Whereas construction of alkyne-con-taining systems had previously been a laborious process, the advent of new synthetic methodology based on organotransition metal complexes has revolutionized the field [2]. Specifically, palladium-catalyzed cross-coupling reactions between alkyne sp-carbon atoms and sp -carbon atoms of arenes and alkenes have allowed for rapid assembly of relatively complex structures [3]. In particular, the preparation of alkyne-rich macrocycles, the subject of this report, has benefited enormously from these recent advances. For the purpose of this review, we Emit the discussion to cychc systems which contain benzene and acetylene moieties only, henceforth referred to as phenylacetylene and phenyldiacetylene macrocycles (PAMs and PDMs, respectively). Not only have a wide... 

A project at the University of Arizona (FEDRIP 1996) will study microbial dehalogenation of several compounds, including chloroform. A major part of the study will focus on the facultative anaerobic bacteria Shewanella putrefaciens sp., which is known to catalyze the transformation of carbon tetrachloride to chloroform and other as yet unidentified products. The organic substrates will also contain metals. It is hoped that the end-products from the biochemical treatment can be subjected to a photolytic finishing process that will completely mineralize any remaining halogenated compounds. 

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