Wilke reaction

A fascinating series of cyclodimeri2ation or cyclotrimeri2ation reactions was first observed in the labs of Wilke to produce 1,5-cyclooctadiene... 

Estimation of fct for Reversible Reactions When the reaction is of the form A B, where B is a nonvolatile product and the equilibrium constant is defined by Cg = K Ca, the expressions for computing /cl become extremely complex. A good discussion of this situation is given in Mass Tran.sfer by Sherwood, Pigford, and Wilke (McGraw-Hill, New York, 1975, p. 317). Three limiting cases are hsted below ... 

Wilkes and co-workers have investigated the chlorination of benzene in both acidic and basic chloroaluminate(III) ionic liquids [66]. In the acidic ionic liquid [EMIM]C1/A1C13 (X(A1C13) > 0.5), the chlorination reaction initially gave chlorobenzene, which in turn reacted with a second molecule of chlorine to give dichlorobenzenes. In the basic ionic liquid, the reaction was more complex. In addition to the... 

Styrene it was possible to activate, tune, and immobilize the well-loiown Wilke complex by use of this unusual biphasic system (Scheme 5.4-3). Obviously, this reaction benefits from this special solvent combination in a new and highly promising manner. 

At first, the reaction was investigated in batch mode, by use of different ionic liquids with wealdy coordinating anions as the catalyst medium and compressed CO2 as simultaneous extraction solvent. These experiments revealed that the activation of Wilke s catalyst by the ionic liquid medium was clearly highly dependent on the nature of the ionic liquid s anion. Comparison of the results in different ionic liquids with [EMIM] as the common cation showed that the catalyst s activity drops in the order [BARF] > [Al OC(CF3)2Ph 4] > [(CF3S02)2N] > [BFJ . This trend is consistent with the estimated nucleophilicity/coordination strength of the anions. 

Interestingly, the specific environment of the ionic solvent system appears to activate the chiral Ni-catalyst beyond a simple anion-exchange reaction. This becomes obvious from the fact that even the addition of a 100-fold excess of Fi[(CF3S02)2N] or Na[BF4] in pure, compressed CO2 produced an at best moderate activation of Wilke s complex in comparison to the reaction in ionic liquids with the corresponding counter-ion (e.g., 24.4 % styrene conversion with 100-fold excess of Fi[(CF3S02)2N], in comparison to 69.9 % conversion in [EMIM][(CF3S02)2N] under otherwise identical conditions). 

Block copolymers with materials such as a polyester (PE) (qv) can be prepd by the reaction of diisocyanate-terminated polyesters with hydroxyl-terminated PMMA according to Wilkes and Grezlak (Ref 21). The basic structure was found to be PMMA-PE-FMMA, with a mw of from 7500 to 47000. The purpose of the work was to produce a stronger copolymer (in terms of stress-strain) by tailoring the amt of each monomer used to produce the copolymer Further information on polymerization can be found in Refs 2a 6a... 

Recently, interesting composite materials incorporating polymeric materials into the sol-gel glasses have been reported by Wilkes and his co-workers [9]. These materials are named ceramers . The properties of ceramers strongly depend on the reaction conditions, i.e., acidity, water content, reaction temperature, the amount of organic polymer, the molecular weight of polymer, solvent, and so on. 

Very recently, Wilkes and co-workers 330,331) have reported the preparation and characterization of hybrid materials, which they named as ceramers . Ceramers were synthesized through the incorporation of polymeric or oligomeric PDMS into silicate glasses by a sol-gel process as shown in Reaction Scheme XXIV. During these reactions the variables such as the type of the alkoxide used, amount of water added, the pH value of the reaction system, and the reaction temperature, were carefully monitored. 

H. Bdnnemann, C. Girard, W. Kopp, and G. Wilke Homogeneous reactions catalysed by Group VIII metal systems, pp. 265-296 (25). 

Rabus R, H Wilkes, A Behrends, A Armstroff, T Fischer, AJ Pierik, F Widdel (2001) Anaerobic initial reaction of -alkanes in a denitrifying bacterium evidence for (1-methylpentyl) succinate as initial product and for involvement of an organic radical in -hexane metabolism. J Bacteriol 183 1707-1715. 

A portion of the Wilk/STA catalyst was re-used for the hydrogenation of successive 10,000 TON batches of 1-hexene with the TOP remaining constant for each run. A separate portion of this catalyst was also used for the 100,000 TON hydrogenation of 1-hexene with a TOP of 4800 hr. In each of these reactions the amount of Rh in the reaction mixture was below the level of detection, less than 1 ppm. 

Many catalytic reactions involve the activation of Si—H bonds and consequently the reaction of silanes with platinum(0) has been studied extensively. The reactions of hydrosilanes with transition-metal complexes, including platinum, has been extensively reviewed by Corey and Braddock-Wilking.58... 

A further example of a reaction which may be optimised in IL/scC02 by selection of the appropriate anion for the IL is catalytic enantioselective hydrovinylation, a synthetically interesting and truly atom economic C-C bond forming reaction [77-79]. The nickel complex below has been developed by Wilke and co-workers as precursor for a highly active and enantioselective catalyst for this process. 

The catalytic cyclo-oligomerization of 1,3-butadiene was first reported by Reed in 1954 using modified Reppe catalysts.4 Wilke et al., however, demonstrated in pioneering, comprehensive and systematic mechanistic investigations, the implications, versatility and the scope of the nickel-catalyzed 1,3-diene cyclo-oligomerization reactions.3,5... 

Although the pioneering, systematic, and comprehensive experimental work of Wilke et al3,5 has led to a thorough understanding of the nickel-catalyzed cyclo-oligomerization reaction of 1,3-butadiene, there are still some essential mechanistic details that are not yet firmly established (vide infra). In the following account, we summarize recent progress in the... 

Similar studies on the reactions of butadiene and bis(ir-allyl)palladium were carried out by Wilke and co-workers (4). Unlike the reactions with nickel complexes, no cyclization took place, and 1,6,10-dodecatriene... 

Other examples from Wilke s group are given in (examples 11-13), leading to highly stereoselective reactions, which have been exploited for asymmetric syntheses in the presence of appropriate asymmetric ligands. This subject requires separate review, however, and will not be treated further here. The reader is referred to the review by Bogdanovic (7).4... 

Reactions of butadiene or other dienes with aldehydes or ketones have been described by Wilke, who has applied them to several substrates, one being vitamin A (example 10, Table IV). 

The second pathway is represented by Eqs. (8)—(11). These reactions involve reduction of the Nin halide to a Ni° complex in a manner similar to the generation of Wilke s bare nickel (37, 38) which can form a C8 bis-77-alkyl nickel (17) in the presence of butadiene [Eq. (9)]. It is reasonable to assume that in the presence of excess alkyaluminum chloride, an exchange reaction [Eq. (10)] can take place between the Cl" on the aluminum and one of the chelating 7r-allyls to form a mono-77-allylic species 18. Complex 18 is functionally the same as 16 under the catalytic reaction condition and should be able to undergo additional reaction with a coordinated ethylene to begin a catalytic cycle similar to Scheme 4 of the Rh system. The result is the formation of a 1,4-diene derivative similar to 13 and the generation of a nickel hydride which then interacts with a butadiene to form the ever-important 7r-crotyl complex [Eq. (11)]. 

It should be noted here again that the catalytic reaction does not involve a change of valence of the metal. In general, catalytic olefin addition reactions that involve a hydride transfer do not require change of valence in the metal catalyst. On the other hand, carbon-carbon bond formation by coupling reactions which involve electron shifts, such as in Wilke s Ni°-catalyzed butadiene oligomerization reaction [Eq. (1)], requires a valence change on the metal. 

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