Transition metal catalysis addition

However, a number of limitations are still evident when tetrafluorohorate and hexafluorophosphate ionic liquids are used in homogeneous catalysis. The major aspect is that these anions are still relatively sensitive to hydrolysis. The tendency to anion hydrolysis is of course much less pronounced than that of the chloroalu-minate melts, hut it still occurs and this has major consequences for their use in transition metal catalysis. For example, the [PF ] anion of l-hutyl-3-methylimida-2olium ([BMIM]) hexafluorophosphate was found (in the author s laboratories) to hydrolyze completely after addition of excess water when the sample was kept for 8 h at 100 °C. Gaseous HF and phosphoric acid were formed. Under the same conditions, only small amounts of the tetrafluorohorate ion of [BMlMjjBFJ was converted into HF and boric acid [10]. The hydrolytic formation of HF from the anion of the ionic liquid under the reaction conditions causes the following problems with... 

Ionic liquids with wealdy coordinating, inert anions (such as [(CF3S02)2N] , [BFJ , or [PFg] under anhydrous conditions) and inert cations (cations that do not coordinate to the catalyst themselves, nor form species that coordinate to the catalyst under the reaction conditions used) can be looked on as innocent solvents in transition metal catalysis. In these cases, the role of the ionic liquid is solely to provide a more or less polar, more or less weakly coordinating medium for the transition metal catalyst, but which additionally offers special solubility for feedstock and products. 

Not all C-H activation chemistry is mediated by transition metal catalysts. Many of the research groups involved in transition metal catalysis for C-H activation have opted for alternative means of catalysis. The activation of methane and ethane in water by the hexaoxo-/i-peroxodisulfate(2—) ion (S2O82) was studied and proceeds by hydrogen abstraction via an oxo radical. Methane gave rise to acetic acid in the absence of external carbon monoxide, suggesting a reaction of a methyl radical with CO formed in situ. Moreover, the addition of (external) CO to the reaction mixture led to an increase in yield of the acid product (Equation (ll)).20... 

Phosphonium salts can be synthesized from unsaturated compounds by addition of a triarylphosphine and an acid in the presence of a palladium or rhodium catalyst. Transition metal catalysis turned out to be effective for the synthesis of organophosphorous compounds. 

During the coverage period of this chapter, reviews have appeared on the following topics reactions of electrophiles with polyfluorinated alkenes, the mechanisms of intramolecular hydroacylation and hydrosilylation, Prins reaction (reviewed and redefined), synthesis of esters of /3-amino acids by Michael addition of amines and metal amides to esters of a,/3-unsaturated carboxylic acids," the 1,4-addition of benzotriazole-stabilized carbanions to Michael acceptors, control of asymmetry in Michael additions via the use of nucleophiles bearing chiral centres, a-unsaturated systems with the chirality at the y-position, and the presence of chiral ligands or other chiral mediators, syntheses of carbo- and hetero-cyclic compounds via Michael addition of enolates and activated phenols, respectively, to o ,jS-unsaturated nitriles, and transition metal catalysis of the Michael addition of 1,3-dicarbonyl compounds. ... 

Many different types of 1,3-dipoles have been described [Ij however, those most commonly formed using transition metal catalysis are the carbonyl ylides and associated mesoionic species such as isomiinchnones. Additional examples include the thiocar-bonyl, azomethine, oxonium, ammonium, and nitrile ylides, which have also been generated using rhodium(II) catalysis [8]. The mechanism of dipole formation most often involves the interaction of an electrophilic metal carbenoid with a heteroatom lone pair. In some cases, however, dipoles can be generated via the rearrangement of a reactive species, such as another dipole [40], or the thermolysis of a three-membered het-erocycHc ring [41]. 

The manifold intermediates in homogeneous transition-metal catalysis are certainly metal complexes and therefore show a behaviour like ordinary coordination compounds associations of phosphorus donors open up multifarious additional controls. Both, substrates and P ligands are Lewis bases that we have to consider and that compete at the coordination centers of the metal, leading to competitive, non-competitive or uncompetitive activation or inhibition processes in analogy to the terminology of enzyme chemistry... 

The entries into transition metal catalysis discussed so far, required the presence of a specific bond (a polar carbon-heteroatom bond for oxidative addition or a carbon-carbon multiple bond for coordination-addition processes) that was sacrificed during the process. If we were able to use selected carbon-hydrogen bonds as sacrificial bonds, then we could not only save a lot of trouble in the preparation of starting materials but we would also provide environmentally benign alternatives to several existing processes. In spite of the progress made in this field the number of such transformations is still scarce compared to the aforementioned reactions. 

It is likely that more silicon-carbon bonds are produced by the hydrosilylation of olefins than by any other method except the direct process. This deceptively simple addition of an Si-H bond to a C-C multiple bond can be promoted by a variety of means, but transition metal catalysis is by far the most significant. Two relatively old catalysts, H2PtCl6 ( Speier s catalyst ) and Pt2(Me2ViSiOSiMe2Vi)3 ( Karstedt s catalyst ), remain the most effective, and the remarkable rates and turnover numbers observed in these systems are among the most impressive in all of organometallic chemistry. The bulk of the literature on hydrosilylation falls outside the scope of this review, and readers are directed to the comprehensive work on hydrosilylation edited by Marciniec.93... 

Biaryls have also been prepared by coupling support-bound aryl halides with aryl-zinc compounds (Figure 5.20) or with aryl(fluoro)silanes [203]. As with Suzuki or Stille couplings, these reactions also require transition metal catalysis. An additional strategy for coupling arenes on solid phase is the oxidative dimerization of phenols (Figure 5.20). 

For a more complete description of the principles of transition metal catalysis, a number of the excellent reviews published recently should be consulted. These include, in addition to those already cited, several reviews of rhodium (89) and palladium (90-93) chemistry, addition (94, 95) and insertion (96) reactions, homogeneous catalytic hydrogenation (97), hydride complex chemistry (98), nitrogen fixation (99), and organometallic complexes as potential synthetic reagents (100). 

Even though the aramatization mechanism from the putative cyclohexadienyl radical intermediate is not well understood (oxidation by the adventitious air is one possibility), the radical addition to an aromatic ring strategy does possess some advantages (a) no transition metal catalysis is required, (b) better yields are obtained than with similar procedures although the reaction is not regiospecific, (c) readily available starting materials may be used. 

The reaction is catalysed by many transition-metal complexes, and a mechanism for the hydrosilylation of an alkene under transition-metal catalysis is depicted in Figure Si5.7. Initial coordination of the alkene to the metal is followed by cis addition of the silicon-hydrogen bond. A hydride migratory insertion and elimination of the product silane complete the cycle. 

Intramolecular addition of amine N-H bonds to carbon-carbon multiple bonds would afford nitrogen heterocycles. To realize catalytic cyclization of a,co-aminoalkenes or aminoalkynes, various catalytic systems have been developed especially with early transition metals such as titanium, zirconium, lanthanide metals, and actinide metals [ 12], Late-transition-metal catalysis based on Ni, Pd, and Rh has also proved to be efficient [ 12], Recently, the ruthenium-catalyzed intramolecular hydroamination of aminoalkynes 15 was reported to afford 5-7-membered ring products 16 in various yields (Eq. 6) [13]. Among... 

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