Catalysis metal-catalyzed

Nguyen DH, Urrutigoity M, Kalck P. Water-soluble hydroformylation catalysis. Metal-catalyzed reactions in water. Weinheim Wiley-VCH 2013. pp. 109-137. 

Transition-Metal Catalyzed Cyclizations. o-Halogenated anilines and anilides can serve as indole precursors in a group of reactions which are typically cataly2ed by transition metals. Several catalysts have been developed which convert o-haloanilines or anilides to indoles by reaction with acetylenes. An early procedure involved coupling to a copper acetyUde with o-iodoaniline. A more versatile procedure involves palladium catalysis of the reaction of an o-bromo- or o-trifluoromethylsulfonyloxyanihde with a triaLkylstaimylalkyne. The reaction is conducted in two stages, first with a Pd(0) and then a Pd(II) catalyst (29). 

The complex Pd-(-)-sparteine was also used as catalyst in an important reaction. Two groups have simultaneously and independently reported a closely related aerobic oxidative kinetic resolution of secondary alcohols. The oxidation of secondary alcohols is one of the most common and well-studied reactions in chemistry. Although excellent catalytic enantioselective methods exist for a variety of oxidation processes, such as epoxidation, dihydroxy-lation, and aziridination, there are relatively few catalytic enantioselective examples of alcohol oxidation. The two research teams were interested in the metal-catalyzed aerobic oxidation of alcohols to aldehydes and ketones and became involved in extending the scopes of these oxidations to asymmetric catalysis. 

Catalytic transformation based on combined enzyme and metal catalysis is described as a new class of methodology for the synthesis of enantiopure compounds. This approach is particularly useful for dynamic kinetic resolution in which enzymatic resolution is coupled with metal-catalyzed racemization for the conversion of a racemic substrate to a single enantiomeric product. 

Polycondensation pol5mers, like polyesters or polyamides, are obtained by condensation reactions of monomers, which entail elimination of small molecules (e.g. water or a hydrogen halide), usually under acid/ base catalysis conditions. Polyolefins and polyacrylates are typical polyaddition products, which can be obtained by radical, ionic and transition metal catalyzed polymerization. The process usually requires an initiator (a radical precursor, a salt, electromagnetic radiation) or a catalyst (a transition metal). Cross-linked polyaddition pol5mers have been almost exclusively used so far as catalytic supports, in academic research, with few exceptions (for examples of metal catalysts on polyamides see Ref. [95-98]). 

S. Cenini, M. Pizzotti, and C. Crotti, Metal Catalyzed Deoxygenation Reactions by Carbon Monoxide of Nitroso and Nitro Compounds (D. Reidel Publishing), 6, (Aspects of Homogeneous Catalysis A Series of Advances), 97-198 (1988). 

Catalysis and Synthesis in the Laboratory. Research on the practical applications of catalysis was not matched in the laboratory. We began a study of metal and non-metal catalyzed reactions early in our sonochemistry program. Our first project was to develop a convenient method of hydrogenating a wide range of olefins. We chose formic acid as our hydrogen source and found it to be effective. For example, with continuous irradiation, palladium catalyzed hydrogenations of olefins are complete in one hour(44). 

Pringle, P.G., Brewin, D., and Smith, M.B., Metal-catalyzed hydrophosphination as a route to water-soluble phosphines, in Aqueous Organometallic Chemistry and Catalysis, Vol. 5, Horvath, I.T. and Joo, F., Eds., Kluwer, Dordrecht, the Netherlands, 1995, p. 111. 

Activation of a C-H bond requires a metallocarbenoid of suitable reactivity and electrophilicity.105-115 Most of the early literature on metal-catalyzed carbenoid reactions used copper complexes as the catalysts.46,116 Several chiral complexes with Ce-symmetric ligands have been explored for selective C-H insertion in the last decade.117-127 However, only a few isolated cases have been reported of impressive asymmetric induction in copper-catalyzed C-H insertion reactions.118,124 The scope of carbenoid-induced C-H insertion expanded greatly with the introduction of dirhodium complexes as catalysts. Building on initial findings from achiral catalysts, four types of chiral rhodium(n) complexes have been developed for enantioselective catalysis in C-H activation reactions. They are rhodium(n) carboxylates, rhodium(n) carboxamidates, rhodium(n) phosphates, and < // < -metallated arylphosphine rhodium(n) complexes. 

The Alder-ene reaction has traditionally been performed under thermal conditions—generally at temperatures in excess of 200 °C. Transition metal catalysis not only maintains the attractive atom-economical feature of the Alder-ene reaction, but also allows for regiocontrol and, in many cases, stereoselectivity. A multitude of transition metal complexes has shown the ability to catalyze the intramolecular Alder-ene reaction. Each possesses a unique reactivity that is reflected in the diversity of carbocyclic and heterocyclic products accessible via the transition metal-catalyzed intramolecular Alder-ene reaction. Presumably for these reasons, investigation of the thermal Alder-ene reaction seems to have stopped almost completely. For example, more than 40 papers pertaining to the transition metal-catalyzed intramolecular Alder-ene reaction have been published over the last decade. In the process of writing this review, we encountered only three recent examples of the thermal intramolecular Alder-ene reaction, two of which were applications to the synthesis of biologically relevant compounds (see Section 10.12.6). 

Another important contribution of transition metal-catalyzed alkyne hydrosilylation continues to be the mechanistic analysis of catalysis. As a relatively simple addition process, hydrosilylation has lent itself to extensive and thorough mechanistic analysis yet, numerous reaction pathways have now been postulated, and it is clear that many paths are possible. Importantly, principles from hydrosilylation reactions often are of use in the understanding of related, more complex transformations. Despite past achievements, much current thinking is based as much on speculation as on solid data. It is likely that continued, detailed exploration of the mechanistic underpinnings of hydrosilylation reactions will lead to new understanding and better reactions. 

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