Ruthenium complexes catalysis

Perfluoroalkylation. Arenes and heteroarenes give perfluoroalkyl derivatives upon reaction with RfS02CI under ruthenium complex catalysis. Pyrroles also undergo this reaction. ... 

Direct C-H bond functionalization via ruthenium complexes catalysis has been well explored [5]. However, the rapid progress for heterocycle synthesis via ruthenium-catalyzed C-H activation has been only achieved since 2011. By utilizing the less expensive and stable ruthenium(II) complex [RuCl2(/ -cymene)]2, the oxidative cyclization reactions with a series of unsaturated small molecules like alkenes and alkynes proved to be a fast access to heterocycles. Herein, this chapter is intended to provide an overview of reported examples for ruthenium-catalyzed C-H bond activation and cyclization for heterocycle synthesis till the end of 2014, including mechanism presentations... 

J. Halpem Developments in homogeneous catalysis [using ruthenium complexes], pp. 146-162 (65). 

An olefin metathesis/double bond isomerization sequence can be promoted by the catalysis of in situ generated ruthenium hydride species from ruthenium complex 1 (Scheme 41 ).68... 

The chemistry of ruthenium has been reviewed in COMC (1982) and COMC (1995)338 339 as well as in Comprehensive Coordination Chemistry II. More recent reviews summarize the synthesis, properties, and applications of diruthenium tetracarboxylates341 as well as ruthenium catalysis in organic synthesis in general.342 Most recent developments and applications of ruthenium complexes in organic synthesis have been reviewed up to 2004.343... 

The concerted delivery of protons from OH and hydride from RuH found in these Shvo systems is related to the proposed mechanism of hydrogenation of ketones (Scheme 7.15) by a series of ruthenium systems that operate by metal-ligand bifunctional catalysis [86]. A series of Ru complexes reported by Noyori, Ohkuma and coworkers exhibit extraordinary reactivity in the enantioselective hydrogenation of ketones. These systems are described in detail in Chapters 20 and 31, and mechanistic issues of these hydrogenations by ruthenium complexes have been reviewed [87]. 

Ruthenium complexes B are stable in the presence of alcohols, amines, or water, even at 60 °C. Olefin metathesis can be realized even in water as solvent, either using ruthenium carbene complexes with water-soluble phosphine ligands [815], or in emulsions. These complexes are also stable in air [584]. No olefination of aldehydes, ketones, or derivatives of carboxylic acids has been observed [582]. During catalysis of olefin metathesis replacement of one phosphine ligand by an olefin can occur [598,809]. 

More synthetic interest is generated by the potentially very useful hydration of dienes. As shown on Scheme 9.6, methylethylketone (MEK) can be produced from the relatively cheap and easily available 1,3-butadiene with combined catalysis by an acid and a transition metal catalyst. Ruthenium complexes of several N-N chelating Hgands (mostly of the phenanthroline and bipyridine type) were found active for this transformation in the presence of Bronsted acids with weakly coordinating anions, typically p-toluenesulfonic acid, TsOH [18,19]. In favourable cases 90 % yield of MEK, based on butadiene, could be obtained. 

W.P. Griffith, Ruthenium Oxidation Complexes, Catalysis by Metal Complexes 34, DOl 10.1007/978-l-4020-9378-4 l, Springer Science+Business Media B.V. 2011... 

W.R Griffith, Ruthenium Oxidation Complexes, Catalysis by Metal Complexes 34, 227... 

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