Olefin metathesis ruthenium catalysis

Vyboishchikov, S. F., Buhl, M., Thiel, W. Mechanism of olefin metathesis with catalysis by ruthenium carbene complexes density functional studies on model systems. Chem.— Eur. J. 2002, 8, 3962-3975. 

The mechanistic investigations presented in this section have stimulated research directed to the development of advanced ruthenium precatalysts for olefin metathesis. It was pointed out by Grubbs et al. that the utility of a catalyst is determined by the ratio of catalysis to the rate of decomposition [31]. The decomposition of ruthenium methylidene complexes, which attribute to approximately 95% of the turnover, proceeds monomolecularly, which explains the commonly observed problem that slowly reacting substrates require high catalyst loadings [31]. This problem has been addressed by the development of a novel class of ruthenium precatalysts, the so-called second-generation catalysts. 

The outstanding performances of five-membered NHC ligands in organometallic chemistry and catalysis prompted Grubbs and co-workers to develop a novel stable four-membered NHC [64]. Following their interest in developing new ruthenium olefin metathesis catalysts, they synthesised and fully characterised complex 51 to study the impact of the architecturally unique NHC ligand on the activity of the Ru-based catalyst [65] (Fig. 3.20). In the RCM of 1 at 40°C in CH Cl with 51 (5 mol% catalyst), the reaction reached completion within 20 min, whereas less than 10 min are required for standard catalysts 14 and 16. It should be noted that catalysts 14 and 16 are able to complete the RCM of 1 with only 1 mol% catalyst at 30°C. 

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... 

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]. 

Promising applications for metal-NHC compounds in materials science and medicinal chemistry are based on the strong metal-carbon bond and the high donor capability of the NHC. The most extensive investigations have been carried out in the field of homogeneous catalysis. Here, NHCs have to be considered as typical directing or innocent spectator ligands, best comparable to trialkylphosphines. The recent successful applications of NHCs in ruthenium-catalyzed olefin metathesis... 

Olefin metathesis is a unique reaction and is only possible by transition metal catalysis. In fact only complexes of Mo, W, Re, and Ru are known to catalyze olefin metathesis. Once it was known that metallocarbenes were the actual catalytic species, a variety of metal carbene complexes were prepared and evaluated as catalysts. Two types of catalysts have emerged as the most useful overall. The molybdenum-based catalysts developed by Schrock and ruthenium-based catalysts developed by Grubbs. 

The most important discoveries in ruthenium catalysis are highlighted and innovative activation processes, some of which are still controversial, are presented in this volume. They illustrate the usefulness in organic synthesis of specific reactions including carbocyclization, cyclopropanation, olefin metathesis, carbonylation, oxidation, transformation of silicon containing substrates, and show novel reactions operating via vinylidene intermediates, radical processes, inert bonds activation as well as catalysis in water. 

The combination of ruthenium and palladium catalysis has been illustrated by the performance of the olefin metathesis—Heck coupling sequence [97,... 

One of the areas gamering attention in catalysis research has been the development of green or enviromnentally benign catalytic systems. For olefin metathesis, the trend has been to develop catalytic systems that can be efficiently recycled. Success in this area has multiple implications for OM processes. First, a recyclable catalyst will give overall more turnovers per catalyst molecule, and thereby be more economical. Second, a catalyst that can be efficiently recycled (low loss of activity over repeated uses) leaches less Ruthenium into the product and thus less expensive processing costs. To this end inunobihzation of the olefin metathesis catalysts on a variety of sohd supports and utilization of nonorganic solvent systems have been explored. 

Rhodium-based catalysis suffers from the high cost of the metal and quite often from a lack of stereoselectivity. This justifies the search for alternative catalysts. In this context, ruthenium-based catalysts look rather attractive nowadays, although still poorly documented. Recently, diruthenium(II,II) tetracarboxylates [42], polymeric and dimeric diruthenium(I,I) dicarboxylates [43], ruthenacarbor-ane clusters [44], and hydride and silyl ruthenium complexes [45 a] and Ru porphyrins [45 b] have been introduced as efficient cyclopropanation catalysts, superior to the Ru(II,III) complex Ru2(OAc)4Cl investigated earlier [7]. In terms of efficiency, electrophilicity, regio- and (partly) stereoselectivity, the most efficient ruthenium-based catalysts compare rather well with the rhodium(II) carboxylates. The ruthenium systems tested so far seem to display a slightly lower level of activity but are somewhat more discriminating in competitive reactions, which apparently could be due to the formation of less electrophilic carbenoid species. This point is probably related to the observation that some ruthenium complexes competitively catalyze both olefin cyclopropanation and olefin metathesis [46], which is at variance with what is observed with the rhodium catalysts. 

For a discussion of mechanistic studies of Ru-alkylidene catalysis of metathesis, see M. S. Sanford and J. A. Love, Mechanism of Ruthenium-Catalyzed Olefin Metathesis Reactions, in Handbook of Metathesis, Vol. 1, R. H. Grubbs, Ed., Wiley-VCH Weinheim, Germany, 2003, pp. 112-131. 

Olefin metathesis has been extensively written on in both books and journals [1-10]. This chapter will focus on ADMET. Of particular interest are the issues of catalysis, mainly functional group tolerance, kinetics, and mechanistic details. The development of late-transition metal catalysts has enormously expanded the scope of ADMET, so particular attention will be given to the well-defined ruthenium-based olefin metathesis catalysts. Pertinent information pertaining to catalysts of Group VI metals will also be provided. Important procedural aspects of ADMET will be presented in conclusion. 

During the past few decades, a wide variety of molecules with transition metal-carhon mulhple bonds have been studied. The chemistry of doubly bonded species - carbenes - is particularly interesting because it leads to several synthetically important transformations, and for this reason, metal carbenes are the main subject of this chapter. Our discussion begins with a classification of metal-carbene complexes based on electronic structure, which provides a way to understand their reactivity patterns. Next, we summarize the mechanistic highlights of three metal-carbene-mediated reactions carbonyl olefinafion, olefin cyclopropanafion, and olefin metathesis. Throughout the second half of the chapter, we focus mainly on ruthenium-carbene olefin metathesis catalysts, in part because of widespread interest in the applications of these catalysts, and in part because of our expertise in this area. We conclude with some perspectives on the chemistry of metal carbenes and on future developments in catalysis. 

In 2008, Piers and coworkers [43] reported the preparation and spectroscopic characterization of ruthenacyclobutane and ruthenium alkylidene/olefin complexes associated with ring-closing metathesis (RCM) catalysis. Exploiting the reversibility associated with the RCM reaction, phosphonium alkylidene complex 28a was reacted with 1 equiv of ethylene at —78 °C, followed by the addition of an excess of RCM product 29 (2-3 equiv), to afford a 90% NMR yield of metallacycle 30 (Scheme 8.9). This use of reverse engineering was found to minimize the formation of the thermodynamically favored, unsubstituted ruthenacycle 23 to only 10% yield. Later studies found that, similar to the phenomena that had been observed with propene, the a-monosubstituted metallacycle derived from ethylene and the propagating alkylidene of 30 could also be observed if the reaction temperature was further lowered (e.g., —76 C) [41]. It was additionally reported that the use of the more bulky phosphonium alkylidene 28b afforded lower reaction yields relative to 28a (60-70% vs. 90%). 

One area of catalysis in which the application of NHCs as ancillary ligands has had a significant impact is ruthenium-catalysed olefin metathesis. While phosphine-bearing first-generation complexes such as Grubbs I have enabled a variety of synthetic chemistry, from natural products and drugs to... 

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