Ruthenium, catalytic activity with functional groups

The acceptance of a (new) catalytically mediated methodology by the target-directed synthetic community strongly depends on the availability, stability, and functional group tolerance of the respective catalysts. With the commercial availability of Grubbs5 benzylidene ruthenium catalyst A [13] and Schrock s even more active, yet highly air- and moisture-sensitive molybdenum catalyst B [14]... 

Since the discovery of ruthenium and molybdenum carbene complexes that efficiently catalyze olefin metathesis under mild reaction conditions and that are compatible with a broad range of functional groups, olefin metathesis has increasingly been used for the preparation of alkenes on insoluble supports. In particular, the ruthenium complexes Cl2(PCy3)2Ru=CHR, developed by Grubbs, show sufficient catalytic activity even in the presence of air and water [781] and are well suited for solid-phase synthesis. 

Ethylenediaminetetraacetic acid or its sodium salt (EDTA) is a well-known com-plexing agent which can form an abundant variety of water-soluble complexes with all metals. EDTA is widely used in industry and environmental studies are concerned with the degradation of its complexes [2] or the bioaccumulation of platinum group metals [3]. Directly related to the aim of this book is the catalytic activity in various carbonylation reactions of the precursor [Ru(EDTA)(H20)], as reported by Taqui Khan and co-workers [4], In fact the two nitrogen and three carboxylate functions bind the ruthenium(III) center, and under a CO atmosphere this complex is reduced to the ruthenium(II) species [Ru(EDTA)(CO)] in which only one carboxylate group... 

Catalytic hydrogenations with ruthenium complexes have been reviewed. Another article deals with the intramolecular stereocontrol of hydrogenation reactions by functional groups in the substrate, and concentrates on the reduction of unsaturated alcohols, ketones, and esters by cationic rhodium and iridium complexes. A review on Enantioselective Synthesis with Optically Active Transition... 

Ruthenium has been known to catalyze olefin metathesis reactions for some time [10], and the development of discrete organometallic complexes has enabled the rational design of improved catalysts with enhanced catalytic activity, functional group tolerance, and selectivity [11]. In particular, catalyst development has provided systems that exhibit the living characteristics necessary to produce well-defined polymeric products. Three ruthenium complexes (1-3, Figure 5.1) are by far the most heavily utilized in ROMP [12,13]. 

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