Ruthenium complexes synthesis

Lachaud F, Jeandon C, Monari A, Assfeld X, Beley M, Ruppert R, Gros PC (2012) New dyads using (metallo)porphyrins as ancillary ligands in polypyridine ruthenium complexes. Synthesis and electronic properties. Dalton Trans 41(41) 12865-12871... 

X-ray crystallography, 3, 623 Ruscodibenzofuran synthesis, 4, 698, 709 Ruthenacyclobutane, 3-cyano-synthesis, 1, 667 Ruthenium complexes with pyridines, 2, 124 triazenido, 5, 675 Rutin... 

Figure 1.29 Synthesis of ruthenium complexes of the chelating ligand bis(dimethylphosphino)-...

Scheme 8 Synthesis of ruthenium polysulfido complexes from low-valent ruthenium complexes...

In 2009, Buchmeiser and co-workers reported the synthesis of a novel ruthenium complex 54 based on a seven-membered NHC ligand [68] (Fig. 3.22). To examine the catalytic activity of complex 54 in the RCM reaction, the authors subjected the complex to a series of typical RCM reactions by using substrates 1, 3, and 5. Pre-catalyst 54 showed only moderate reactivity with 1 and 3 and no reaction occurred with 5. 

More recently, these authors have reported the synthesis of a new thiophene-based analogue of (I ,i )-Me-DuPHOS called UlluPHOS. The facial recognition and enantioselection associated with ruthenium complexes of UlluPHOS and Me-DuPHOS were shown to be similarly high in various hydrogenations of p-keto esters (Scheme 8.32). The most important difference between these two ligands was found by comparing the reaction rates. Indeed, the authors have observed that the use of UlluPHOS considerably increased the activity of the complexes. 

Further improvements in activity of the ruthenium carbene complexes were achieved by incorporation of methyl groups in 3,4-position of imidazol-2-ylidene moiety. Introduction of sulfur in the trara-position to the N-heterocyclic carbene leads to increased stability of the resulting ruthenium complexes. The synthesis and the first applications of these new rathenium complexes are described herein. 

Olefin-metathesis is a useful tool for the formation of unsaturated C-C bonds in organic synthesis.186 The most widely used catalysts for olefin metathesis include alkoxyl imido molybdenum complex (Schrock catalyst)187 and benzylidene ruthenium complex (Grubbs catalyst).188 The former is air- and moisture-sensitive and has some other drawbacks such as intolerance to many functional groups and impurities the latter has increased tolerance to water and many reactions have been used in aqueous solution without any loss of catalytic efficiency. 

Ring-closing metathesis has been successfully used in the synthesis of [3.5.0], [4.5.0], and [5.5.0] ring systems <2001TL8231>. The ruthenium complex 160 was employed on both symmetrical and unsymmetrical substrates with equal success, as outlined in Equation (15). Compounds 161-164 were synthesized in this fashion. 

Synthesis of block copolymers of norbornene derivatives, with different side groups, has been reported via ROMP [101]. Initially, exo-N-bulyl-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide was polymerized in acetone at room temperature with a ruthenium initiator (Scheme 40). The conversion of the reaction was quantitative. Subsequent addition of norbornene derivative carrying a ruthenium complex led to the formation of block copolymers in 85% yield. Due to the presence of ruthenium SEC experiments could not be performed. Therefore, it was not possible to determine the molecular weight... 

SYNTHESIS AND CHARACTERIZATION OF COMPLEXES 9.16.7.1 Synthetic Strategies for Ruthenium Complexes... 

S. Kojima, T. Hasegawa, T. Yonemura, K. Sasaki, K. Yamamoto, Y. Makimura, T. Takahashi, T. Suzuki, Y. Susuki, and K. Kobayashi, Ruthenium complexes carrying a disialo complex-type oligosaccharide Enzymatic synthesis and its application to a luminescent probe to detect influenza viruses, Chem. Commun. (2003) 1250-1251. 

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... 

Table 6 Selective synthesis of a-vinylsilanes with a cationic ruthenium complex...

The greater reactivity of terminal olefins compared to their more hindered di-and tri-substituted counterparts became evident in the model studies (Sect. 2.2.1) and in the total synthesis of epothilones A, B and E (Sects. 2.2.2-2.2.4). Suitably positioned disubstituted olefins can, however, participate in RCM reactions employing the molybdenum initiator 1 [19], and this is demonstrated in the total synthesis of epothilone B (5) (Sect. 2.2.3). As expected this transformation proved impossible using the ruthenium complex 3. 

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