Organometallic ruthenium

The method is not restricted to secondary aryl alcohols and very good results were also obtained for secondary diols [39], a- and S-hydroxyalkylphosphonates [40], 2-hydroxyalkyl sulfones [41], allylic alcohols [42], S-halo alcohols [43], aromatic chlorohydrins [44], functionalized y-hydroxy amides [45], 1,2-diarylethanols [46], and primary amines [47]. Recently, the synthetic potential of this method was expanded by application of an air-stable and recyclable racemization catalyst that is applicable to alcohol DKR at room temperature [48]. The catalyst type is not limited to organometallic ruthenium compounds. Recent report indicates that the in situ racemization of amines with thiyl radicals can also be combined with enzymatic acylation of amines [49]. It is clear that, in the future, other types of catalytic racemization processes will be used together with enzymatic processes. 

Berger, I., Hanif, M., Nazarov, A. A., Hartinger, C. G., John, R. O. Kuznetsov, M. L. et al. In Vitro Anticancer Activity and Biologically Relevant Metabolization of Organometallic Ruthenium Complexes with Carbohydrate-Based Ligands. Chemistry Europ. Journal 14, 9046-9057 (2008). 

DKR of alcohol acetylation One-pot t-BuOH Organometallic Ruthenium catalyst for alcohol CA lipase + ROAc 22... 

Consequently, organometallic ruthenium(II) and osmium(II) arene complexes have recently attracted interest as anticancer agents [51]. The presence of a 7i-bonded arene in Ru11 (and Os11) complexes can have a dramatic influence on their chemical reactivity. There is a delicate balance between electron donation from the arene into the empty Ru 4d orbitals and back-donation from the filled 4d6 orbitals into vacant arene orbitals. This is influenced by the donor-acceptor power of the arene (e.g. hexamethylbenzene as a strong donor, in contrast to biphenyl which may act as acceptor) and by the other ligands on Ru11 which can influence the... 

Therrien et al. have developed organometallic ruthenium porphyrin compounds for anticancer photodynamic therapy. These combine synergistically the photodynamic action of porphyrins with the DNA damage-related cytotoxicity of Run-arene... 

The organometallic ruthenium-arene fragments improved the aqueous solubility of the otherwise insoluble porphyrins without modifying the photophysical properties of the photosensitizer. Additionally, the presence of the ruthenium on the porphyrins facilitated uptake into melanoma cells [160]. 

Chen H, Parkinson JA, Morris RE, Sadler PJ (2003) Highly selective binding of organometallic ruthenium ethylenediamine complexes to nucleic acids novel recognition mechanisms. J Am Chem Soc 125 173-186... 

Dorcier A, Dyson PJ, Gossens C, Rothlisberger U, Scopelliti R, Tavemelli I (2005) Binding of organometallic ruthenium(II) and osmium(II) complexes to an oligonucleotide a combined mass spectrometric and theoretical study. Organometallics 24 2114—2123... 

Ang WH, Daldini E, Scolaro C, Scopelliti R, Juillerat-Jeannerat L, Dyson PJ (2006) Development of organometallic ruthenium-arene anticancer drugs that resist hydrolysis. Inorg Chem 45 9006-9013... 

Novakova O, Chen H, Vrana O, Rodger A, Sadler PJ, Brabec V (2003) DNA interactions of monofunctional organometallic ruthenium(II) antitumor complexes in cell-free media. Biochemistry 42 11544—11554... 

Dougan SJ, Sadler PJ (2007) The design of organometallic ruthenium arene anticancer agents. Chimia 61 704-715... 

Liu H-K, Bemers-Price SJ, Wang F, Parkinson JA, Xu J, Bella J, Sadler PJ (2006) Diversity in guanine-selective DNA binding modes for an organometallic ruthenium arene complex. Angew Chem Int Ed Engl 45 8153-8156... 

Hu W, Luo Q, Ma X, Wu K, Liu J, Chen Y, Xiong S, Wang J, Sadler PJ, Wang F (2009) Arene control over thiolate to sulfinate oxidation in albumin by organometallic ruthenium anticancer complexes. Chem Eur J 15 6586-6594... 

Ang WH, De Luca A, Chapuis-Bemasconi C, Juillerat-Jeanneret L, Lo Bello M, Dyson PJ (2007) Organometallic ruthenium inhibitors of glutathione-S-transferase Pl-1 as anticancer drugs. ChemMedChem 2 1799-1806... 

Hartinger CG, Casini A, Duhot C, Tsybin YO, Messori L, Dyson PJ (2008) Stability of an organometallic ruthenium-ubiquitin adduct in the presence of glutathione relevance to antitumour activity. J Inorg Biochem 102 2136-2141... 

Casini A, Gabbiani C, Michelucci E, Pieraccini G, Moneti G, Dyson PJ, Messori L (2009) Exploring metallodrug-protein interactions by mass spectrometry comparisons between platinum coordination complexes and an organometallic ruthenium compound. J Biol Inorg Chem 14 761-770... 

Bergamo A, Masi A, Dyson PJ, Sava G (2008) Modulation of the metastatic progression of breast cancer with an organometallic ruthenium compound. Int J Oncol 33 1281-9... 

Ang WH, Daldini E, Juillerat-Jeanneret L, Dyson PJ (2007) Strategy to tether organometallic ruthenium-arene anticancer compounds to recombinant human serum albumin. Inorg Chem 46(22) 9048-9050... 

Little is known about the chemical nature of the recently isolated carbon clusters (C o> C70, Cg4, and so forth). One potential application of these materials is as highly dispersed supports for metal catalysts, and therefore the question of how metal atoms bind to C40 is of interest. Reaction of C o with organometallic ruthenium and platinum re nts has shown that metals can be attached directly to the carbon framework. Ihe native geometry of transition metal, and an x-ray difi action analysis of the platinum complex [(CgHg)3P]2Pt( () -C6o) C4HgO revealed a structure similar to that known for [(C4Hs)3P]2Pt( n -ethylene). The reactivity of C40 is not like that of relatively electron-rich planar aromatic molecules su( as benzene. The carbon-carbon double bonds of C40 react like those of very electron-deficient arenes and alkcnes. 

Dias, A.R., Garcia, M.H., Rodrigues, J.C., Petersen, J.C., Bjpmholm, T., Geisler, T. Third-harmonic generation in organometallic ruthenium(II) derivatives containing coordinated p-substituted benzonitriles. 1. Mater. Chem. 5, 1861-1865 (1995)... 

Recently, organometallic ruthenium chemistry has found its way into biological applications. Treating [Cp Ru(MeCN)3][CF3S03] with amino acids in THF yields -coordlnated amino acid complexes of the type [Cp Ru(jj -Haa0H)][CF3S03], where HaaOH = L-HPheOH (phenylalanine) or L-HTrpOH (tryptophan), as shown in equation (24). Similarly, dipeptide and cyclopeptide complexes can be synthesized under parallel conditions. These types of complexes are essentially Cp Ru labeled peptides, which could have a notable impact on the analysis of protein receptor sites. ... 

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