19093-34-6Relevant articles and documents
Tagaki et al.
, p. 6131 (1968)
Enantioselective oxidation of thioethers to sulfoxides by means of a structural template with chiral-at-metal ruthenium complexes
Li, Zheng-Zheng,Yao, Su-Yang,Ye, Bao-Hui
, p. 141 - 150 (2015/02/05)
Treatment of cis-[Ru(bpy)2Cl2]·2H2O or Δ/Λ-[Ru(bpy)2(py)2]2+ (bpy=2,2′-bipyridine, py=pyridine) with the prochiral thioether ligands 2-alkylthiobenzoic acid (HOS-R) produces the corresponding thioether complexes rac-[Ru(bpy)2(OS-R)](PF6) (R=Me (rac-1), iPr (rac-2), 2-benzylthiobenzonate (Bn) (rac-3)) and Δ/Λ-[Ru(bpy)2(OS-R)](PF6) (R=Me (Δ-1/Λ-1), iPr (Δ-2/Λ-2), Bn (Δ-3/Λ-3)) with retention of the configurations at chiral metal centers. In situ oxidation of the thioether complexes by metachloroperoxybenzoic acid provides the corresponding sulfoxide complexes rac-[Ru(bpy)2(OSO-R)](PF6) (OSO-R is 2-alkylsulfinylbenzonate, R=Me (rac-1a), iPr (rac-2a), Bn (rac-3a)), Δ-[Ru(bpy)2{(R)-OSO-R}](PF6) (R=Me (Δ-1a), iPr (Δ-2a), Bn (Δ-3a)), and Λ-[Ru(bpy)2{(S)-OSO-R}](PF6) (R=Me (Λ-1a), iPr (Λ-2a), Bn (Λ-3a)) in yields of 95% with 98% ee values. The absolute configurations at the metal centers and sulfur atoms were determined by means of X-ray crystallography. The results indicate that the configurations of the metal centers are retained and have the function of controlling sulfoxide chirality during the oxidation process. The Δ metal-centered configuration enantioselectively generates an R-configuration sulfoxide, and the Λ configuration enantioselectively forms an S-configuration sulfoxide in the course of the in situ oxidation reaction, thereby resulting in a predetermined chirality of the sulfoxide ligands. The predetermined chirality of sulfoxides (S)-HOSO-R and (R)-HOSO-R were obtained by the treatments of the corresponding sulfoxide complexes Δ-[Ru(bpy)2{(R )-OSO-R}](PF6) and Λ-[Ru(bpy)2{(S)-OSO-R}](PF6) with trifluoroacetic acid in yields of 90% with 83.5-92.9% ee values.
Cis-platinum complexes with chelating amines and sulphinyl carboxylates
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, (2008/06/13)
STR1 Platinum (II) complexes of formula (I) where: Am is a monodentate amine, or (Am)2 is a bidentate amine, B represents a straight or branched alkyl residue or a single bond, R is selected from the group of hydrogen, (C3 -C8) cycloalkyl, phenyl or naphthyl which may be substituted by halogens (I, Br, Cl, F), trihalomethane, hydroxyl, (C1 -C4)-alkoxyl, (C1 -C7)-acylamino, (C1 -C7)-sulphamido, allyl, phenoxyl, haloalkoxyl, nitro, cyano, azido, with condition that when R is hydrogen B is different from a single bond, Q is a residue of formula --(CH2)n1 --CRa Rb --(CH2)n2 --, 1,2- or 2,3-naphthalene, benzo-1,3-dioxolan-5,6-diyl, substituted or unsubstituted 1,2-phenylene, Ra and Rb are selected independently of each other from the group of hydrogen, allyl, linear or branched (C1 -C8)-alkyl, --(CH2)p OH, --(CH2 CH2 O)q --CH3, or taken together with the carbon atom to which they are bonded form a (C3 -C8) cycloalkyl, or heterocyclic tetrahydropyran-4,4-diyl, n1 and n2 are independently zero or the integer 1, p is an integer from 2 to 6, and q is an integer from 1-3, X- is a biocompatible anion such as chloride, bromide, iodide, nitrate, perchlorate, or one equivalent of sulphate or phosphate, or an anion of a monovalent C1 -C4 organic acid such as acetate, propionate or chloroacetate, or of an aromatic acid such as benzoate, or of a heteroaromatic acid such as nicotinate are described. The compounds are useful as anti-tumor drugs.
