29634-49-9Relevant academic research and scientific papers
Enantioselective syntheses of sulfoxides in octahedral ruthenium(II) complexes via a chiral-at-metal strategy
Li, Zheng-Zheng,Wen, A-Hao,Yao, Su-Yang,Ye, Bao-Hui
, p. 2726 - 2733 (2015)
The preparation of chiral 2-(alkylsulfinyl)phenol compounds by enantioselective coordination-oxidation of the thioether ruthenium complexes with a chiral-at-metal strategy has been developed. The enantiomerically pure sulfoxide complexes δ-[Ru(bpy)2{(R)-LO-R}](PF6) (bpy is 2,2′-bipyridine, HLO-R is 2-(alkylsulfinyl)phenol, R = Me (δ-1a), Et (δ-2a), iPr (δ-3a), Bn (δ-4a), and Nap (δ-5a)) and δ-[Ru(bpy)2{(S)-LO-R}](PF6) (R = Me (δ-1a), Et (δ-2a), iPr (δ-3a), Bn (δ-4a), and Nap (δ-5a)) have been synthesized by the reaction of δ-[Ru(bpy)2(py)2]2+ or δ-[Ru(bpy)2(py)2]2+ with the prochiral thioether ligands 2-(alkylthio)phenol (HL-R), followed by enantioselective oxidation with m-CPBA as oxidant. The X-ray crystallography was used to verify the stereochemistry of ruthenium complexes and sulfur atoms. The configurations of the ruthenium complexes are stable during the coordination and oxidation reactions. Moreover, the chiral sulfoxide ligands are enantioselectively generated by controlling of the configuration of ruthenium centers in the course of oxidation reaction. That is, the δ configuration at the ruthenium center generates the S sulfoxide ligand; on the contrary, the δ configuration of the ruthenium complex originates the R sulfoxide ligand. Acidolysis of δ-[Ru(bpy)2{(R)-LO-R}](PF6) and δ-[Ru(bpy)2{(S)-LO-R}](PF6) complexes in the presence of TFA-MeCN afforded the chiral ligands (R)-HLO-R and (S)-HLO-R in 96-99% ee values, respectively. Importantly, the chiral ruthenium complexes can be recycled as δ/δ-[Ru(bpy)2(MeCN)2](PF6)2 and reused in a next reaction cycle with complete retention of the configurations at ruthenium centers.
Structure Property Relationships of Carboxylic Acid Isosteres
Lassalas, Pierrik,Gay, Bryant,Lasfargeas, Caroline,James, Michael J.,Tran, Van,Vijayendran, Krishna G.,Brunden, Kurt R.,Kozlowski, Marisa C.,Thomas, Craig J.,Smith, Amos B.,Huryn, Donna M.,Ballatore, Carlo
, p. 3183 - 3203 (2016/05/19)
The replacement of a carboxylic acid with a surrogate structure, or (bio)-isostere, is a classical strategy in medicinal chemistry. The general underlying principle is that by maintaining the features of the carboxylic acid critical for biological activity, but appropriately modifying the physicochemical properties, improved analogs may result. In this context, a systematic assessment of the physicochemical properties of carboxylic acid isosteres would be desirable to enable more informed decisions of potential replacements to be used for analog design. Herein we report the structure-property relationships (SPR) of 35 phenylpropionic acid derivatives, in which the carboxylic acid moiety is replaced with a series of known isosteres. The data set generated provides an assessment of the relative impact on the physicochemical properties that these replacements may have compared to the carboxylic acid analog. As such, this study presents a framework for how to rationally apply isosteric replacements of the carboxylic acid functional group.
