7205-58-5Relevant articles and documents
Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
supporting information, p. 3723 - 3728 (2021/04/07)
We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
Production of Alkyl Aryl Sulfides from Aromatic Disulfides and Alkyl Carboxylates via a Disilathiane–Disulfide Interchange Reaction
Nakajima, Takumi,Takano, Ken,Maeda, Hiromu,Ogiwara, Yohei,Sakai, Norio
supporting information, p. 4103 - 4107 (2021/11/10)
The results of this study show that disilathiane is an effective mediator in the synthesis of alkyl aryl sulfides with disulfides and alkyl carboxylates. Mechanistic studies suggest that disilathiane promotes cleavage of the sulfur–sulfur bond of disulfides to generate thiosilane as a key intermediate. Diselenides were also applicable to this transformation to produce the corresponding selenides.
A mild and chemoselective CALB biocatalysed synthesis of sulfoxides exploiting the dual role of AcOEt as solvent and reagent
Anselmi, Silvia,Liu, Siyu,Kim, Seong-Heun,Barry, Sarah M.,Moody, Thomas S.,Castagnolo, Daniele
supporting information, p. 156 - 161 (2021/01/14)
A mild, chemoselective and sustainable biocatalysed synthesis of sulfoxides has been developed exploiting CALB and using AcOEt with a dual role of more environmentally friendly reaction solvent and enzyme substrate. A series of sulfoxides, including the drug omeprazole, have been synthesised in high yields and with excellent E-factors.
Discovery of carboxyl-containing biaryl ureas as potent RORγt inverse agonists
Sun, Nannan,Huang, Yafei,Yu, Mingcheng,Zhao, Yunpeng,Chen, Ji-An,Zhu, Chenyu,Song, Meiqi,Guo, Huimin,Xie, Qiong,Wang, Yonghui
supporting information, (2020/07/21)
GSK805 (1) is a potent RORγt inverse agonist, but a drawback of 1 is its low solubility, leading to a limited absorption in high doses. We have explored detailed structure-activity relationship on the amide linker, biaryl and arylsulfonyl moieties of 1 trying to improve solubility while maintaining RORγt activity. As a result, a novel series of carboxyl-containing biaryl urea derivatives was discovered as potent RORγt inverse agonists with improved drug-like properties. Compound 3i showed potent RORγt inhibitory activity and subtype selectivity with an IC50 of 63.8 nM in RORγ FRET assay and 85 nM in cell-based RORγ-GAL4 promotor reporter assay. Reasonable inhibitory activity of 3i was also achieved in mouse Th17 cell differentiation assay (76percent inhibition at 0.3 μM). Moreover, 3i had greatly improved aqueous solubility at pH 7.4 compared to 1, exhibited decent mouse PK profile and demonstrated some in vivo efficacy in an imiquimod-induced psoriasis mice model.
Site-Selective C?S Bond Formation at C?Br over C?OTf and C?Cl Enabled by an Air-Stable, Easily Recoverable, and Recyclable Palladium(I) Catalyst
Scattolin, Thomas,Senol, Erdem,Yin, Guoyin,Guo, Qianqian,Schoenebeck, Franziska
supporting information, p. 12425 - 12429 (2018/09/18)
This report widens the repertoire of emerging PdI catalysis to carbon–heteroatom, that is, C?S bond formation. While Pd0-catalyzed protocols may suffer from the formation of poisonous sulfide-bound off-cycle intermediates and lack of selectivity, the mechanistically diverse PdI catalysis concept circumvents these challenges and allows for C?S bond formation (S–aryl and S–alkyl) of a wide range of aryl halides. Site-selective thiolations of C?Br sites in the presence of C?Cl and C?OTf were achieved in a general and a priori predictable fashion. Computational, spectroscopic, X-ray, and reactivity data support dinuclear PdI catalysis to be operative. Contrary to air-sensitive Pd0, the active PdI species was easily recovered in the open atmosphere and subjected to multiple rounds of recycling.
C-H Alkenylation of Heteroarenes: Mechanism, Rate, and Selectivity Changes Enabled by Thioether Ligands
Gorsline, Bradley J.,Wang, Long,Ren, Peng,Carrow, Brad P.
supporting information, p. 9605 - 9614 (2017/07/24)
Thioether ancillary ligands have been identified that can greatly accelerate the C-H alkenylation of O-, S-, and N-heteroarenes. Kinetic data suggest thioether-Pd-catalyzed reactions can be as much as 800× faster than classic ligandless systems. Furthermore, mechanistic studies revealed C-H bond cleavage as the turnover-limiting step, and that rate acceleration upon thioether coordination is correlated to a change from a neutral to a cationic pathway for this key step. The formation of a cationic, low-coordinate catalytic intermediate in these reactions may also account for unusual catalyst-controlled site selectivity wherein C-H alkenylation of five-atom heteroarenes can occur under electronic control with thioether ligands even when this necessarily involves reaction at a more hindered C-H bond. The thioether effect also enables short reaction times under mild conditions for many O-, S-, and N-heteroarenes (55 examples), including examples of late-stage drug derivatization.
A Convenient, Mild, and Green Synthesis of NH-Sulfoximines in Flow Reactors
Degennaro, Leonardo,Tota, Arianna,De Angelis, Sonia,Andresini, Michael,Cardellicchio, Cosimo,Capozzi, Maria Annunziata,Romanazzi, Giuseppe,Luisi, Renzo
supporting information, p. 6486 - 6490 (2017/09/13)
NH-sulfoximines are emerging as useful and important targets in drug discovery and synthetic organic chemistry. We report herein the development of an efficient, convenient, and sustainable continuous-flow strategy, for the direct, straightforward preparation of NH-sulfoximines by using sulfides or sulfoxides as suitable starting material. The flow process uses PhI(OAc)2 as the oxidant and aqueous solutions of ammonia as the N source. The scope of the reaction has been demonstrated by using several substituted sulfides and sulfoxides including enantioenriched and biologically relevant starting materials. The flow strategy was found to be more convenient with respect to conventional batch processing.
Carbon-sulphur cross coupling reactions catalyzed by nickel-based coordination polymers based on metalloligands
Kumar, Gulshan,Hussain, Firasat,Gupta, Rajeev
, p. 15023 - 15031 (2017/11/14)
This work illustrates two Ni2+ based coordination polymers (CPs, 1-Ni and 2-Ni) synthesized using two related Co3+ based metalloligands offering appended arylcarboxylate groups. The crystal structure of 1-Ni displays a porous 3D network having well-defined major and minor pores whereas 2-Ni exhibits a somewhat densely packed structure. Both CPs supported the exchange of coordinated water molecules and the inclusion of iodine within their porous structure whereas binding studies illustrated that the Ni(ii) ion in these CPs can bind thiophenol, a reagent used in the C-S cross coupling reactions. The two CPs functioned as the reusable heterogeneous catalysts for the C-S cross coupling reactions between substituted aromatic halides and thiophenol as well as cyclohexanethiol and ethanethiol.
NOVEL GLUCOKINASE ACTIVATOR COMPOUNDS, COMPOSITIONS CONTAINING SUCH COMPOUNDS, AND METHODS OF TREATMENT
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Page/Page column 52, (2014/07/08)
Novel pyridine-2-carboxamide derivatives of formula I: and pharmaceutically acceptable salts thereof are disclosed as useful for treating or preventing type 2 diabetes and similar conditions. The compounds are effective as glucokinase activating agents. Pharmaceutical compositions and methods of treatment are also included.
Cu-catalyzed one-pot synthesis of unsymmetrical diaryl thioethers by coupling of aryl halides using a thiol precursor
Prasad,Sekar, Govindasamy
supporting information; experimental part, p. 1008 - 1011 (2011/05/08)
An efficient Cu-catalyzed one-pot approach for the synthesis of unsymmetrical diaryl thioethers using potassium ethyl xanthogenate as a thiol surrogate is developed. This new protocol avoids usage of intricate thiols and makes use of its easily available xanthate as a precursor, and thiol will be generated in situ to prepare the diaryl thioethers through a Cu-catalyzed double arylation. This strategy was further successfully utilized for the synthesis of symmetrical diaryl thioethers, aryl alkyl thioethers, and benzothiazoles. (Figure Presented)
