Cu-catalyzed sulfenylation of imidazol[1,2-a]pyridine via C–H functionalization using a combination of Na2S2O3 and halides

A novel copper-catalysed sulfenylation method by using the inorganic salt Na2S2O3 and alkyl halides (Cl, Br, I) or iodobenzene homologues is described. The reactions proceeded smoothly, giving regioselective 2-phenylimidazo[1,2-a]pyridine thioether derivatives in good yields via a C–H functionalization process. More importantly, this method has extended the existing methods by offering a better method which can make both alkyl and aryl thioether derivatives under one set of reaction conditions.

[1]  Sheng Zhang,et al.  Catalyst-free thiolation of indoles with sulfonyl hydrazides for the synthesis of 3-sulfenylindoles in water , 2016 .

[2]  Qing Liu,et al.  Sulfination of alcohols with sodium sulfinates promoted by BF3·OEt2: an unexpected access , 2016 .

[3]  Xuefeng Jiang,et al.  Ligand-Controlled Divergent Cross-Coupling Involving Organosilicon Compounds for Thioether and Thioester Synthesis. , 2016, Organic letters.

[4]  Wei Zhao,et al.  A reusable catalytic system for sulfide oxidation and epoxidation of allylic alcohols in water catalyzed by poly(dimethyl diallyl) ammonium/polyoxometalate , 2016 .

[5]  S. Adimurthy,et al.  Dual role of p-tosylchloride: copper-catalyzed sulfenylation and metal free methylthiolation of imidazo[1,2-a]pyridines. , 2016, Organic & biomolecular chemistry.

[6]  Zai-Qun Liu,et al.  Introducing ferrocene into imidazo[1,2-a]pyridine by Groebke three-component-reaction for scavenging radicals and inhibiting DNA oxidation , 2015 .

[7]  K. Jiang,et al.  Selective remote C-H sulfonylation of aminoquinolines with arylsulfonyl chlorides via copper catalysis. , 2015, Chemical communications.

[8]  T. Tu,et al.  Copper-catalyzed electrophilic amination of sodium sulfinates at room temperature. , 2015, Chemical communications.

[9]  Xuefeng Jiang,et al.  Mechanistic Study of a Photocatalyzed C-S Bond Formation Involving Alkyl/Aryl Thiosulfate. , 2015, Chemistry.

[10]  Aihua Zhou,et al.  Regioselective C−S Bond Formation between Flavones and Arylsulfonyl Chlorides through the Use of Ammonium Iodide , 2015 .

[11]  Hiroshi Banno,et al.  Synthetic Studies on Centromere-Associated Protein-E (CENP-E) Inhibitors: 2. Application of Electrostatic Potential Map (EPM) and Structure-Based Modeling to Imidazo[1,2-a]pyridine Derivatives as Anti-Tumor Agents. , 2015, Journal of medicinal chemistry.

[12]  Laura M Sanz,et al.  Carbamoyl Triazoles, Known Serine Protease Inhibitors, Are a Potent New Class of Antimalarials. , 2015, Journal of medicinal chemistry.

[13]  Pengfei Sun,et al.  Direct thiolation of methoxybenzenes with thiols under metal-free conditions by iodine catalysis , 2015 .

[14]  Guoqi Zhang,et al.  Phosphoric Acid-Mediated Synthesis of Vinyl Sulfones through Decarboxylative Coupling Reactions of Sodium Sulfinates with Phenylpropiolic Acids. , 2015, The Journal of organic chemistry.

[15]  Xiaohong Chen,et al.  Copper-Catalyzed γ-Sulfonylation of α,β-Unsaturated Carbonyl Compounds by Means of Silyl Dienol Ethers. , 2015, Organic letters.

[16]  Xuefeng Jiang,et al.  CO2-promoted oxidative cross-coupling reaction for C-S bond formation via masked strategy in an odourless way. , 2015, Chemical communications.

[17]  Neetu Singh,et al.  A Direct Metal-Free Decarboxylative Sulfono Functionalization (DSF) of Cinnamic Acids to α,β-Unsaturated Phenyl Sulfones. , 2015, Organic letters.

[18]  B. Liu,et al.  Nickel-catalyzed direct thiolation of unactivated C(sp(3))-H bonds with disulfides. , 2015, Chemical communications.

[19]  S. Yin,et al.  Nickel-catalyzed direct thiolation of C(sp(3))-H bonds in aliphatic amides. , 2015, Organic letters.

[20]  Jidan Liu,et al.  Copper-mediated ortho C-H sulfonylation of benzoic acid derivatives with sodium sulfinates. , 2015, Chemical communications.

[21]  A. Corma,et al.  Stabilized naked sub-nanometric Cu clusters within a polymeric film catalyze C-N, C-C, C-O, C-S, and C-P bond-forming reactions. , 2015, Journal of the American Chemical Society.

[22]  A. Hajra,et al.  Iodine-catalyzed regioselective thiolation of imidazo[1,2-a]pyridines using sulfonyl hydrazides as a thiol surrogate. , 2015, Organic & biomolecular chemistry.

[23]  Shucheng Wang,et al.  Iodine–triphenylphosphine mediated sulfenylation of imidazoheterocycles with sodium sulfinates , 2015 .

[24]  Han Wang,et al.  Reaction of arynes with sulfoxides. , 2015, Organic letters.

[25]  S. Berteina‐Raboin,et al.  Iodine-catalyzed regioselective sulfenylation of imidazoheterocycles in PEG400 , 2015 .

[26]  Xiaomei Zhang,et al.  Sulfide synthesis through copper-catalyzed C-S bond formation under biomolecule-compatible conditions. , 2015, Chemical communications.

[27]  C. Caballero-George,et al.  Modulation of Calcium Signaling of Angiotensin AT1, Endothelin ETA, and ETB Receptors by Silibinin, Quercetin, Crocin, Diallyl Sulfides, and Ginsenoside Rb1 , 2014, Planta Medica.

[28]  B. Breit,et al.  Direct transformation of terminal alkynes to branched allylic sulfones. , 2014, Journal of the American Chemical Society.

[29]  T. Suhara,et al.  Biological evaluation of the radioiodinated imidazo[1,2-a]pyridine derivative DRK092 for amyloid-β imaging in mouse model of Alzheimer's disease , 2014, Neuroscience Letters.

[30]  Chaoying Yu,et al.  Heterogeneously copper-catalyzed oxidative synthesis of imidazo[1,2-a]pyridines using 2-aminopyridines and ketones under ligand- and additive-free conditions , 2014 .

[31]  Huanfeng Jiang,et al.  Copper-catalyzed aerobic oxidative N-S bond functionalization for C-S bond formation: regio- and stereoselective synthesis of sulfones and thioethers. , 2014, Chemistry.

[32]  S. Adimurthy,et al.  N-chlorosuccinimide-promoted regioselective sulfenylation of imidazoheterocycles at room temperature. , 2014, Organic letters.

[33]  Yiming Li,et al.  A highly efficient Cu-catalyzed S-transfer reaction: from amine to sulfide. , 2014, Organic letters.

[34]  Ronghua Zhang,et al.  Cs2CO3 promoted direct C–H bond sulfenylation of imidazo[1,2-a]pyridines and related heteroarenes in ionic liquid , 2014 .

[35]  J. Gómez-Jeria.  An analysis of the electronic structure of an imidazo [1,2-a] pyrrolo [2,3-c] pyridine series and their anti-bovine viral diarrhea virus activity. , 2014 .

[36]  H. Doucet,et al.  Benzenesulfonyl chlorides: new reagents for access to alternative regioisomers in palladium-catalysed direct arylations of thiophenes , 2014 .

[37]  Yunyang Wei,et al.  Aerobic Multicomponent Tandem Synthesis of 3‐Sulfenylimidazo[1,2‐a]pyridines from Ketones, 2‐Aminopyridines, and Disulfides , 2013 .

[38]  S. Santra,et al.  Copper‐Catalyzed Synthesis of Imidazo[1,2‐a]pyridines through Tandem Imine Formation‐Oxidative Cyclization under Ambient Air: One‐Step Synthesis of Zolimidine on a Gram‐Scale , 2013 .

[39]  Steve Price,et al.  Discovery of 2-{3-[2-(1-isopropyl-3-methyl-1H-1,2-4-triazol-5-yl)-5,6-dihydrobenzo[f]imidazo[1,2-d][1,4]oxazepin-9-yl]-1H-pyrazol-1-yl}-2-methylpropanamide (GDC-0032): a β-sparing phosphoinositide 3-kinase inhibitor with high unbound exposure and robust in vivo antitumor activity. , 2013, Journal of medicinal chemistry.

[40]  H. Liu,et al.  Efficient access to 1,4-benzothiazine: palladium-catalyzed double C-S bond formation using Na2S2O3 as sulfurating reagent. , 2013, Organic letters.

[41]  Xingwei Li,et al.  Palladium-catalyzed desulfitative arylation of azoles with arylsulfonyl hydrazides. , 2012, Organic & biomolecular chemistry.

[42]  D. Sullivan,et al.  Malaria-infected mice are completely cured by one 6 mg/kg oral dose of a new monomeric trioxane sulfide combined with mefloquine. , 2012, Journal of medicinal chemistry.

[43]  S. Kerwin,et al.  Cytotoxic 1,2-dialkynylimidazole-based aza-enediynes: aza-Bergman rearrangement rates do not predict cytotoxicity. , 2011, Journal of medicinal chemistry.

[44]  Thomas Ruhland,et al.  Discovery of 1-[2-(2,4-dimethylphenylsulfanyl)phenyl]piperazine (Lu AA21004): a novel multimodal compound for the treatment of major depressive disorder. , 2011, Journal of medicinal chemistry.

[45]  S. D. De Keersmaecker,et al.  Structure-activity relationship of 4(5)-aryl-2-amino-1H-imidazoles, N1-substituted 2-aminoimidazoles and imidazo[1,2-a]pyrimidinium salts as inhibitors of biofilm formation by Salmonella typhimurium and Pseudomonas aeruginosa. , 2011, Journal of medicinal chemistry.

[46]  K. Pavelić,et al.  Novel amidino-substituted thienyl- and furylvinylbenzimidazole: derivatives and their photochemical conversion into corresponding diazacyclopenta[c]fluorenes. synthesis, interactions with DNA and RNA, and antitumor evaluation. 4. , 2008, Journal of medicinal chemistry.

[47]  J. Yadav,et al.  Cu(OTf)2-catalyzed synthesis of imidazo[1,2-a]pyridines from α-diazoketones and 2-aminopyridines , 2007 .

[48]  K. Pavelić,et al.  Novel cyano- and amidino-substituted derivatives of styryl-2-benzimidazoles and benzimidazo[1,2-a]quinolines. Synthesis, photochemical synthesis, DNA binding, and antitumor evaluation, part 3. , 2007, Journal of medicinal chemistry.

[49]  R. Steudel,et al.  Sulphur compounds: CLVII. Determination of cysteine-S-sulphonate by ionpair chromatography and its formation by autoxidation of cysteine persulphide , 1992 .

[50]  C. Christophersen,et al.  Organic Sulfur Compounds from Marine Organisms , 1986 .

[51]  J. M. Anderson,et al.  Timing of covalency changes in nucleophilic substitutions at sulfenyl sulfur. Influence of meta and para substitutuents on the rate of reaction of aryl Bunte salts with cyanide ion , 1968 .

[52]  J. L. Kice.  A Kinetic Study of the Acid Hydrolysis of a Bunte Salt , 1963 .

[53]  H. Bunte.  Zur Constitution der unterschwefligen Säure , 1874 .