Transition-Metal-Free C-S Bond Formation: Synthesis of Polysubstituted Diaryl Sulfides and α-Thioarylcarbonyl Compounds.

A transition-metal-free protocol for the construction of C-S bonds has been developed. Acetylacetone acts as a new and green aryl source for the synthesis of polysubstituted diarylsulfides bearing a free hydroxy group and a ketone group, which provides a new access to a series of flavonoids containing a thioaryl group. In addition, a series of α-thioarylcarbonyl compounds are obtained in good to excellent yields.

[1]  C. Su,et al.  Efficient Generation of C-S Bonds via a By-Product-Promoted Selective Coupling of Alcohols, Organic Halides, and Thiourea , 2017 .

[2]  Xuefeng Jiang,et al.  Cu(ii)-catalyzed sulfide construction: both aryl groups utilization of intermolecular and intramolecular diaryliodonium salt. , 2017, Chemical communications.

[3]  N. Huang,et al.  Disulfide-Directed C–H Hydroxylation for Synthesis of Sulfonyl Diphenyl Sulfides and 2-(Phenylthio)phenols with Oxygen as Oxidant , 2017 .

[4]  Sangit Kumar,et al.  Transition-Metal-Free Selective Oxidative C(sp3)-S/Se Coupling of Oxindoles, Tetralone, and Arylacetamides: Synthesis of Unsymmetrical Organochalcogenides. , 2017, Organic letters.

[5]  M. Májek,et al.  Metal-free radical thiolations mediated by very weak bases. , 2016, Organic & biomolecular chemistry.

[6]  K. Lu,et al.  Iodine-catalysed regioselective thiolation of flavonoids using sulfonyl hydrazides as sulfenylation reagents. , 2016, Organic & biomolecular chemistry.

[7]  Steven H. Liang,et al.  Sulfur Containing Scaffolds in Drugs: Synthesis and Application in Medicinal Chemistry. , 2016, Current topics in medicinal chemistry.

[8]  S. H. Siddiki,et al.  Hydrodeoxygenation of sulfoxides to sulfides by a Pt and MoOx co-loaded TiO2 catalyst , 2016 .

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

[10]  S. Shimizu,et al.  A mild and facile synthesis of aryl and alkenyl sulfides via copper-catalyzed deborylthiolation of organoborons with thiosulfonates. , 2015, Chemical communications.

[11]  M. Gholinejad One‐Pot Copper‐Catalysed Thioetherification of Aryl Halides Using Alcohols and Lawesson's Reagent in Diglyme , 2015 .

[12]  Xi‐Cun Wang,et al.  Chemo‐Controlled Cross‐Coupling of Di(hetero)aryl Disulfides with Grignard Reagents: CC vs. CS Bond Formation , 2015 .

[13]  Mao‐Lin Hu,et al.  High activity and stability in the cross-coupling of aryl halides with disulfides over Cu-doped hierarchically porous zeolite ZSM-5. , 2015, Chemical communications.

[14]  Wei Zhang,et al.  One-pot synthesis of 3,5-disubstituted and polysubstituted phenols from acyclic precursors. , 2015, Organic letters.

[15]  R. Fasan,et al.  Intermolecular carbene S–H insertion catalysed by engineered myoglobin-based catalysts , 2015, Chemical science.

[16]  Yi‐chen Liu,et al.  Transition-metal-catalyzed C-S bond coupling reaction. , 2014, Chemistry, an Asian journal.

[17]  H. Liu,et al.  Transfer of sulfur: from simple to diverse. , 2013, Chemistry, an Asian journal.

[18]  Yunyang Wei,et al.  Iodine‐Catalyzed Selective Synthesis of 2‐Sulfanylphenols via Oxidative Aromatization of Cyclohexanones and Disulfides , 2013 .

[19]  C. Bolm,et al.  Copper-Catalyzed Synthesis of α-Thioaryl Carbonyl Compounds Through SS and CC Bond Cleavage , 2013 .

[20]  J. Zou,et al.  K2CO3 promoted direct sulfenylation of indoles: a facile approach towards 3-sulfenylindoles , 2013 .

[21]  Arunandan Kumar,et al.  Potassium tert-butoxide-mediated synthesis of unsymmetrical diaryl ethers, sulfides and selenides from aryl bromides , 2013 .

[22]  Amit Kumar,et al.  Transition-metal-free synthesis of unsymmetrical diaryl chalcogenides from arenes and diaryl dichalcogenides. , 2013, The Journal of organic chemistry.

[23]  Chin‐Fa Lee,et al.  Highly regioselective synthesis of aryl chalcogenides through C-H functionalization of arenes. , 2012, Chemical communications.

[24]  B. Ranu,et al.  Microwave-assisted reaction of aryl diazonium fluoroborate and diaryl dichalcogenides in dimethyl carbonate: a general procedure for the synthesis of unsymmetrical diaryl chalcogenides , 2012 .

[25]  Huajian Xu,et al.  Chan-Lam-type S-arylation of thiols with boronic acids at room temperature. , 2012, The Journal of organic chemistry.

[26]  Itaru Osaka,et al.  Thienoacene‐Based Organic Semiconductors , 2011, Advanced materials.

[27]  Kuo‐Wei Huang,et al.  Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols. , 2011, The Journal of organic chemistry.

[28]  M. Gholinejad,et al.  One-Pot Thioetherification of Aryl Halides Using Thiourea and Alkyl Bromides Catalyzed by Copper(I) Iodide Free from Foul-Smelling Thiols in Wet Polyethylene Glycol (PEG 200) , 2010 .

[29]  Minyong Li,et al.  Synthesis and Evaluation of New Antagonists of Bacterial Quorum Sensing in Vibrio harveyi , 2009, ChemMedChem.

[30]  C. Bolm,et al.  Copper-catalyzed cross-couplings with part-per-million catalyst loadings. , 2009, Angewandte Chemie.

[31]  Ri‐Yuan Tang,et al.  Solvent-free copper-catalyzed oxidative S-arylation of 1,2-diaryldisulfides with aryltrimethoxysilane , 2009 .

[32]  Phil Ho Lee,et al.  Palladium-catalyzed carbon-sulfur cross-coupling reactions with indium tri(organothiolate) and its application to sequential one-pot processes. , 2008, The Journal of organic chemistry.

[33]  P. Langer,et al.  Regioselective synthesis of 4-alkyl- and 4-aryl-6-(perfluoroalkyl)salicylic acid derivatives by formal [3+3] cyclocondensation of 1,3-bis(silyloxy)-1,3-butadienes with 3-silyloxy-1-(perfluoroalkyl)prop-2-en-1-ones , 2008 .

[34]  C. Bolm,et al.  Iron-catalyzed S-arylation of thiols with aryl iodides. , 2008, Angewandte Chemie.

[35]  J. Ying,et al.  The first N-heterocyclic carbene-based nickel catalyst for C-S coupling. , 2007, Organic letters.

[36]  N. Taniguchi Convenient synthesis of unsymmetrical organochalcogenides using organoboronic acids with dichalcogenides via cleavage of the S-S, Se-Se, or Te-Te bond by a copper catalyst. , 2007, The Journal of organic chemistry.

[37]  Hsin-Hung Chen,et al.  1,1,1-tris(hydroxymethyl)ethane as a new, efficient, and versatile tripod ligand for copper-catalyzed cross-coupling reactions of aryl iodides with amides, thiols, and phenols. , 2006, Organic letters.

[38]  J. Hartwig,et al.  Highly efficient and functional-group-tolerant catalysts for the palladium-catalyzed coupling of aryl chlorides with thiols. , 2006, Chemistry.

[39]  Sangit Kumar,et al.  Microwave-assisted copper-catalyzed preparation of diaryl chalcogenides. , 2006, The Journal of organic chemistry.

[40]  J. Hartwig,et al.  A general and long-lived catalyst for the palladium-catalyzed coupling of aryl halides with thiols. , 2006, Journal of the American Chemical Society.

[41]  Andrea Brancale,et al.  New arylthioindoles: potent inhibitors of tubulin polymerization. 2. Structure-activity relationships and molecular modeling studies. , 2006, Journal of medicinal chemistry.

[42]  J. Spindler,et al.  Pd2(dba)3/Xantphos-catalyzed cross-coupling of thiols and aryl bromides/triflates , 2005 .

[43]  T. Itoh,et al.  A general palladium-catalyzed coupling of aryl bromides/triflates and thiols. , 2004, Organic letters.

[44]  N. Taniguchi Alkyl- or arylthiolation of aryl iodide via cleavage of the S-S bond of disulfide compound by nickel catalyst and zinc. , 2004, The Journal of organic chemistry.

[45]  J. Haorah,et al.  Nitrosation of glycine ethyl ester and ethyl diazoacetate to give the alkylating agent and mutagen ethyl chloro(hydroximino)acetate. , 2004, Chemical research in toxicology.

[46]  T. Onami,et al.  Magnesium-induced copper-catalyzed synthesis of unsymmetrical diaryl chalcogenide compounds from aryl iodide via cleavage of the Se-Se or S-S bond. , 2004, The Journal of organic chemistry.

[47]  S. Ley,et al.  Modern Synthetic Methods for Copper‐Mediated C(aryl) ? O, C(aryl) ? N, and C(aryl) ? S Bond Formation , 2003 .

[48]  P. Caboni,et al.  Phenylpyrazole insecticide photochemistry, metabolism, and GABAergic action: ethiprole compared with fipronil. , 2003, Journal of agricultural and food chemistry.

[49]  Peter Langer,et al.  [3+3] cyclizations of 1,3-bis(silyl enol ether)s with 1,1-diacetylcyclopentane and 1,1-diacetylcyclopropane. , 2003, Angewandte Chemie.

[50]  J. Šrogl,et al.  A mild, nonbasic synthesis of thioethers. The copper-catalyzed coupling of boronic acids with N-thio(alkyl, aryl, heteroaryl)imides. , 2002, Organic letters.

[51]  W. Greenlee,et al.  Design and synthesis of piperidinyl piperidine analogues as potent and selective M2 muscarinic receptor antagonists. , 2000, Bioorganic & medicinal chemistry letters.

[52]  T. Mitsudo,et al.  Metal-catalyzed carbon-sulfur bond formation. , 2000 .

[53]  Herradura Ps,et al.  Copper-mediated cross-coupling of aryl boronic acids and alkyl thiols. , 2000 .

[54]  P. Pietta,et al.  Flavonoids as antioxidants. , 2000, Journal of natural products.

[55]  T. Liljefors,et al.  Novel potent ligands for the central nicotinic acetylcholine receptor: synthesis, receptor binding, and 3D-QSAR analysis. , 2000, Journal of medicinal chemistry.

[56]  R. Volante,et al.  Palladium-Catalyzed Synthesis of Aryl Sulfides from Aryl Triflates , 1998 .

[57]  J. Hartwig Transition Metal Catalyzed Synthesis of Arylamines and Aryl Ethers from Aryl Halides and Triflates: Scope and Mechanism. , 1998, Angewandte Chemie.

[58]  B. Marjanović,et al.  Flavonoids as Antioxidants , 1994 .

[59]  D. Lightner,et al.  An Improved Procedure for Mono C-Alkylation of Pentane-2.4-Dione with ω-Bromoacid Esters , 1990 .

[60]  O. Baldovino-Pantaleón,et al.  Alkyl- and arylthiolation of aryl halides catalyzed by fluorinated bis-imino-nickel NNN pincer complexes [NiCl2{C5H3N-2,6-(CHNArf)2}] , 2006 .

[61]  J. Clark,et al.  Hydrogen bonding in organic synthesis. Part 7. Intermolecular self-condensation of some enolisable ketones in the presence of fluoride , 1977 .