- The Aryl Sulfide Synthesis via Sulfide Transfer
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Aryl sulfides are in great demands in drugs and materials sciences. To avoid using nucleophilic and noxious thiols, many efforts have been focused on exploring novel sulfide resources. Herein, a reductive Pd-catalyzed, Ni-mediated method to synthesize aryl sulfides via a sulfide transfer reaction is developed. The utility and scope of this reaction is exemplified by various aryl electrophiles and aryl sulfides. Mechanistic studies reveal two competing catalytic cycles of sulfide transfer and aryl transfer in this reaction, where the former one is favored over the later one because of the large energy barrier difference during the transmetalation. Moreover, two important chemicals are late-stage functionalized by this method, exhibiting the potential applications in drugs and materials science.
- Huang, Hui,Li, Xiang,Liang, Xinyu,Lin, Qijie,Ma, Bowei,Pei, Shurui,Shi, Qinqin,Wang, Song,Wang, Zhi-Xiang,Wen, Kaikai,Zhang, Bei-Bei,Zhang, Meng
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supporting information
(2022/05/14)
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- Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
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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.
- Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
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supporting information
p. 3723 - 3728
(2021/04/07)
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- A Nickel-Doped Dehydrobenzoannulene-Based Two-Dimensional Covalent Organic Framework for the Reductive Cleavage of Inert Aryl C-S Bonds
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The development of metalated covalent organic frameworks (COFs) is useful for generating recyclable catalytic systems for practical applications. Herein, we report the synthesis, characterization, and catalytic properties of an azine-linked two-dimensional (2D) COF containing nickel-doped dehydrobenzoannulene (DBA) units. We demonstrate that Ni-DBA-2D-COF can be used to reductively cleave the aryl C-S bonds of several organosulfur compounds utilizing dimethylethylsilane as the reducing agent. The Ni-DBA-2D-COF catalytic system displays excellent recyclability and good yields. This work highlights a rare example of utilizing metalated DBA complexes to perform catalytic transformations.
- Haug, W. Karl,McGrier, Psaras L.,Morman, Blake T.,Thomas, Christine M.,Wolfson, Eric R.
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supporting information
p. 5521 - 5525
(2020/04/09)
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- Iridium-Catalyzed ortho-C-H Borylation of Thioanisole Derivatives Using Bipyridine-Type Ligand
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A simple iridium catalytic system was developed that allows for a variety of 2-borylthioanisoles to be easily synthesized via ortho-selective C-H borylation of thioanisole derivatives. Once introduced, boryl and methylthio groups were converted by palladium-catalyzed transformations. Density functional theory calculations revealed that weak interactions, such as hydrogen bonding between the C-H bond of the SCH3 group and the oxygen atom of the boryl ligand, control the ortho-selectivity.
- Kuninobu, Yoichiro,Naito, Morio,Torigoe, Takeru,Yamanaka, Masahiro,Zeng, Jialin
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supporting information
(2020/05/08)
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- Copper-Catalyzed Methylthiolation of Aryl Iodides and Bromides with Dimethyl Disulfide in Water
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An efficient route to aryl methyl sulfides through the copper-catalyzed coupling reaction of aryl iodides or bromides with dimethyl disulfide in water is described. Electron-donating and electron-withdrawing functional groups in the substrates were tolerated, and the corresponding products were obtained in moderate to good yields.
- Wang, Ying-Yu,Wu, Xiang-Mei,Yang, Ming-Hua
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supporting information
(2020/07/20)
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- Photocatalytic Deoxygenation of Sulfoxides Using Visible Light: Mechanistic Investigations and Synthetic Applications
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The photocatalytic deoxygenation of sulfoxides to generate sulfides facilitated by either Ir[(dF(CF3)ppy)2(dtbbpy)]PF6 or fac-Ir(ppy)3 is reported. Mechanistic studies indicate that a radical chain mechanism operates, which proceeds via a phosphoranyl radical generated from a radical/polar crossover process. Initiation of the radical chain was found to proceed via two opposing photocatalytic quenching mechanisms, offering complementary reactivity. The mild nature of the radical deoxygenation process enables the reduction of a wide range of functionalized sulfoxides, including those containing acid-sensitive groups, in typically high isolated yields.
- Clarke, Aimee K.,Parkin, Alison,Rossi-Ashton, James A.,Taylor, Richard J. K.,Unsworth, William P.
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p. 5814 - 5820
(2020/07/21)
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- A visible-light photocatalytic thiolation of aryl, heteroaryl and vinyl iodides
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The general catalytic synthesis of aryl and vinyl thioethers from readily available halides remains a challenge. Herein we report a unified method for the thiolation of aryl and vinyl iodides with dialkyl disulfides using visible light photoredox catalysis. A range of thioether products bearing diverse functional groups can be accessed in high yield and with excellent chemoselectivity. We demonstrate the versatility of this method through the expedient synthesis of a family of thioether-rich natural products. A detailed investigation of the photocatalytic mechanism is presented from both steady-state and time-resolved luminescent quenching as well as transient absorption spectroscopy experiments.
- Czyz,Weragoda,Monaghan,Connell,Brzozowski,Scully,Burton,Lupton,Polyzos
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supporting information
p. 1543 - 1551
(2018/03/08)
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- Lewis Acid–Base Interaction-Controlled ortho-Selective C?H Borylation of Aryl Sulfides
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An iridium/bipyridine-catalyzed ortho-selective C?H borylation of aryl sulfides was developed. High ortho-selectivity was achieved by a Lewis acid–base interaction between a boryl group of the ligand and a sulfur atom of the substrate. This is the first example of a catalytic and regioselective C?H transformation controlled by a Lewis acid–base interaction between a ligand and a substrate. The C?H borylation reaction could be conducted on a gram scale, and with a bioactive molecule as a substrate, demonstrating its applicability to late-stage regioselective C?H borylation. A bioactive molecule was synthesized from an ortho-borylated product by converting the boryl and methylthio groups of the product.
- Li, Hong Liang,Kuninobu, Yoichiro,Kanai, Motomu
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p. 1495 - 1499
(2017/02/05)
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- Copper-mediated methylthiolation of aryl halides with DMSO
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A copper-mediated methylthiolation of aryl halides with the widely available DMSO is described. The procedure tolerates a series of functional groups such as methoxy, nitro, chloro, fluoro, trifluoromethyl, formyl and methoxycarbonyl groups. Thus, it represents a simple and facile methylthiolation procedure.
- Luo, Fang,Pan, Changduo,Li, Liping,Chen, Fan,Cheng, Jiang
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supporting information; experimental part
p. 5304 - 5306
(2011/06/21)
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- Mild and efficient deoxygenation of sulfoxides to sulfides using HFCL 4/KBH4 system
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HfCl4/KBH4 was found to be a facile, efficient, convenient, and chemoselective system for the deoxygenation of dialkyl, diaryl, and aryl alkyl sulfoxides, especially for the reduction of dibenzyl sulfoxide to the corresponding sulfides under mild conditions. In addition, the HfCl 4/KBH4 system could be used in reduction of some other sulfur-bearing substrates to the corresponding sulfides, such as 2,2'-dibenzothiazolyl disulfide, but this reducing system could not reduce sulfolane, diphenyl sulfone, p-toluenesulfonic acid, and p-toluenesulfonyl chloride to their corresponding thiophenols. Copyright
- Zhang, Jianghua,Gao, Xinqin,Zhang, Chengyi,Zhang, Cheng,Luan, Jiming,Zhao, Defeng
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experimental part
p. 1794 - 1801
(2010/07/14)
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- Photoinduced nucleophilic substitution of aryl halides with potassium thioacetate - A one-pot approach to aryl methyl and diaryl sulfides
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Aryl methyl sulfides and diaryl sulfides were prepared by photoinduced reactions of potassium thioacetate with aryl halides under entrainment conditions. Without isolation, the arene thiolates obtained by the aromatic substitution were quenched with methyl iodide to afford the aryl methyl sulfides in 26-59% yields in a "one-pot" procedure together with the diaryl sulfides in variable yields (3-31 %). By optimization of the reaction conditions it was possible to improve the formation of the Ar2S, going from moderate to good yields (64-83%). Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Schmidt, Luciana C.,Rey, Valentina,Penenory, Alicia B.
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p. 2210 - 2214
(2007/10/03)
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- Co-condensation reactions of substituted aromatic compounds with lithium atoms at 77 K
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Lithium atoms were co-condensed with +I-substituted benzene derivatives like trimethyl(phenyl)silane and tert-butylbenzene in the presence of THF at 77 K, which resulted in C-H bond activation, to produce the aryllithium compound as well as the coupling o
- Dunne, John P.,Bockmeyer, Matthias,Tacke, Matthias
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p. 458 - 466
(2007/10/03)
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- Prostaglandin endoperoxide H synthase biosynthesis inhibitors
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The present invention describes pyridazinone compounds of formula I which are cyclooxygenase (COX) inhibitors, and in particular, are selective inhibitors of cyclooxygenase-2 (COX-2). COX-2 is the inducible isoform associated with inflammation, as opposed to the constitutive isoform, cyclooxygenase-1 (COX-1) which is an important “housekeeping” enzyme in many tissues, including the gastrointestinal (GI) tract and the kidneys. The selectivity of these compounds for COX-2 minimizes the unwanted GI and renal side-effects seen with currently marketed non-steroidal anti-inflammatory drugs (NSAIDs).
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- Alkyl- and Arylthiodediazoniations of Dry Arenediazonium o-Benzenedisulfonimides. Efficient and Safe Modifications of the Stadler and Ziegler Reactions to Prepare Alkyl Aryl and Diaryl Sulfides
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The reaction between dry arenediazonium o-benzenedisulfonimides 1 and sodium thiolates in anhydrous methanol represents an efficient and safe procedure, of general validity, for the preparation of unfunctionalized or variously functionalized alkyl aryl and diaryl sulfides. As a rule, the reaction temperature was maintained at 0-5°C for the alkylthiodediazoniations and at room temperature (20-25°C) for the arylthiodediazoniations. The sulfide yields are generally high; of the 63 considered examples, 43 gave yields greater than 80% and 13 were between 70% and 80%. Lower yields were obtained only when sterically hindered diazonium salts or thiols were used. A good amount of the o-benzenedisulfonimide (8) was always recovered from the reactions and could be reused to prepare salts 1. The copious experimental data collected in homogeneous conditions have offered several starting points for the study of the mechanism of these reactions.
- Barbero, Margherita,Degani, Iacopo,Diulgheroff, Nicola,Dughera, Stefano,Fochi, Rita,Migliaccio, Mara
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p. 5600 - 5608
(2007/10/03)
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- Substituted pyrazolyl benzenesulfonamides for use in veterinary therapies
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A method of using pyrazolyl benzenesulfonamide compounds in treating inflammation and inflammation-related disorders in companion animals is disclosed.
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- Substituted pyrazolyl benzenesulfonamides for the treatment of inflammation
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A class of pyrazolyl benzenesulfonamide compounds is described for use in treating inflammation and inflammation-related disorders. Compounds of particular interest are defined by Formula II: STR1 or a pharmaceutically-acceptable salt thereof.
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- Sulfoximine-titanium reagents in enantioselective trimethylsilylcyanations of aldehydes
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Chiral titanium reagents derived from optically active sulfoximines and Ti(O-i-Pr)4 promote the asymmetric addition of trimethysilyl cyanide to aldehydes affording cyanohydrins in high yields with good enantioselectivities (up to 91% ee). The ligand structure and the reaction conditions have been optimized. With substoichiometric amounts of the sulfoximine-titanium reagent the product is obtained in decreased yield with lower enantiomeric excess. The molecular structures of (R)-S-(2-hydroxypheny)-S-methyl sulfoximine [(R)-4a] and (R)-S-(2-hydroxyphenyl)-S-(1.1-dimethylethyl) sulioximine [(R)-4d) have been determined by X-ray diffraction analysis. Acta Chemica Scandinavica 1996.
- Bolm, Garsten,Mueller, Peter,Harms, Klaus
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p. 305 - 315
(2007/10/03)
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- Oxidation of Alkylthio Substituted Tricarbonyl(η6-arene)chromium(0) Complexes to Alkylsulfinyl Substituted Tricarbonyl(η6-arene)chromium(0) Complexes
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Dimethyldioxirane efficiently oxidises tricarbonylchromium(0) complexes of alkylthio substituted arenes to tricarbonylchromium(0) complexes of alkylsulfinyl substituted arenes.The diastereoselectivity of oxidation of ortho substituted complexes, which was determined by inter alia X-ray crystal structure analyses of tricarbonyl6-1-methoxy-2-(methylsulfinyl)benzene>-chromium(0) 20x, 6-1-(tert-butylsulfinyl)-2-methoxybenzene>tricarbonylchromium(0) 23x and tricarbonyl6-1-(ethylsulfinyl)-2-methoxybenzene)chromium(0) 21y, is dependent on the alkylthio substituent and is reversed when this substituent is changed from methylthio to tert-butylthio.
- Perez-Encabo, Alfonso,Perrio, Stephane,Slawin, Alexandra M. Z.,Thomas, Susan E.,Wierzchleyski, Adam T.,Williams, David J.
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p. 629 - 642
(2007/10/02)
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- Carbophilic versus thiophilic attack in the reaction of metallated aromates and heteroaromates with carbon disulfide
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Copper(I) halides catalyse the formation of carbodithioates RCSSLi in the reaction of aryl- or heteroaryl-lithium reagents with carbon disulfide.Subsequent addition of methyl iodide gives the dithioesters RCSSCH3 in highh yields.Appreciable amounts of the methyl sulfides RSCH3 and tars are obtained when the reaction with CS2 is carried out in the absence of copper(I) salts, especially in the case of more basic organoalkali compounds.
- Verkruijsse, H. D.,Brandsma, L.
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