- Unprecedented regioselective tosylation studies of 2-ene 4,5,6,7-polyol derived from d-ribose
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[DMAPTs]+Cl- was employed as a new facile unprecedented regioselective tosylation procedure for 2-ene 4,5,6,7-polyol derived from d-ribose involving chemoselective ditosylation and regioselective allylic tosyl hydrolysis upon work up with sat. NaCl (brine) solution in a single operation by minimizing the side products obtained under classical regioselective tosylation. The same reagent was also employed for rapid quantitative base free tosylation of aniline, phenol, and 2-naphthol. A tentative mechanism for the afore said regioselective tosylation was also proposed.
- Dhonthulachitty, Chiranjeevi,Kothakapu, Sridhar Reddy,Neella, Chandra Kiran
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Read Online
- Identification of organophosphorus simulants for the development of next-generation detection technologies
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Organophosphorus (OP) chemical warfare agents (CWAs) represent an ongoing threat but the understandable widespread prohibition of their use places limitations on the development of technologies to counter the effects of any OP CWA release. Herein, we describe new, accessible methods for the identification of appropriate molecular simulants to mimic the hydrogen bond accepting capacity of the PO moiety, common to every member of this class of CWAs. Using the predictive methodologies developed herein, we have identified OP CWA hydrogen bond acceptor simulants for soman and sarin. It is hoped that the effective use of these physical property specific simulants will aid future countermeasure developments.
- Ellaby, Rebecca J.,Clark, Ewan R.,Allen, Nyasha,Taylor, Faith R.,Ng, Kendrick K. L.,Dimitrovski, Milan,Chu, Dominique F.,Mulvihill, Daniel P.,Hiscock, Jennifer R.
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p. 2008 - 2014
(2021/03/16)
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- Facile synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazides
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A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.
- Chen, Rongxiang,Xu, Shaohong,Shen, Fumin,Xu, Canran,Wang, Kaikai,Wang, Zhanyong,Liu, Lantao
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- Nickel-Catalyzed Photodehalogenation of Aryl Bromides
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Herein, we describe a Ni-catalyzed photodehalogenation of aryl bromides under visible-light irradiation that utilizes tetrahydrofuran as hydrogen source. The protocol obviates the need for exogeneous amine reductants or photocatalysts and is characterized by its simplicity and broad scope, including challenging substrate combinations.
- Higginson, Bradley,Sanjosé-Orduna, Jesus,Gu, Yiting,Martin, Ruben
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supporting information
p. 1633 - 1636
(2021/04/23)
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- Practical Electro-Oxidative Sulfonylation of Phenols with Sodium Arenesulfinates Generating Arylsulfonate Esters
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A practical and sustainable synthesis of arylsulfonate esters has been developed through electro-oxidation. This reaction employed the stable and readily available phenols and sodium arenesulfinates as the starting materials and took place under mild reaction conditions without additional oxidants. A wide range of arylsulfonate esters including those bearing functional groups were produced in good to excellent yields. This reaction could also be conducted at a gram scale without a decrease of reaction efficiency. Those results well demonstrated the potential synthetic value of this reaction in organic synthesis.
- Tian, Zhibin,Gong, Qihang,Huang, Tianzeng,Liu, Long,Chen, Tieqiao
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p. 15914 - 15926
(2021/05/04)
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- The Synthesis and Catalytic Activity of New Mixed NHC-Phosphite Nickel(0) Complexes
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Herein we describe the synthesis and isolation of the first low-valent NHC-phosphite nickel complexes of general formula Ni(NHC)[P(OAr)3]2. These three-coordinate Ni(0) compounds were fully characterized, including by X-ray crystallography that highlighted their trigonal planar geometry. The representative complex Ni(IMes)[P(OPh)3]2 was used to show that a phosphite ligand is readily substituted in the presence of an aldehyde or nitrile. These stoichiometric studies then led to an investigation of their catalytic properties in the Suzuki-Miyaura cross-coupling reactions between aryl tosylates and aryl boronic acids, a first for such a NHC-Ni catalyst. Finally, mechanistic investigations led to the isolation of a well-defined oxidative addition product.
- Dorta, Reto,Duczynski, Jeremy,Moggach, Stephen A.,Sobolev, Alexandre N.,Stewart, Scott G.
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supporting information
(2020/01/21)
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- Quantum Dot-Catalyzed Photoreductive Removal of Sulfonyl-Based Protecting Groups
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This Communication describes the use of CuInS2/ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl-protected phenols. For a series of aryl sulfonates with electron-withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD-binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor–acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.
- Perez, Kaitlyn A.,Rogers, Cameron R.,Weiss, Emily A.
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supporting information
p. 14091 - 14095
(2020/06/08)
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- Palladium-Catalyzed Cyclobutanation of Aryl Sulfonates through both C-O and C-H Cleavage
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A palladium-catalyzed cyclobutanation of aryl sulfonates with strained alkenes has been developed. The methodology is featured to achieve the cleavage of both C-O and C-H bonds of phenol derivatives in one pot. Under the reaction conditions, in addition t
- Zhang, Liangwei,Liu, Long,Huang, Tianzeng,Dong, Qizhi,Chen, Tieqiao,Chen, Tieqiao
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p. 2189 - 2196
(2020/06/05)
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- Highly-chemoselective step-down reduction of carboxylic acids to aromatic hydrocarbons: Via palladium catalysis
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Aryl carboxylic acids are among the most abundant substrates in chemical synthesis and represent a perfect example of a traceless directing group that is central to many processes in the preparation of pharmaceuticals, natural products and polymers. Herein, we describe a highly selective method for the direct step-down reduction of carboxylic acids to arenes, proceeding via well-defined Pd(0)/(ii) catalytic cycle. The method shows a remarkably broad substrate scope, enabling to direct the classical acyl reduction towards selective decarbonylation by a redox-neutral mechanism. The utility of this reaction is highlighted in the direct defunctionalization of pharmaceuticals and natural products, and further emphasized in a range of traceless processes using removable carboxylic acids under mild, redox-neutral conditions orthogonal to protodecarboxylation. Extensive DFT computations were conducted to demonstrate preferred selectivity for the reversible oxidative addition and indicated that a versatile hydrogen atom transfer (HAT) pathway is operable.
- Liu, Chengwei,Qin, Zhi-Xin,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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p. 5736 - 5742
(2019/06/18)
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- Synthesis and DFT studies of novel aryloxymaleimides via nucleophilic substitution of tosyloxy group
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Maleimide skeleton distributes widely in a great many substances, and maleimides are very useful building blocks in organic synthesis and many related disciplines, like bioconjugation. As an excellent leaving group, tosyloxy (-OTs) group are very popular
- Yan, Maocai,Zhang, Zhen,Zhou, Jinhui,Li, Wei,Zhang, Chunyan,Zhang, Jingchang,Wang, Huannan,Yang, Xuelu,Fan, Shuai,Yang, Zhaoyong
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p. 155 - 160
(2019/04/26)
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- Electron Donor-Acceptor Complex Enabled Decarboxylative Sulfonylation of Cinnamic Acids under Visible-Light Irradiation
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Visible-light-induced decarboxylative sulfonylation of cinnamic acids with aryl sulfonate phenol esters enabled by the electron donor-acceptor complex is developed. The method offers a mild and green approach for the synthesis of vinyl sulfones with excellent functional group compatibility under photocatalyst and oxidant-free conditions.
- Ge, Qian-Qian,Qian, Jia-Sheng,Xuan, Jun
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p. 8691 - 8701
(2019/08/30)
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- Mild alkaline hydrolysis of hindered esters in non-aqueous solution
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Sterically hindered esters of carboxylic acids, which are considered very resistant to saponification, were rapidly and efficiently saponified in a non-aqueous medium using NaOH in MeOH/CH2Cl2 (1:9) at room temperature. Furthermore, this reaction protocol was extended and successfully applied to the hydrolysis of tosylates and N-tosyl indoles.
- Theodorou, Vassiliki,Alagiannis, Michalis,Ntemou, Nikoleta,Brentas, Alexios,Voulgari, Pinelopi,Polychronidou, Vasiliki,Gogou, Marina,Giannelos, Marios,Skobridis, Konstantinos
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p. 308 - 319
(2018/11/26)
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- Hypervalent Iodine(III)-Catalyzed Balz–Schiemann Fluorination under Mild Conditions
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An unprecedented hypervalent iodine(III) catalyzed Balz–Schiemann reaction is described. In the presence of a hypervalent iodine compound, the fluorination reaction proceeds under mild conditions (25–60 °C), and features a wide substrate scope and good functional-group compatibility.
- Xing, Bo,Ni, Chuanfa,Hu, Jinbo
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p. 9896 - 9900
(2018/07/31)
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- A Predictive Model for the Decarboxylation of Silver Benzoate Complexes Relevant to Decarboxylative Coupling Reactions
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Decarboxylative coupling reactions offer an attractive route to generate functionalized arenes from simple and readily available carboxylic acid coupling partners, yet they are underutilized due to limitations in the scope of carboxylic acid coupling partner. Here we report that the field effect parameter (F) has a substantial influence on the rate of decarboxylation of well-defined silver benzoate complexes. This finding provides the opportunity to surpass current substrate limitations associated with decarboxylation and to enable widespread utilization of decarboxylative coupling reactions.
- Crovak, Robert A.,Hoover, Jessica M.
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p. 2434 - 2437
(2018/02/28)
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- Pd-Catalyzed Conversion of Aryl Iodides to Sulfonyl Fluorides Using SO2 Surrogate DABSO and Selectfluor
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A one-pot Pd-catalyzed conversion of aryl iodide to aryl sulfonyl fluorides using DABSO and Selectfluor has been developed generating aryl sulfonyl fluorides in good to excellent yields. The reaction results in the generation of electronically and sterically diverse sulfonyl fluorides. Additionally, sulfonyl fluorides can be converted to aryl sulfonamides and sulfonic esters using Cs2CO3 under mild conditions.
- Tribby, Ariana L.,Rodríguez, Ismeraí,Shariffudin, Shamira,Ball, Nicholas D.
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supporting information
p. 2294 - 2299
(2017/02/26)
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- Ionic liquid brush as an efficient and reusable heterogeneous catalytic assembly for the tosylation of phenols and alcohols in neat water
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A very efficient and reusable heterogeneous ionic liquid brush assembly was developed. The catalyst exhibits high catalytic activity for the tosylation of phenols and alcohols in neat water. Moreover, the catalyst shows outstanding stability and reusability, and it can be simply and effectively recovered and reused five times without noticeable loss of catalytic activity.
- Feng, Simin,Li, Jing,Wei, Junfa
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supporting information
p. 4743 - 4746
(2017/07/12)
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- Method for synthesizing cis-tritosylate
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The invention discloses a method for preparing cis-tritosylate. The cis-tritosylate shown in structural formula (II) is obtained by carrying out a reaction between a compound shown in structural formula (I) and toluene sulfonyl chloride in an anhydrous pyridine solvent according to an equal molar ratio. According to the method, use of an inorganic alkali catalyst Na2CO3 or K2CO3 is avoided, problems about hydrolysis of the toluene sulfonyl chloride are solved, and an obtained product is high in yield and free of other side reaction, and is not required to be separated by virtue of a method of column chromatography and the like.
- -
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Paragraph 0016
(2017/08/29)
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- Facile removal of tosyl chloride from tosylates using cellulosic materials, e.g., filter paper
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Excess tosyl chloride used in the tosylation of alcohols is quickly and easily removed by reacting it with cellulosic materials, e.g., filter paper, and filtering.
- Schoonover, Daniel V.,Gibson, Harry W.
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supporting information
p. 242 - 244
(2016/12/27)
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- Pd/Indanone-Based Ligands: An Efficient Catalyst System for Ullmann-Type, Suzuki-Miyaura, and Mizoroki-Heck Cross-Coupling Reactions with Aryl Tosylates and Aryl Halides
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2-Hydroxyindan-1-ones have been efficiently synthesized and successfully applied as ligands in Pd-catalyzed Ullmann type, Suzuki-Miyaura, and Mizoroki-Heck cross-coupling reactions with aryl tosylates and aryl halides. The ligands are air- and moisture-stable and have shown high catalytic activity with Pd(OAc) 2 in these cross-coupling reactions. The system tolerates a variety of functional groups in the product and can be re-used at least three times with maximum efficiency..
- Waheed, Mohammed,Ahmed, Naseem
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supporting information
p. 4372 - 4382
(2017/09/12)
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- Copper-Catalyzed C-S Bond Formation via the Cleavage of C-O Bonds in the Presence of S8 as the Sulfur Source
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Useful and applicable methods for one-pot and odorless synthesis of unsymmetrical and symmetrical diaryl sulfides via C-O bond activation are presented. First, a new efficient procedure for the synthesis of unsymmetrical sulfides using the cross-coupling reaction of phenolic esters such as acetates, tosylates, and triflates and with arylboronic acid or triphenyltin chloride as the coupling partners is reported. Depending on the reaction, S 8 /KF or S 8 /NaO t -Bu system is found to be an effective source of sulfur in the presence of copper salts and in poly(ethylene glycol) as a green solvent. Then, the synthesis of symmetrical diaryl sulfides from phenolic compounds by using S 8 as the sulfur source and NaO t -Bu in anhydrous DMF at 120 °C under N 2 is described. By these protocols, the synthesis of a variety of unsymmetrical and symmetrical sulfides become easier than the available protocols in which thiols and aryl halides are directly used for the preparation of the sulfides.
- Rostami, Abed,Rostami, Amin,Ghaderi, Arash,Gholinejad, Mohammad,Gheisarzadeh, Sajedeh
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p. 5025 - 5038
(2017/10/06)
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- A High Mobility Reactor Unit for R&D Continuous Flow Transfer Hydrogenations
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A suitcase sized mobile reactor unit (MRU) weighing in at less than 10 kg was designed for laboratory scale transfer hydrogenations in continuous flow. Simple cyclohexene and a cosolvent in combination with a palladium-on-charcoal packed bed reactor provided a setup with isolation of nearly all products without the need for further purification. Several functional groups including olefins, triple bonds, nitro-groups, carbonyls, and so forth were effectively reduced with retention times as low as 2 min. Additionally, standard protection groups such as Cbz, benzyl, and allyl ether or esters were removed in high yields. To prove the flexibility of the setup an example of the Mizoroki-Heck reaction was also performed on the MRU. Finally, two scale-up transfer hydrogenation experiments were performed affording isolation of the desired target compounds in 0.5 and 0.8 mol scales with less than 4 h of continuous operation on the MRU.
- Jensen, Rasmus K.,Thykier, Nikolaj,Enevoldsen, Martin V.,Lindhardt, Anders T.
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supporting information
p. 370 - 376
(2017/03/24)
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- Direct Carboxylation of Aryl Tosylates by CO2 Catalyzed by in situ-Generated Ni0
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A novel Ni0-catalyzed carboxylation of aryl tosylates with carbon dioxide has been achieved under moderate temperatures and atmospheric pressure. In this procedure, the active Ni0 species is generated in situ by simply mixing the Ni0 precatalyst [NiBr2(bipy)] with an excess of manganese metal. This approach requires neither a glove-box nor the tedious preparation of sophisticated intermediate organometallic derivatives. This mild, convenient, and user-friendly process is successfully applied to the valorization of carbon dioxide and the synthesis of versatile reactants with broad tolerance of substituents.
- Rebih, Fatima,Andreini, Manuel,Moncomble, Aurlien,Harrison-Marchand, Anne,Maddaluno, Jacques,Durandetti, Muriel
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supporting information
p. 3758 - 3763
(2016/03/08)
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- METAL OXIDE CATALYZED RADIOFLUORINATION
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Inter alia, the first titania-catalyzed [18F]-radiofluorination in highly aqueous medium is provided. In embodiments, the method utilizes titanium dioxide, 1 : 1 acetonitrile- thexyl alcohol solvent mixture and tetrabutylammonium bicarbonate as a base. Radiolabeling may be directly performed with aqueous [18F]fluoride without the need for drying/azeotroping step, which reduces radiosynthesis time while keeping high fluoride conversion. The general applicability of the synthetic strategy to the synthesis of the wide range of PET probes from tosylated precursors is demonstrated.
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Paragraph 0109
(2016/02/28)
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- A Mild Strategy for the Preparation of Phenols via the Ligand-Free Copper-Catalyzed O-Arylation of para -Toluenesulfonic Acid
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A facile and simple ligand-free copper-catalyzed reaction to synthesize substituted phenols is reported. The reaction presumably proceeds via an O-arylsulfonate intermediate that is hydrolyzed to afford good to excellent yields of up to 88%. This protocol provides an alternative to existing reports which use strong hydroxide salts as the direct hydroxylation partner. Demonstrating a wide substrate scope and functional group tolerance, this protocol can also be applied to inexpensive and commercially available carboxylic acids to yield phenols.
- Tan, Bryan Yong-Hao,Teo, Yong-Chua
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supporting information
p. 1814 - 1819
(2016/07/16)
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- Gold(I)-Catalyzed N-Desulfonylative Amination versus N-to-O 1,5-Sulfonyl Migration: A Versatile Approach to 1-Azabicycloalkanes
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Valuable 1-azabicycloalkane derivatives have been synthesized through a novel gold(I)-catalyzed desulfonylative cyclization strategy. An ammoniumation reaction of ynones substituted at the 1-position with an N-sulfonyl azacycle took place in the presence of a gold cation by intramolecular cyclization of the disubstituted sulfonamide moiety onto the triple bond. Depending on the size of the heterocyclic ring and substitution of the substrates, two unprecedented forms of nucleophilic attack on the sulfonyl group were exploited, that is, a N-desulfonylation in the presence of an external protic O nucleophile (37–87 %, 10 examples) and a unique N-to-O 1,5-sulfonyl migration (60–98 %, 9 examples).
- Miaskiewicz, Solène,Gaillard, Boris,Kern, Nicolas,Weibel, Jean-Marc,Pale, Patrick,Blanc, Aurélien
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p. 9088 - 9092
(2016/07/26)
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- Homocoupling of iodoarenes and bromoalkanes using photoredox gold catalysis: A light enabled Au(III) reductive elimination
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The formation of homocoupled alkane byproducts have been identified in the reduction of bromoalkanes via photoredox gold catalysis with dimeric Au(I) complexes. This prompted further investigation into the mechanism of formation of these byproducts and the diversity of C-X bonds amenable to this transformation. Examples were found when considering bromoalkanes while a wide variety of iodoarenes underwent this process in good to excellent yields. The light enabled homocoupling of iodoarenes made possible by photoredox gold catalysis is reported.
- Tran, Huy,McCallum, Terry,Morin, Mathieu,Barriault, Louis
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supporting information
p. 4308 - 4311
(2016/09/09)
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- DBN hexafluorophosphate salts as convenient sulfonylating and phosphonylating agents
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Air-stable N-sulfonyl and N-phosphonyl DBN hexafluorophosphate salts have been synthesised under mild conditions as sulfonylating and phosphonylating agents. These salts are highly efficient in the sulfonylation and phosphonylation of a range of N- and O-nucleophiles to generate sulfonamides, sulfonate esters, phosphoramidates and phosphonate esters in good yields.
- Jones, Caroline S.,Bull, Steven D.,Williams, Jonathan M. J.
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p. 8452 - 8456
(2016/09/28)
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- An efficient practical tosylation of phenols, amines, and alcohols employing mild reagent [DMAPTs]+Cl?
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Efficient exploration of [DMAPTs]+Cl?for base free and chromatography free preparation of sulfonate esters from phenols and alcohols and sulfonamides from amines was achieved in excellent yields. Majority of the phenols irrespective of their substituents electronic nature underwent tosylation nearly at same reaction rate with an average yield of 95%. For amines, ring activating substituents favors rapid sulfonylation while the ring deactivating substituents relatively lowers the rate of tosylation. Furthermore the reagent was employed for Chemoselective sulfonylation as well as solvent free tosylation of phenols and amines.
- Dhonthulachitty, Chiranjeevi,Kothakapu, Sridhar Reddy,Neella, Chandra Kiran
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supporting information
p. 4620 - 4623
(2016/09/23)
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- Chromatography-Free and Eco-Friendly Synthesis of Aryl Tosylates and Mesylates
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Two chromatography-free and eco-friendly protocols have been developed to synthesize aryl tosylates and mesylates by the tosylation and mesylation of the corresponding hydroxyarenes, respectively. These protocols are superior to other known ones regarding
- Lei, Xiangyang,Jalla, Anusha,Abou Shama, Mhd A.,Stafford, Jamie M.,Cao, Billy
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supporting information
p. 2578 - 2585
(2015/09/01)
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- Dimerization of Aryl Sulfonates by in situ Generated Nickel(0)
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A mild and user-friendly nickel-catalyzed method for the reductive homocoupling of aromatic tosylates is presented. The reaction proceeds between room temperature and 60 °C, with stable substrates (ArOTs) easily prepared from inexpensive and commercially available phenols or naphthols. It relies on a catalytic amount (10 mol%) of a robust catalyst (NiBr2bipy) that does not require the preparation of sensitive organometallic intermediates. Yields are good to excellent.
- Maddaluno, Jacques,Durandetti, Muriel
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supporting information
p. 2385 - 2388
(2015/10/19)
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- Titania-catalyzed radiofluorination of tosylated precursors in highly aqueous medium
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Nucleophilic radiofluorination is an efficient synthetic route to many positron-emission tomography (PET) probes, but removal of water to activate the cyclotron-produced [18F]fluoride has to be performed prior to reaction, which significantly increases overall radiolabeling time and causes radioactivity loss. In this report, we demonstrate the possibility of 18F-radiofluorination in highly aqueous medium. The method utilizes titania nanoparticles, 1:1 (v/v) acetonitrile-thexyl alcohol solvent mixture, and tetra-n-butylammonium bicarbonate as a phase-transfer agent. Efficient radiolabeling is directly performed with aqueous [18F]fluoride without the need for a drying/azeotroping step to significantly reduce radiosynthesis time. High radiochemical purity of the target compound is also achieved. The substrate scope of the synthetic strategy is demonstrated with a range of aromatic, aliphatic, and cycloaliphatic tosylated precursors.
- Sergeev, Maxim E.,Morgia, Federica,Lazari, Mark,Wang, Christopher,Van Dam, R. Michael
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supporting information
p. 5686 - 5694
(2015/05/20)
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- Selective Aromatic C-H Hydroxylation Enabled by η6-Coordination to Iridium(III)
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We report an aromatic C-H hydroxylation protocol in which the arene is activated through η6-coordination to an iridium(III) complex. η6-Coordination of the arene increases its electrophilicity and allows for high positional selectivity of hydroxylation at the site of least electron density. Through investigation of intermediate η5-cyclohexadienyl adducts and arene exchange reactions, we evaluate incorporation of arene π-activation into a catalytic cycle for C-H functionalization.
- D'Amato, Erica M.,Neumann, Constanze N.,Ritter, Tobias
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supporting information
p. 4626 - 4631
(2015/10/06)
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- Iodine-induced synthesis of sulfonate esters from sodium sulfinates and phenols under mild conditions
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An iodine-induced synthesis of sulfonate esters via cross-coupling reactions of sodium sulfinates with phenols is reported. This synthetic route is low-cost, facile, green and efficient, and could afford the target products with good to excellent yields u
- Gao, Jian,Pan, Xiaojun,Liu, Juan,Lai, Junyi,Chang, Liming,Yuan, Gaoqing
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p. 27439 - 27442
(2015/03/31)
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- CuI catalyzed sulfonylation of organozinc reagents with sulfonyl halides
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In this study, a facile CuI catalyzed synthesis of sulfones involving a nucleophilic addition of functionalized organozinc reagents to organic sulfonyl chlorides is realized. This reaction proceeds efficiently at room temperature, giving rise to various functional group substituted sulfones, generally in moderate to high yields. The method provides a novel, simple, and promising strategy for functionalized sulfone synthesis in the research field of sulfur chemistry. the Partner Organisations 2014.
- Fu, Ying,Zhu, Wenbo,Zhao, Xingling,Huegel, Helmut,Wu, Zhouqiang,Su, Yuhu,Du, Zhengyin,Huang, Danfeng,Hu, Yulai
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p. 4295 - 4299
(2014/06/23)
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- Palladium-catalyzed intramolecular oxidative coupling involving double C(sp2)-H bonds for the synthesis of annulated biaryl sultams
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The palladium-catalyzed intramolecular oxidative coupling described herein involves a double C(sp2)-H bond functionalization in sulfonanilides, providing a workable access to biaryl sultams annulated into a six-membered ring that are otherwise difficult to obtain by literature methods. The other synthetic applications of this protocol including the synthesis of biaryl sultams containing a seven-membered ring and analogous sultones are also presented.
- Laha, Joydev K.,Jethava, Krupal P.,Dayal, Neetu
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p. 8010 - 8019
(2015/03/18)
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- Copper-catalysed coupling of aryl tosylates with sodium arylsulfinates
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Diaryl sulfones derivatives were easily synthesised from aryl tosylates and sodium arylsulfinates in high yields using [Cu(CH3CN)4]PF6 as catalyst. The transformation is efficient, simple and the starting materials are readily available.
- Wang, Chunjie,Zhang, Hui,Li, Zhiwei,Wang, Ziyun
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p. 639 - 642
(2015/02/02)
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- Facile synthesis of 1-Alkoxy-1H-benzo- and 7-azabenzotriazoles from peptide coupling agents, mechanistic studies, and synthetic applications
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(1H-Benzo[d][1,2,3]triazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP), 1H-benzo[d][1,2,3]triazol-1-yl 4- methylbenzenesulfonate (Bt-OTs), and 3H-[1,2,3]triazolo[4,5-b]pyridine-3-yl 4-methylbenzenesulfonate (At-OTs) are classically utilized in peptide synthesis for amide-bond formation. However, a previously undescribed reaction of these compounds with alcohols in the presence of a base, leads to 1-alkoxy-1H-benzo- (Bt-OR) and 7-azabenzotriazoles (At-OR). Although BOP undergoes reactions with alcohols to furnish 1-alkoxy-1H-benzotriazoles, Bt-OTs proved to be superior. Both, primary and secondary alcohols undergo reaction under generally mild reaction conditions. Correspondingly, 1-alkoxy-1H-7-azabenzotriazoles were synthesized from At-OTs. Mechanistically, there are three pathways by which these peptide-coupling agents can react with alcohols. From 31P{1H}, [18O]-labeling, and other chemical experiments, phosphonium and tosylate derivatives of alcohols seem to be intermediates. These then react with BtO- and AtO- produced in situ. In order to demonstrate broader utility, this novel reaction has been used to prepare a series of acyclic nucleoside-like compounds. Because BtO- is a nucleofuge, several Bt-OCH2Ar substrates have been evaluated in nucleophilic substitution reactions. Finally, the possible formation of Pd πallyl complexes by departure of BtO- has been queried. Thus, alpha-allylation of three cyclic ketones was evaluated with 1-(cinnamyloxy)-1H-benzo[d][1,2,3]triazole, via in situ formation of pyrrolidine enamines and Pd catalysis.
- Lakshman, Mahesh K.,Singh, Manish K.,Kumar, Mukesh,Chamala, Raghu Ram,Yedulla, Vijayender R.,Wagner, Domenick,Leung, Evan,Yang, Lijia,Matin, Asha,Ahmad, Sadia
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supporting information
p. 1919 - 1932
(2014/11/07)
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- Cross-coupling reactions of pyrimidin-2-yl sulfonates with phenols and anilines: An efficient approach to C2-functionalized pyrimidines
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Pyrimidin-2-yl sulfonates, as an efficient reaction partner, which can be easily prepared from cheap commercial materials, were coupled with phenols and anilines to give a wide array of C2-aryloxy- and arylaminopyrimidines in good to excellent yields under mild reaction conditions. Copyright
- Quan, Zhengjun,Jing, Fuqiang,Zhang, Zhang,Da, Yuxia,Wang, Xicun
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supporting information
p. 1495 - 1502
(2014/01/06)
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- One-pot tandem reactions for direct conversion of thiols and disulfides to sulfonic esters, alcohols to bis(indolyl)methanes and synthesis of pyrroles catalyzed by N-chloro reagents
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A convenient synthesis of sulfonic esters from thiols and disulfides has been described. In situ preparation of sulfonyl chlorides from thiols is accomplished by oxidation with Chloramin-T, tetra-butylammonium chloride (t-Bu4NCl) and water. The sulfonyl chlorides are then further allowed to react with phenol derivatives in the same reaction vessel. Also, a facile synthesis of bis(indolyl)methanes from alcohols using TCCA/KBr/wet-SiO2, and N-substituted pyrroles by reaction of hexane-2,5-dione with primary amines has been accomplished under mild condition with excellent yields.
- Veisi, Hojat,Ataee, Meral,Fatolahi, Leila,Lotfi, Shahram
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p. 111 - 117
(2013/07/26)
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- One-pot tandem reactions for direct conversion of thiols and disulfides to sulfonic esters, and Paal-Knorr synthesis of pyrrole derivatives catalyzed by TCCA
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A convenient synthesis of sulfonic esters from thiols and disulfides is described. In situ preparation of sulfonyl chlorides from thiols is accomplished by oxidation with trichloroisocyanuric acid (TCCA), tetra-butylammonium chloride (t-Bu4NCl), and water. The sulfonyl chlorides are then further allowed to react with phenol derivatives in the same reaction vessel. Also, a facile synthesis of N-substituted pyrroles by the reaction of hexane-2,5-dione with primary amines has been accomplished using TCCA as a catalyst under mild condition with excellent yields.
- Hemmati, Saba,Mojtahedi, Mohammad Majid,Abaee, Mohammad Saeed,Vafajoo, Zahra,Saremi, Shokufe Ghahri,Noroozi, Mohammad,Sedrpoushan, Alireza,Ataee, Meral
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p. 347 - 357
(2013/09/23)
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- Direct C-C bond construction from arylzinc reagents and aryl halides without external catalysts
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Direct cross-coupling between an arylzinc reagent and an aryl halide was accomplished without any external catalyst, enabling efficient and selective formation of the corresponding biaryl compound with broad functional group compatibility. Direct cross-coupling between a diarylzinc compound and an aryl iodide was accomplished without using any external catalyst. The reaction is efficient and selective, enabling formation of the corresponding biaryl compounds with broad functional group compatibility. The reaction is proposed to proceed by a thermally initiated single electron transfer (SET) route. Copyright
- Minami, Hiroki,Wang, Xuan,Wang, Chao,Uchiyama, Masanobu
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supporting information
p. 7891 - 7894
(2014/01/06)
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- Metal-free arylation of oxygen nucleophiles with diaryliodonium salts
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Phenols and carboxylic acids are efficiently arylated with diaryliodonium salts. The reaction conditions are mild, metal free, and avoid the use of halogenated solvents, additives, and excess reagents. The products are obtained in good-to-excellent yields after short reaction times. Steric hindrance is very well tolerated, both in the nucleophile and diaryliodonium salt. The scope includes ortho- and halo-substituted products, which are difficult to obtain by metal-catalyzed protocols. Many functional groups are tolerated, including carbonyl groups, heteroatoms, and alkenes. Unsymmetric salts can be chemoselectively utilized to obtain products with hitherto unreported levels of steric congestion. The arylation has been extended to sulfonic acids, which can be converted to sulfonate esters by two different approaches. With recent advances in efficient synthetic procedures for diaryliodonium salts the reagents are now inexpensive and readily available. The iodoarene byproduct formed from the iodonium reagent can be recovered quantitatively and used to regenerate the diaryliodonium salt, which improves the atom economy. Copyright
- Jalalian, Nazli,Petersen, Tue B.,Olofsson, Berit
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supporting information
p. 14140 - 14149,10
(2012/12/12)
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- Replacing conventional carbon nucleophiles with electrophiles: Nickel-catalyzed reductive alkylation of aryl bromides and chlorides
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A general method is presented for the synthesis of alkylated arenes by the chemoselective combination of two electrophilic carbons. Under the optimized conditions, a variety of aryl and vinyl bromides are reductively coupled with alkyl bromides in high yields. Under similar conditions, activated aryl chlorides can also be coupled with bromoalkanes. The protocols are highly functional-group tolerant (-OH, -NHTs, -OAc, -OTs, -OTf, -COMe, -NHBoc, -NHCbz, -CN, -SO2Me), and the reactions are assembled on the benchtop with no special precautions to exclude air or moisture. The reaction displays different chemoselectivity than conventional cross-coupling reactions, such as the Suzuki-Miyaura, Stille, and Hiyama-Denmark reactions. Substrates bearing both an electrophilic and nucleophilic carbon result in selective coupling at the electrophilic carbon (R-X) and no reaction at the nucleophilic carbon (R-[M]) for organoboron (-Bpin), organotin (-SnMe3), and organosilicon (-SiMe2OH) containing organic halides (X-R-[M]). A Hammett study showed a linear correlation of σ and σ(-) parameters with the relative rate of reaction of substituted aryl bromides with bromoalkanes. The small ρ values for these correlations (1.2-1.7) indicate that oxidative addition of the bromoarene is not the turnover-frequency determining step. The rate of reaction has a positive dependence on the concentration of alkyl bromide and catalyst, no dependence upon the amount of zinc (reducing agent), and an inverse dependence upon aryl halide concentration. These results and studies with an organic reductant (TDAE) argue against the intermediacy of organozinc reagents.
- Everson, Daniel A.,Jones, Brittany A.,Weix, Daniel J.
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supporting information; experimental part
p. 6146 - 6159
(2012/05/07)
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- Nickel-catalyzed C-P coupling of aryl mesylates and tosylates with H(O)PR1R2
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A method was developed for the nickel-catalyzed phosphonylation of aryl mesylates and tosylates with H(O)PR1R2. To the best of our knowledge, this is the first example of nickel-catalyzed C-P coupling of aryl mesylates and tosylates. Most of the substrates gave moderate to good yields under our catalytic system.
- Shen, Chaoren,Yang, Guoqiang,Zhang, Wanbin
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supporting information; body text
p. 3500 - 3505
(2012/05/20)
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- Synthesis of sulfonamides and sulfonic esters via reaction of amines and phenols with thiols using H2O2-POCl3 system
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Phosphorus oxychloride efficiently promoted the synthesis of sulfonamides and sulfonic esters from thiols with hydrogen peroxide in the presence of Amberlite IRA-400 (OH-). This method has been applied to a variety of substrates including nucleophilic and sterically hindered amines, and also phenols with excellent yields of sulfonamides and sulfonic esters. In most cases these reactions are highly selective, simple, and clean, affording products in excellent yields and high purity.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Abbasi, Jamshid
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supporting information; experimental part
p. 5095 - 5101
(2012/07/28)
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- Cs2CO3 catalyzed rapid and efficient conversion of amines into sulfonamides; Alcohols and phenols into sulfonic esters
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A simple and efficient method has been developed for the sulfonylation of several amines, alcohols, and phenols by p-toluenesulphonylchloride (p-TsCl) in the presence of catalytic amount of Cs2CO3 at 25C to obtain sulfonamides and sulfonic esters in very good yields. Cs2CO3 has been found to be highly efficient catalyst. Taylor & Francis Group, LLC.
- Reddy, M. B. Madhusudana,Pasha
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experimental part
p. 1867 - 1875
(2011/10/11)
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- Profiling sulfonate ester stability: Identification of complementary protecting groups for sulfonates
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(Figure presented) Sulfonation is prized for its ability to impart water-solubility to hydrophobic molecules such as dyes. This modification is usually performed as a final step, since sulfonated molecules are poorly soluble in most organic solvents, which complicates their synthesis and purification. This work compares the intrinsic lability of different sulfonate esters, identifying new sulfonate protecting groups and mild, selective cleavage conditions.
- Miller, Stephen C.
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supporting information; experimental part
p. 4632 - 4635
(2010/09/17)
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- Decarboxylative cross-coupling of aryl tosylates with aromatic carboxylate salts
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(Figure Presented) A bimetallic copper/palladium catalyst system is disclosed that enables the use of tosylates as carbon electrophiles in decarboxylative coupling reactions. A variety of aromatic carboxylate salts, regardless of their substitution pattern, have been coupled with these inexpensive and readily available electrophiles to give the corresponding biaryl compounds in good yields (see scheme).
- Goossen, Luksa J.,Rodriguez, Nuria,Lange, Paul P.,Linder, Christophe
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supporting information; experimental part
p. 1111 - 1114
(2010/04/29)
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- Neopentylglycolborylation of aryl mesylates and tosylates catalyzed by Ni-based mixed-ligand systems activated with Zn
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(Chemical Presented) The mixed-ligand system NiCl2(dppp)/dppf is shown to be an effective catalyst for the neopentylglycolborylation of ortho-, meta-, and para-substituted electron-rich and electrondeficient aryl mesylates and tosylates. The ad
- Wilson, Daniela A.,Wilson, Christopher J.,Moldoveanu, Costel,Resmerita, Ana-Maria,Corcoran, Patrick,Hoang, Lisa M.,Rosen, Brad M.,Percec, Virgil
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supporting information; experimental part
p. 1800 - 1801
(2010/04/24)
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- Suzuki-Miyaura coupling of aryl tosylates and mesylates in water
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The palladium complex (0.5 mol-%) of a water-soluble sulfonated fluorenylphosphane (cataCXium Fsulf) enables the facile Suzuki-Miyaura coupling of various (heterocyclic) aryl tosylates and aryl mesylate with various (heterocyclic) boronic acids in excellent yields (> 95%) using water as the reaction solvent.
- Pschierer, Jan,Plenio, Herbert
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supporting information; experimental part
p. 2934 - 2937
(2010/08/07)
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