- TosMIC and its derivatives as versatile sulfonylating agents for the synthesis of p-toluenesulfonylarenes from aryl halides and arylboronic acids
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An efficient copper(II) catalyzed sulfonyation of aryl halides has been achieved using TosMIC (p-toluenesulfonylmethyl isocyanide) as a sulfonylating agent. This newly developed sulfonylation approach provides an easy access for the synthesis of diaryl sulfones from aryl bromides, iodides and boronic acids with TosMIC under neutral conditions. This method is useful for the sulfonylation of aryl boronic acids under similar conditions. This is the first report on the sulfonylation of aryl bromides, iodides and boronic acids using TosMIC.
- Ravi Kumar,Ramesh,Banik, Swarnayu,Subba Reddy
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- Nano copper catalyzed synthesis of symmetrical/unsymmetrical sulfones from aryl/alkyl halides and p-toluenesulfonylmethylisocyanide: TosMIC as a tosyl source
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A magnetically induced nano copper-catalyzed efficient and mild route for the synthesis of diaryl and alkyl/aryl sulfones from aryl/alkyl halides and tosylmethyl isocyanide (TosMIC) has been developed. A variety of aryl and alkyl sulfones have been obtained in very good to excellent yields. Sulfones containing molecules have medicinal relevance as they are known to possess various activities such as antifungal, anti-HIV, antitumor, and anticancer. Herein, a magnetically induced nano copper-catalyzed efficient and mild route for the synthesis of biaryl and alkyl/aryl sulfones from aryl/alkyl halides and tosylmethyl isocyanide (TosMIC) has been developed. A variety of aryl and alkyl sulfones have been obtained in very good to excellent yields. In this newly developed protocol TosMIC acts as sulfonyl source. The catalyst can magnetically be recovered and recycled five times without significant loss in activity.
- Phanindrudu, Mandalaparthi,Jaya, Pogula,Likhar, Pravin R.,Tiwari, Dharmendra Kumar
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- Organic photoredox catalysis enabled cross-coupling of arenediazonium and sulfinate salts: Synthesis of (un)symmetrical diaryl/alkyl aryl sulfones
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We disclose herein the first transition-metal-and external oxidant/reductant-free visible-light-mediated synthesis of (un)symmetrical diaryl/alkyl aryl sulfones from arenediazonium tetrafluoroborates and sodium sulfinates using eosin Y as an organic photoredox catalyst. The utilization of visible light as an inexpensive and ecosustainable energy source, operational simplicity, ambient temperature and clean reaction in aqueous acetonitrile are the salient features of the developed protocol. The desired sulfones were also synthesized via a one-pot, two-step process directly from anilines and sulfinate salts in good to excellent yields.
- Chawla, Ruchi,Yadav, Lal Dhar S.
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supporting information
p. 4761 - 4766
(2019/05/24)
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- Cross-Coupling of Sodium Sulfinates with Aryl, Heteroaryl, and Vinyl Halides by Nickel/Photoredox Dual Catalysis
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An efficient photoredox/nickel catalyzed sulfonylation reaction of aryl, heteroaryl, and vinyl halides has been achieved for the first time. This newly developed sulfonylation protocol provides a versatile method for the synthesis of diverse aromatic sulfones at room temperature and shows excellent functional group tolerance. The electrophilic coupling partners are not limited to aryl, heteroaryl, and vinyl bromides and iodides, but also includes less reactive aryl chlorides as suitable substrates for this transformation.
- Yue, Huifeng,Zhu, Chen,Rueping, Magnus
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supporting information
p. 1371 - 1375
(2018/01/27)
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- Copper(i)-catalyzed sulfonylative Suzuki-Miyaura cross-coupling
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Using a simple copper(i) catalyst has allowed a high yielding sulfonylative-Suzuki-Miyaura cross-coupling reaction to be developed. The process provides a single step route to diaryl sulfones from the direct combination of aryl boronic acids, sulfur dioxide and aryl iodides, and represents the first sulfonylative variant of a classic cross-coupling reaction. Sulfur dioxide is delivered from the surrogate reagent, DABSO. Variation of the reaction conditions allowed interruption of the sulfonylative-Suzuki coupling, resulting in the formation of a presumed Cu-sulfinate intermediate. These sulfinates could be trapped as their sodium salts and treated with electrophiles to allow access to arylalkyl sulfones, β-hydroxyl sulfones, sulfonamides and sulfonyl fluorides.
- Chen, Yiding,Willis, Michael C.
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p. 3249 - 3253
(2017/04/04)
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- Magnetically separable copper ferrite nanoparticles-catalyzed synthesis of diaryl, alkyl/aryl sulfones from arylsulfinic acid salts and organohalides/boronic acids
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A recyclable, inexpensive, non-toxic and environmentally benign catalytic system comprised of magnetically separable copper ferrite (CuFe 2O4) nanoparticles has been developed for the synthesis of diaryl, alkyl/aryl sulfones. Arylsulfinic acid salts are coupled with various alkyl/aryl halides/boronic acids to afford the corresponding diaryl, alkyl/aryl sulfones in good to excellent yields under the identical catalytic system. A wide range of functional group tolerance, with facile recovery of the catalyst by application of an external magnetic field, and consistently high catalytic efficiency for five consecutive cycles render the protocol operationally attractive.
- Srinivas,Rawat, Vikas S.,Konda, Kavitha,Sreedhar, Bojja
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p. 805 - 817
(2014/04/03)
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- Regioselectivity control of radiation-induced reaction: Electron beam-induced Fries rearrangement of sulfonamide within a β-cyclodextrin inclusion complex
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EB (electron beam) irradiation of sulfonamide within a β-cyclodextrin (β-CD) inclusion complex in the solid state induced the solvent-free Fries rearrangement, which proceeded at a shorter reaction time with reversed regioselectivity by inclusion into the β-CD, compared with that of sulfonamide crystals; the β-CD as a restricted nanospace had a large effect on the reactivity and regioselectivity of the solvent-free EB-Fries rearrangement. The Royal Society of Chemistry 2006.
- Kato, Jun,Kakehata, Hiroyuki,Maekawa, Yasunari,Yamashita, Takashi
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p. 4498 - 4500
(2008/09/19)
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- Graphite/methanesulfonic acid (GMA) as a new reagent for sulfonylation of phenols and thia-Fries rearrangement of aryl sulfonates to sulfonylphenols
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A new facile method for direct sulfonylation of phenols was developed. Graphite in methanesulfonic acid (GMA) was used to prepare sulfonylphenols by sulfonylation of phenol and naphthalene derivatives with p-toluenesulfonic acid (=4-methylbenzenesulfonic acid) (Table 1) and the thia-Fries rearrangement of aryl sulfonates (Table 4). Mechanistic studies showed that the sulfonylation reaction of phenols in GMA occurred through an initial sulfonate formation followed by a thia-Fries rearrangement of the aryl sulfonate by an intermolecular mechanism (Scheme 3).
- Sharghi, Hashem,Shahsavari-Fard, Zahra
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- Al2O3/MeSO3H (AMA) as a new reagent for the thia-Fries rearrangement of arylsulfonates to hydroxyaryl sulfones
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A new facile method for thia-Fries rearrangement of arylsulfonates has been developed. A variety of arylsulfonates rearrange in excellent yields in the presence of Al2O3/MeSO3H as a new reagent without the use of any solve
- Sharghi, Hashem,Shahsavari-Fard, Zahra
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p. 2491 - 2501
(2007/10/03)
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- Fries rearrangement of arylsulfonates and sulfonanilides under microwave irradiation
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Fries rearrangements of arylsulfonates and sulfonanilides under microwave irradiation afforded hydroxy and aminoaryl sulfones respectively in very short times and in excellent yields. The conversion showed high selectivity to produce 2- and 4- hydroxyaryl sulfones as the major and minor products respectively from arylsulfonates and 2-aminoaryl sulfones exclusively from aryl sulfonanilides.
- Das, Biswanath,Madhusudhan, Purushotham,Venkataiah, Bollu
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p. 200 - 201
(2007/10/03)
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- Thia-Fries rearrangement of aryl sulfonates in dry media under microwave activation
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An AlCl3-ZnCl2 mixture supported on silica gel is found to be a new efficient medium for the thia-Fries rearrangement of aryl sulfonates in solvent-free conditions under microwave dielectric heating. (C) 2000 Elsevier Science Ltd.
- Moghaddam, Firouz Matloubi,Dakamin, Mohammad G.
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p. 3479 - 3481
(2007/10/03)
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- Synthesis and reactivity of a novel group of hydroxylamine-containing 2π- and 4π-components
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The synthesis of hydroxylamine-based reagents, alkene 2, alkyne 3 and a butadienyl variant pyrone 4 are described. While the relative instability of alkyne 3 has limited further evaluation, alkene 2 and pyrone 4 successfully participate in 1,3-dipolar and Diels-Alder cycloaddition reactions respectively. Reaction of 4 with DMAD gives O-arylated hydroxylamine 13, the structure of which is confirmed by crystallographic analysis.
- Pearce, Alan J.,Walter, Daryl S.,Frampton, Christopher S.,Gallagher, Timothy
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p. 847 - 852
(2007/10/03)
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- Salicylic acid derivatives
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The heat-sensitive recording material disclosed comprises a colorless or pale colored dyestuff precursor, one or more salicylic acid derivative of the formula (1) or metal salt of the derivative and an aliphatic amide compound having 18?60 carbon atoms in molecular structure, and is excellent in thermal response and preservation stability of white portions and images. STR1 wherein X1 and X2 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aralkyl group or an aryl group, Y1 and Y2 are an oxygen atom or a sulfur atom, R1 is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R2 is an alkyl group, an alkenyl group, an aralkyl group or an aryl group.
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- Modification of photochemical behaviour upon cyclodextrin complexation: Photo-Fries rearrangement of sulphonate esters
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Irradiation of solid cyclodextrin complexes of phenyl benzenesulfonate and phenyl para-toluenesulfonate shows a remarkable ortho-selectivity by yielding exclusively the corresponding ortho-rearranged products in contrast to the formation of ortho- and par
- Pitchumani, K.,Manickam, M. C. Durai,Srinivasan, C.
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p. 1074 - 1076
(2007/10/02)
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- Design and Synthesis of Novel 6,7-Imidazotetrahydroquinoline Inhibitors of Thymidylate Synthase Using Iterative Protein Crystal Structure Analysis
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Antifolate inhibitors of thymidylate synthase (TS) have primarily been based on the structure of folic acid.This paper describes the identification and development of novel 6,7-imidazotetrahydroquinoline TS inhibitors by iterative ligand design, synthesis, and crystallographic analysis of protein-inhibitor complexes.Beginning with a high-resolution crystal structure of E. coli TS (TS, EC 2.1.1.45), an imidazotetrahydroquinoline inhibitor was designed de novo to occupy the folate binding pocket.Structural modifications of the initial compound 1h (Ki ca. 5 μM human/E. coli TS) were then made on the basis of feedback from additional cocrystal structures and activity data.An amino group in the 2-position of the imidazole was found to increase the potency of the series by 1-2 orders of magnitude.Other substitutions on the imidazole ring (1-CH3, 2-CH3, 2-NHCH3, 2-SCH3) generally led to weaker inhibition.Additional improvements in activity were obtained by modification of the substituents on the tetrahydroquinoline nitrogen, bringing the Ki of three of the compounds below 15 nM against the human TS enzyme.The compounds were tested for cytotoxicity and were shown to inhibit the growth of three tumor cell lines in vitro.
- Reich, Siegfried H.,Fuhry, Mary Ann M.,Nguyen, Dzuy,Pino, Mark J.,Welsh, Katherine M.,et al.
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p. 847 - 858
(2007/10/02)
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- Cation-exchanged Montmorillonite Clays as Lewis Acid Catalysts in the Fries Rearrangement of Phenyl Toluene-p-sulphonate
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Cation-exchanged montmorillonite clays catalyse the Fries rearrangement of phenyl toluene-p-sulphonate to give selectively 2- and 4-hydroxyphenyl p-tolyl sulphones as major and minor products respectively.
- Pitchumani, Kasi,Pandian, A.
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p. 1613 - 1614
(2007/10/02)
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