- Spontaneous resolution of aromatic sulfonamides: Effective screening method and discrimination of absolute structure
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(Chemical Equation Presented) An effective screening method combining parallel synthesis and solid-state CD measurements was established to identify achiral aromatic sulfonamides that show spontaneous resolution with rapidity. We found that 4 of the 12 achiral sulfonamides crystallized as chiral crystals through this method. The chirality of each sulfonamide was discriminated by solid-state CD spectra and Flack parameter in an X-ray analysis. Correspondence between the observed Cotton effect and the absolute configuration could be confirmed by time-dependent DFT calculations.
- Kato, Takako,Okamoto, Iwao,Tanatani, Aya,Hatano, Terutaka,Uchiyama, Masanobu,Kagechika, Hiroyuki,Masu, Hyuma,Katagiri, Kosuke,Tominaga, Masahide,Yamaguchi, Kentaro,Azumaya, Isao
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- A green, catalyst-free method for the synthesis of sulfonamides and sulfonylazides
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A novel, green method for the efficient synthesis of sulfonamide and sulfonylazide derivatives by the reaction of sulfonyl chlorides with amines or sodium azide under catalyst-free conditions has been developed. The reactions proceed with high yields and excellent selectivities in short reaction times. Copyright Taylor & Francis Group, LLC.
- Jafarpour, Maasoumeh,Rezaeifard, Abdolreza,Golshani, Tayebeh
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- Multi-Stimuli-Responsive Interconversion between Bowl- And Capsule-Shaped Self-Assembled Zinc(II) Complexes
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Self-assembled metal-organic architectures have great potential to undergo major structural changes into different architectures. Such molecular transformation is widely applicable to responsive systems like drug delivery and allosteric catalysis. A great
- Endo, Kenichi,Ube, Hitoshi,Shionoya, Mitsuhiko
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- Metal-Free β-Amino Alcohol Synthesis: A Two-step Smiles Rearrangement
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A novel method for the synthesis of β-amino alcohols has been demonstrated under mild reaction conditions with a broad scope via a two-step Smiles rearrangement. What is more, theoretical calculations have been performed to confirm the rationality of the mechanism. The method has been proved to be notably effective for N-arylated amino alcohols, which are difficult to synthesize by traditional methods.
- Yang, Di,Xie, Cai-Xia,Wu, Xiao-Tian,Fei, Luo-Ran,Feng, Lei,Ma, Chen
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- Pd-Catalyzed Cross-Coupling Reactions Promoted by Biaryl Phosphorinane Ligands
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We report the use of biaryl phosphorinanes as ligands for Pd-catalyzed cross-coupling reactions. A modular synthesis was developed that employs a double conjugate addition of primary biaryl phosphines into 1,1,5,5-tetraalkyl penta-1,4-diene-3-ones. Notably, this synthesis does not require the use of copper, a known contaminant in structurally related biaryl phosphane ligands. Using the synthetic strategy described above, we synthesized a library of biaryl phosphorinanes, varying their substitution about phosphorus and the steric and electronic nature of the biaryl motif. We then benchmarked their performance as ligands in Pd-catalyzed cross coupling reactions such as aryl sulfonamidation, aryl alkoxylation, and aryl amination in the presence of soluble organic bases. In each reaction studied, many ligands outperformed biaryl phosphanes known to promote the given transformation. Detailed substrate scopes were determined using high-throughput screening technology. Several biaryl phosphorinanes and their corresponding Pd(II) oxidative-addition complexes were extensively characterized using NMR spectroscopy and X-ray crystallography. General observations support that biaryl phosphorinanes promote reductive elimination and form robust catalysts with palladium. In many cases the use of these biaryl phosphorinanes may be advantageous over the use of biaryl phosphanes with respect to lower catalyst loadings, shorter reaction times, and robustness.
- Laffoon, Joshua D.,Chan, Vincent S.,Fickes, Michael G.,Kotecki, Brian,Ickes, Andrew R.,Henle, Jeremy,Napolitano, José G.,Franczyk, Thaddeus S.,Dunn, Travis B.,Barnes, David M.,Haight, Anthony R.,Henry, Rodger F.,Shekhar, Shashank
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- A Cascade Reaction of Michael Addition and Truce-Smiles Rearrangement to Synthesize Trisubstituted 4-Quinolone Derivatives
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A novel transition-metal-free cascade reaction to synthesize 4-quinolone derivatives has been demonstrated. Michael addition and Truce-Smiles rearrangement are included in this protocol, providing a broad scope of 4-quinolones in moderate-to-excellent yields. This work serves as an example of the use of sulfonamides through Truce-Smiles rearrangement to build heterocyclic compounds under mild conditions.
- Xie, Caixia,Yang, Di,Wang, Xinfeng,Ma, Chen
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- Sulphonamidic Groups as Electron-Withdrawing Units in Ureido-Based Anion Receptors: Enhanced Anion Complexation versus Deprotonation
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A sulphonamidic moiety was utilized as an electron-withdrawing group for enhancement of anion complexation features of urea-based receptors. A series of receptors varying in acidity of sulphonamidic and urea NH groups was synthesized and thoroughly tested. The individual complexation properties reflect deprotonation/complexation equilibrium in a given molecule as a function of the substitution. The receptors containing electron-donating groups in conjugation to the sulphonamidic moiety showed higher association constants towards H2PO4? and carboxylate anions, while those containing electron-withdrawing groups inclined to deprotonation of sulphonamidic NH. The deprotonation issue can be avoided by alkylation at the early step of receptor synthesis or it can be utilized for insertion of suitable groups that enable its anchoring on various substrates to form more elaborated receptor structures.
- ?imková, Ludmila,Císa?ová, Ivana,Cu?ínová, Petra,Ludvík, Ji?í,Sykora, Jan,Salvadori, Karolína
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p. 1401 - 1411
(2020/08/05)
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- Arylation and alkenylation of activated alkyl halides using sulfonamides
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A variety of quaternary aryl amino acid derivatives can be synthesised using tandem SN2/Smiles rearrangement chemistry involving aryl sulfonamides and α-chloro carbonyl compounds. The reaction harnesses a sulfur dioxide extrusion pathway to construct a C-N and C-Caryl bond under simple conditions with no requirement for organometallics or transition metal catalysts. The reaction is also successful for alkenyl sulfonamides, producing sterically congested quaternary alkene amino acid derivatives.
- Greaney, Michael F.,Johnson, Stuart,Kovács, Ervin
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supporting information
p. 3222 - 3224
(2020/03/23)
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- Highly chemo- and regioselective C-P cross-coupling reaction of quinone imine ketals with Ar2P(O)H to construct: Ortho -amino triarylphosphine derivatives
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A highly chemo- and regioselective approach for the construction of ortho-amino triarylphosphine oxides has been achieved through a C-P cross-coupling reaction involving quinone imine ketals (QIKs) with Ar2P(O)H and catalyzed via a Lewis base. This alternative protocol provided a wide substrate scope with excellent yields (82-95%), and a variety of ortho-amino triarylphosphines were obtained with high yields (87-95%) via further reductive reaction. Furthermore, this reaction could be scaled-up and several synthetic transformations were accomplished for the construction of functionalized organophosphorus.
- Liu, Teng,Li, Yongqin,Cheng, Feixiang,Shen, Xianfu,Liu, Jianjun,Lin, Jun
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supporting information
p. 3536 - 3541
(2019/07/10)
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- Rearrangement Reaction Based on the Structure of N-Fluoro- N-alkyl Benzenesulfonamide
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A novel rearrangement reaction based on the structure of N-fluoro-N-alkyl benzenesulfonamide was developed. The reaction proceeded readily at 50 °C in formic acid and generated a variety of benzenesulfonamides and aldehydes or ketones simultaneously. The reaction mechanism is believed to be a concerted mechanism that consist of 1,2-aryl migration with the departure of fluorine anion via an SN2 mechanism. This rearrangement reaction features an interesting reaction mechanism, mild reaction conditions, simple operations, and a broad substrate scope.
- Wang, Han-Ying,Pu, Xiao-Qiu,Yang, Xian-Jin
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p. 13103 - 13110
(2018/10/20)
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- A highly efficient heterogeneous copper-catalyzed Chan-Lam coupling reaction of sulfonyl azides with arylboronic acids leading to: N -arylsulfonamides
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A heterogeneous Chan-Lam coupling reaction between sulfonyl azides and arylboronic acids was achieved in MeOH at room temperature in the presence of 10 mol% of an l-proline-functionalized MCM-41-immobilized copper(i) complex [MCM-41-l-proline-CuCl] under air, yielding a variety of N-arylsulfonamides in excellent yields. The new heterogeneous copper complex can be prepared from commercially readily available and inexpensive reagents, and recovered by simple filtration of the reaction solution and recycled at least 8 times without any decreases in activity.
- You, Chongren,Yao, Fang,Yan, Tao,Cai, Mingzhong
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p. 43605 - 43612
(2016/05/24)
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- Palladium-Catalyzed Enantioselective 1,1-Fluoroarylation of Aminoalkenes
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The development of an enantioselective palladium-catalyzed 1,1-fluoroarylation of unactivated aminoalkenes is described. The reaction uses arylboronic acids as the arene source and Selectfluor as the fluorine source to generate benzylic fluorides in good yields with excellent enantioselectivities. This transformation, likely proceeding through an oxidative Heck mechanism, affords 1,1-difunctionalized alkene products.
- He, Ying,Yang, Zhenyu,Thornbury, Richard T.,Toste, F. Dean
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supporting information
p. 12207 - 12210
(2015/10/12)
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- Copper-catalyzed mild nitration of protected anilines
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A practical copper-catalyzed direct nitration of protected anilines, by using one equivalent of nitric acid as the nitrating agent, has been developed. This procedure features mild reaction conditions, wide structural scope (with regard to both N-protecting group and arene substitution), and high functional-group tolerance. Dinitration with two equivalents of nitric acid is also feasible. Practical and reliable: A Cu-catalyzed selective nitration of para- and ortho-substituted aniline derivatives by using one equivalent of HNO3 has been developed that produces water as the only stoichiometric byproduct (see scheme; PG=protecting group). This method is compatible with strongly electron-deficient substrates, enabling dinitration (by using 2.0 equiv of HNO3). This method allows for a rapid access to relevant nitrogen-containing heterocyclic architectures.
- Hernando, Elier,Castillo, Rafael R.,Rodríguez, Nuria,G?mez Arrayás, Ram?n,Carretero, Juan C.
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supporting information
p. 13854 - 13859
(2016/02/18)
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- Structure-guided design of potent diazobenzene inhibitors for the BET bromodomains
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BRD4, characterized by two acetyl-lysine binding bromodomains and an extra-terminal (ET) domain, is a key chromatin organizer that directs gene activation in chromatin through transcription factor recruitment, enhancer assembly, and pause release of the RNA polymerase II complex for transcription elongation. BRD4 has been recently validated as a new epigenetic drug target for cancer and inflammation. Our current knowledge of the functional differences of the two bromodomains of BRD4, however, is limited and is hindered by the lack of selective inhibitors. Here, we report our structure-guided development of diazobenzene-based small-molecule inhibitors for the BRD4 bromodomains that have over 90% sequence identity at the acetyl-lysine binding site. Our lead compound, MS436, through a set of water-mediated interactions, exhibits low nanomolar affinity (estimated Ki of 30-50 nM), with preference for the first bromodomain over the second. We demonstrated that MS436 effectively inhibits BRD4 activity in NF-κB-directed production of nitric oxide and proinflammatory cytokine interleukin-6 in murine macrophages. MS436 represents a new class of bromodomain inhibitors and will facilitate further investigation of the biological functions of the two bromodomains of BRD4 in gene expression.
- Zhang, Guangtao,Plotnikov, Alexander N.,Rusinova, Elena,Shen, Tong,Morohashi, Keita,Joshua, Jennifer,Zeng, Lei,Mujtaba, Shiraz,Ohlmeyer, Michael,Zhou, Ming-Ming
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p. 9251 - 9264
(2014/01/06)
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- ZnO and ZnO-nanoparticles: Efficient and reusable heterogeneous catalysts for one-pot synthesis of N-acylsulfonamides and sulfonate esters
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Commercially available and preparative ZnO nanoparticles are reported as efficient and reusable catalysts for the chemoselective synthesis of N-acylsulfonamides and sulfonate esters. A one-pot sequential sulfonylation and acylation of amines took place to afford the N-acylsulfonamides in excellent yields under solvent-free conditions. The ZnO catalyst can be reused for without significant loss of catalytic activity.
- Tamaddon, Fatemeh,Sabeti, Mohammad Reza,Jafari, Abbas Ali,Tirgir, Farhang,Keshavarz, Elham
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experimental part
p. 41 - 45
(2012/01/12)
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- Synthesis and biological evaluation of naphthoquinone analogs as a novel class of proteasome inhibitors
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Screening of the NCI Diversity Set-1 identified PI-083 (NSC-45382) a proteasome inhibitor selective for cancer over normal cells. Focused libraries of novel compounds based on PI-083 chloronaphthoquinone and sulfonamide moieties were synthesized to gain a better understanding of the structure-activity relationship responsible for chymotrypsin-like proteasome inhibitory activity. This led to the demonstration that the chloronaphthoquinone and the sulfonamide moieties are critical for inhibitory activity. The pyridyl group in PI-083 can be replaced with other heterocyclic groups without significant loss of activity. Molecular modeling studies were also performed to explore the detailed interactions of PI-083 and its derivatives with the β5 and β6 subunits of the 20S proteasome. The refined model showed an H-bond interaction between the Asp-114 and the sulfonamide moiety of the PI-083 in the β6 subunit.
- Lawrence, Harshani R.,Kazi, Aslamuzzaman,Luo, Yunting,Kendig, Robert,Ge, Yiyu,Jain, Sanjula,Daniel, Kenyon,Santiago, Daniel,Guida, Wayne C.,Sebti, Said M.
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experimental part
p. 5576 - 5592
(2010/09/15)
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- Analgesic agents without gastric damage: Design and synthesis of structurally simple benzenesulfonanilide-type cyclooxygenase-1-selective inhibitors
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In order to create novel analgesic agents without gastric disturbance, structurally simple cyclooxygenase-1 (COX-1) inhibitors with a benzenesulfonanilide skeleton were designed and synthesized. As a result, compounds 11f and 15a, which possess a p-amino group on the benzenesulfonyl moiety and p-chloro group on the anilino moiety, showed COX-1-selective inhibition. Moreover compound 11f, which is the most potent compound in this study showed more potent analgesic activity than that of aspirin at 30 mg/kg by po. The anti-inflammatory activity and gastric damage, however, were very weak or not detectably different from aspirin. Since the structure of our COX-1 inhibitors are very simple, they may be useful as lead compounds for superior COX-1 inhibitors as analgesic agents without gastric disturbance.
- Zheng, Xiaoxia,Oda, Hiroyuki,Takamatsu, Kayo,Sugimoto, Yukio,Tai, Akihiro,Akaho, Eiichi,Ali, Hamed Ismail,Oshiki, Toshiyuki,Kakuta, Hiroki,Sasaki, Kenji
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p. 1014 - 1021
(2007/10/03)
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- Highly specific N-monomethylation of primary aromatic amines
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A synthetic methodology for the specific conversion of primary aromatic amines into their N-monomethyl derivatives under very mild conditions is presented. Anilines are treated with 4-nitrobenzenesulfonyl (nosyl) chloride to generate the corresponding sulfonamides 2 in high yields. The subsequent N-methylation reaction of the sulfonamides 2 with a solution of diazomethane is rapid and quantitative. Removal of the nosyl protecting group is readily carried out using the reagent system mercaptoacetic acid/1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) affording the N-monomethylated aromatic amines 4. The procedure is convenient, efficient, and gives rise to the N-monomethyl-anilines exclusively.
- Le Pera, Adolfo,Leggio, Antonella,Liguori, Angelo
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p. 6100 - 6106
(2007/10/03)
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- Effect of para substitution on dissociation of N-phenylbenzenesulfonamides
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The reaction of substituted anilines and benzenesulfonyl chlorides has been used to prepare 49 substituted N-phenylbenzenesulfonamides of general formula 4-X-C6H4SO2NHC6H4-Y- 4′. Their purity was checked by elemental analysis. The substituents X and Y include H, CH3, CH3O, Cl, Br, CN, and NO2. The dissociation constants of all compounds were determined by potentiometric titration in methanol, acetonitrile, N,N-dimethylformamide, and pyridine. The obtained dissociation constants, pKHA, were correlated with various sets of substituent constants. It was found that the effects of substituents X and Y on the dissociation are best described by using the Hammett equation with σp constants and the Yukawa-Tsuno equation with σp- and σp constants, respectively. This result confirms the direct conjugation of Y substituent with the reaction centre. The explained variability using the additive model was above 96% in all the solvents used. The data also provided information about the transmission effect of the SO2 group. The average dissociation constants were further processed by the latent variables methods, principal components and conjugated deviations analyses.
- Mansfeld, Martin,Parik, Patrik,Ludwig, Miroslav
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p. 1479 - 1490
(2007/10/03)
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- Bimolecular nucleophilic displacement at tertiary carbon centers: Aminolyses of 2-cyano-2-propyl and 1-cyanocyclooctyl arenesulfonates
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Kinetic studies were carried out on the reactions of anilines with 2-cyano-2-propyl and 1-cyanocyclooctyl arenesulfonates in acetonitrile at 50·0°C. The second-order rate constants for the former are in general greater than those for the latter but the rates of the two become comparable for a strong nucleofuge. The cross-interaction constants, ρXZ (and βXZ), are considerably smaller (ca -0·04) than those for the primary (ca 0·33) and secondary (ca 0·12) compounds. The negative sign and small magnitude are consistent with a dissociative SN2 mechanism with a loose transition state structure. The ab initio MO theoretical results for Cl- + RCl?ClR + Cl- at the MP2 level (MP2/6-31 + G*//MP2/6-31 + G*) confirm the looseness of the transition state for the tertiary (R) alkyl compounds. The average r*(Cl...Cl) value is 4·88 ± 0·03 A, which is larger than those for the reactions at primary (4·68± 0·02 A) and secondary (4·80 ± 0·02 A) carbon centers. Thus a looser transition state with a smaller magnitude of ρXZ for the tertiary carbon centers has a larger theoretical r*(Cl-Cl) value.
- Oh, Hyuck Keun,Kwon, Young Bong,Chung, Dong Soo,Lee, Ikchoon
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p. 683 - 688
(2007/10/03)
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