- Cp?Ir(III)-Catalyzed Mild and Broad C-H Arylation of Arenes and Alkenes with Aryldiazonium Salts Leading to the External Oxidant-Free Approach
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Reported herein is the development of Cp?Ir(III)-catalyzed direct C-H arylation of arenes and alkenes using aryldiazonium tetrafluoroborates, the use of which as an aryl precursor and also as an oxidant via C-N2 bond cleavage was a key to success in achieving a mild and external oxidant-free procedure. Mechanistic experiments and DFT calculations revealed the turnover-limiting step to be closely related to the formation of an Ir(V)-aryl intermediate rather than the presupposed C-H cleavage. Under the developed mild arylation conditions, a wide range of benzamides were smoothly arylated. In addition, synthetic utility of the current C-H arylation procedure was also demonstrated successfully for the (Z)-selective arylation of enamides and C8-selective reaction of quinoline N-oxides.
- Shin, Kwangmin,Park, Sung-Woo,Chang, Sukbok
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- Aqueous and Visible-Light-Promoted C-H (Hetero)arylation of Uracil Derivatives with Diazoniums
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Direct C5 (hetero)arylation of uracil and uridine substrates with (hetero)aryl diazonium salts under photoredox catalysis with blue light was reported. The coupling proceeds efficiently with diazonium salts and heterocycles in good functional group tolerance at room temperature in aqueous solution without transition-metal components. A plausible radical mechanism has been proposed.
- Liu, An-Di,Wang, Zhao-Li,Liu, Li,Cheng, Liang
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p. 16434 - 16447
(2021/11/16)
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- Discovery and structure-activity relationship studies of 1-aryl-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione derivatives as potent dual inhibitors of indoleamine 2,3-dioxygenase 1 (IDO1) and trytophan 2,3-dioxygenase (TDO)
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Indoleamine 2,3-dioxygenase 1 (IDO1) and tryptophan 2,3-dioxygenase (TDO), which mediate kynurenine pathway of tryptophan degradation, have emerged as potential new targets in immunotherapy for treatment of cancer because of their critical role in immunosuppression in the tumor microenvironment. In this investigation, we report the structural optimization and structure-activity relationship studies of 1-phenyl-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione derivatives as a new class of IDO1/TDO dual inhibitors. Among all the obtained dual inhibitors, 1-(3-chloro-4-fluorophenyl)-6-fluoro-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione (38) displayed the most potent IDO1 and TDO inhibitory activities with IC50 (half-maximal inhibitory concentration) values of 5 nM for IDO1 and 4 nM for TDO. It turned out that compound 38 was not a PAINS compound. Compound 38 could efficiently inhibit the biofunction of IDO1 and TDO in intact cells. In LL2 (Lewis lung cancer) and Hepa1-6 (hepatic carcinoma) allograft mouse models, this compound also showed considerable in vivo anti-tumor activity and no obvious toxicity was observed. Therefore, 38 could be a good lead compound for cancer immunotherapy and deserving further investigation.
- Pan, Shulei,Zhou, Yangli,Wang, Qiusheng,Wang, Yanlin,Tian, Chenyu,Wang, Tianqi,Huang, Luyi,Nan, Jinshan,Li, Linli,Yang, Shengyong
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- Modular and Selective Arylation of Aryl Germanes (C?GeEt3) over C?Bpin, C?SiR3 and Halogens Enabled by Light-Activated Gold Catalysis
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Selective C (Formula presented.) –C (Formula presented.) couplings are powerful strategies for the rapid and programmable construction of bi- or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd-catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd0/PdII catalysis) in the presence of the valuable functionalities C?BPin, C?SiMe3, C?I, C?Br, C?Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C?Ge with aryl diazonium salts. Contrary to previous light-/gold-catalyzed couplings of Ar–N2+, which were specialized in Ar–N2+ scope, we present conditions to efficiently couple electron-rich, electron-poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron-poor Ar–N2+ salts are readily activated by gold under blue-light irradiation, there is a competing dissociative deactivation pathway for excited electron-rich Ar–N2+, which requires an alternative photo-redox approach to enable productive couplings.
- Dahiya, Amit,Fricke, Christoph,Funes-Ardoiz, Ignacio,Gevondian, Avetik G.,Schoenebeck, Franziska,Sherborne, Grant J.
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supporting information
p. 15543 - 15548
(2020/06/22)
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- Transition-Metal- A nd Light-Free Directed Amination of Remote Unactivated C(sp3)-H Bonds of Alcohols
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Due to the great value of amino alcohols, new methods for their synthesis are in high demand. Abundant aliphatic alcohols represent the ideal feedstock for the method development toward this important motif. To date, transition-metal-catalyzed approaches for the directed remote amination of alcohols have been well established. Yet, they have certain disadvantages such as the use of expensive catalysts and limited scope. Very recently, transition-metal-free visible-light-induced radical approaches have emerged as new powerful tools for directed remote amination of alcohols. Relying on 1,5-HAT reactivity, these methods are limited to β-or δ- A mination only. Herein, we report a novel transitionmetal- A nd visible-light-free room-temperature radical approach for remote β-, γ-, and δ-C(sp3)-N bond formation in aliphatic alcohols using mild basic conditions and readily available diazonium salt reagents.
- Kurandina, Daria,Yadagiri, Dongari,Rivas, Monica,Kavun, Aleksei,Chuentragool, Padon,Hayama, Keiichi,Gevorgyan, Vladimir
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supporting information
p. 8104 - 8109
(2019/06/13)
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- Palladium catalyzed stereocontrolled synthesis of C-aryl glycosides using glycals and arenediazonium salts at room temperature
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A stereocontrolled synthesis of aryl-C-glycosides was achieved using glycals and aryldiazonium salts in the presence of palladium acetate. A wide range of glycals including d-glucal, d-galactal, l-rhamnal, d-xylal and d-ribal underwent C-arylation at the anomeric carbon in the presence of different aryldiazonium tetrafluoroborates and gave synthetically useful 2,3-deoxy-3-keto-α-aryl-C-glycosides in good to excellent yields. Broad substrate scope, simple operation and room temperature reactions make this protocol very attractive in organic synthesis.
- Singh, Adesh Kumar,Kandasamy, Jeyakumar
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supporting information
p. 5107 - 5112
(2018/07/29)
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- Ligand-Assisted Gold-Catalyzed Cross-Coupling with Aryldiazonium Salts: Redox Gold Catalysis without an External Oxidant
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Gold-catalyzed C(sp)-C(sp2) and C(sp2)-C(sp2) cross-coupling reactions are accomplished with aryldiazonium salts as the coupling partner. With the assistance of bpy ligand, gold(I) species were oxidized to gold(III) by diazonium without any external oxidants. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the nitrogen extrusion followed by AuIII reductive elimination as the key step.
- Cai, Rong,Lu, Mei,Aguilera, Ellen Y.,Xi, Yumeng,Akhmedov, Novruz G.,Petersen, Jeffrey L.,Chen, Hao,Shi, Xiaodong
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supporting information
p. 8772 - 8776
(2015/11/27)
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- An easy route to (hetero)arylboronic acids
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An unprecedented spontaneous reactivity between diazonium salts and diboronic acid has been unveiled, leading to a versatile arylboronic acid synthesis directly from (hetero)arylamines. This fast reaction (35 min overall) tolerates a wide range of functional groups and is carried out under very mild conditions. The radical nature of the reaction mechanism has been investigated.
- Erb, William,Hellal, Akila,Albini, Mathieu,Rouden, Jacques,Blanchet, Jerome
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supporting information
p. 6608 - 6612
(2014/06/09)
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- Chiral anion phase transfer of aryldiazonium cations: An enantioselective synthesis of C3-diazenated pyrroloindolines
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Herein is reported the first asymmetric utilization of aryldiazonium cations as a source of electrophilic nitrogen. This is achieved through a chiral anion phase-transfer pyrroloindolinization reaction that forms C3-diazenated pyrroloindolines from simple tryptamines and aryldiazonium tetrafluoroborates. The title compounds are obtained in up to 99% yield and 96% ee. The air- and water-tolerant reaction allows electronic and steric diversity of the aryldiazonium electrophile and the tryptamine core. Live and let diazene: Chiral anion phase transfer of aryldiazonium cations has been utilized to prepare C3-diazenated pyrroloindolines. The air- and water-tolerant reaction allows electronic and steric diversity in the aryldiazonium electrophile and the tryptamine core, with the products being obtained in up to 99% yield and 96% ee (MTBE=methyl tert-butyl ether).
- Nelson, Hosea M.,Reisberg, Solomon H.,Shunatona, Hunter P.,Patel, Jigar S.,Toste, F. Dean
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supporting information
p. 5600 - 5603
(2014/06/10)
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- PREPARATION OF 3,3-DIALKXOY-1-METHYLENEPROPYL ARENES
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The invention discloses a method for the preparation of 3,3-dialkxoy-1-methylenepropyl arenes from crotonaldehyde and aryldiazonium salts, and intermediates for the preparation of perfumes.
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Page/Page column 20
(2012/11/14)
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- PREPARATION OF 4,4-DIALKOXY-1-BUTEN-1-YLARENES
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The invention discloses a method for the preparation of 4,4-dialkoxy-1-buten-1-ylarenes from crotonaldehyde and aryldiazonium salts, n-buten-1-als and n-butan-1-als derived thereof, their use as fragrances, use of this method in and intermediates for the
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Page/Page column 35
(2012/11/14)
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- Rates and mechanisms of the thermal solvolytic decomposition of arenediazonium ions
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Arenediazonium tetrafluoroborates have been prepared and the kinetics of solvolysis have been investigated in water, trifluoroethanol, water-trifluoroethanol mixtures, hexafluoropropan-2-ol, trifluoroacetic acid, and ethanol by a UV method. A heterolytic mechanism involving short-lived aryl cations leads to products derived from nucleophilic capture of the aryl cations by solvent or a solute. Ionic solutes in aqueous trifluoroethanol and trifluoromethoxybenzene in trifluoroethanol have no kinetic effect and neither does replacement of the tetrafluoroborate counter-ion by chloride in trifluoroethanol. Rate constants for any one compound are not very solvent dependent, the reactions generally being characterised by high enthalpies of activation and appreciably positive entropies of activation. Compounds with 4-Cl, 4-F, 4-NO2, and 4-MeO substituents proved too unreactive for kinetic studies, but for different reasons. In ethanol, a radical reaction with characteristically different activation parameters competes with the heterolytic path and leads to hydrodediazoniation (reduction) by hydrogen atom abstraction from the CH2 group of ethanol.
- Canning, Peter S. J.,McCrudden, Katharine,Maskill, Howard,Sexton, Brian
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p. 2735 - 2740
(2007/10/03)
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