- Photoinduced Acetylation of Anilines under Aqueous and Catalyst-Free Conditions
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A green and efficient visible-light induced functionalization of anilines under mild conditions has been reported. Utilizing nontoxic, cost-effective, and water-soluble diacetyl as photosensitizer and acetylating reagent, and water as the solvent, a variety of anilines were converted into the corresponding aryl ketones, iodides, and bromides. With advantages of environmentally friendly conditions, simple operation, broad substrate scope, and functional group tolerance, this reaction represents a valuable method in organic synthesis.
- Yang, Yu-Ming,Yan, Wei,Hu, Han-Wei,Luo, Yimin,Tang, Zhen-Yu,Luo, Zhuangzhu
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p. 12344 - 12353
(2021/09/02)
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- Palladium-Catalyzed Decarbonylative Iodination of Aryl Carboxylic Acids Enabled by Ligand-Assisted Halide Exchange
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We report an efficient and broadly applicable palladium-catalyzed iodination of inexpensive and abundant aryl and vinyl carboxylic acids via in situ activation to the acid chloride and formation of a phosphonium salt. The use of 1-iodobutane as iodide source in combination with a base and a deoxychlorinating reagent gives access to a wide range of aryl and vinyl iodides under Pd/Xantphos catalysis, including complex drug-like scaffolds. Stoichiometric experiments and kinetic analysis suggest a unique mechanism involving C?P reductive elimination to form the Xantphos phosphonium chloride, which subsequently initiates an unusual halogen exchange by outer sphere nucleophilic substitution.
- Boehm, Philip,Cacherat, Bastien,Lee, Yong Ho,Martini, Tristano,Morandi, Bill
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supporting information
p. 17211 - 17217
(2021/07/02)
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- Electrochemical oxidations of thioethers: Modulation of oxidation potential using a hydrogen bonding network
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A highly efficient chemo-selective electrochemical oxidation of thioethers to sulfoxides and sulfones was developed. The hydrogen bonding network generated from hexafluoro-2-propanol (HFIP) and acetic acid (AcOH) plays an important role in the modulation of oxidation potential. The hydrogen bonding network complexes strongly with the sulfoxide, making it less prone to further oxidation. Therefore, thioethers can be selectively electrochemically oxidized to sulfoxides and over-oxidization could be minimized. Moreover, this modulation of oxidization via hydrogen bonding was supported by density functional theory (DFT) calculations and cyclic voltammetry experiments.
- Liu, Shiwen,Chen, Bocheng,Yang, Yi,Yang, Yuhao,Chen, Qianjin,Zeng, Xiaojun,Xu, Bo
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- Selective Late-Stage Oxygenation of Sulfides with Ground-State Oxygen by Uranyl Photocatalysis
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Oxygenation is a fundamental transformation in synthesis. Herein, we describe the selective late-stage oxygenation of sulfur-containing complex molecules with ground-state oxygen under ambient conditions. The high oxidation potential of the active uranyl cation (UO22+) enabled the efficient synthesis of sulfones. The ligand-to-metal charge transfer process (LMCT) from O 2p to U 5f within the O=U=O group, which generates a UV center and an oxygen radical, is assumed to be affected by the solvent and additives, and can be tuned to promote selective sulfoxidation. This tunable strategy enabled the batch synthesis of 32 pharmaceuticals and analogues by late-stage oxygenation in an atom- and step-efficient manner.
- Li, Yiming,Rizvi, S. Aal-e-Ali,Hu, Deqing,Sun, Danwen,Gao, Anhui,Zhou, Yubo,Li, Jia,Jiang, Xuefeng
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supporting information
p. 13499 - 13506
(2019/08/21)
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- Method for catalyzing deaminized boric acid esterification or halogenation of arylamine
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The invention belongs to the technical field of organic synthesis and in particular discloses a method for catalyzing deaminized boric acid esterification or halogenation of arylamine. The method comprises the following steps: putting arylamine and a nitroso type compound into a mixed solvent, and performing a reaction at 0-5 DEG; and further adding a raw material capable of providing a functionalization group A and a catalysis amount of a reaction accelerator, and performing deamination functionalization reaction under light radiation at 10-50 DEG C, so as to obtain a product that an amino site of the arylamine is modified by the functionalization group A. Due to synergetic control on substrates, reaction solvents, material mixing modes, temperatures, reaction accelerators and addition amounts, boric acid esterification or halogenation of arylamine, particularly electron donating substituted arylamine which is hard to treat effectively in technical schemes of the industry, can be achieved.
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Paragraph 0063; 0076-0078
(2020/01/12)
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- Dihydropyrimidine compound and uses of dihydropyrimidine compound in drugs
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The present invention relates to a dihydropyrimidine compound and uses of the dihydropyrimidine compound as drugs, particularly as drugs for treatment and prevention of hepatitis B, particularly to acompound represented by a general formula (I) or (Ia) or an enantiomer, a diastereomer, a tautomer, a hydrate, a solvate or a pharmaceutically acceptable salt thereof, wherein each variable is definedin the specification. The invention further relates to uses of the compound represented by a general formula (I) or (Ia) or the enantiomer, the diastereomer, the tautomer, the hydrate, the solvate orthe pharmaceutically acceptable salt thereof as drugs, especially as drugs for treatment and prevention of hepatitis B. The formulas (I) and (Ia) are defined in the specification.
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Paragraph 1203; 1204; 1205; 1206
(2019/01/16)
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- DIHYDROPYRIMIDINE COMPOUNDS AND USES THEREOF IN MEDICINE
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Provided herein are a dihydropyrimidine compound and a pharmaceutical application thereof, especially the application used for treating and preventing HBV diseases. Specifically, provided herein is a compound having Formula (I) or (Ia), or an enantiomer, a diastereoisomer, a tautomer, a hydrate, a solvate, or a pharmaceutically acceptable salt thereof, wherein the variables of the formulas are as defined in the specification. Also provided herein is use of the compound having Formula (I) or (Ia), or an enantiomer, a diastereoisomer, a tautomer, a hydrate, a solvate, or a pharmaceutically acceptable salt thereof as a medicine, especially for treating and preventing HBV diseases.
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Paragraph 00447
(2019/01/17)
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- Sulfoxide and sulfone compounds, as well as selective synthesis method and application thereof
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The invention discloses a method for selectively synthesizing a sulfoxide compound shown as a formula (II) and a sulfone compound shown as a formula (III). In a reaction solvent, thioether (I) is usedas a reaction raw material and oxygen as an oxidation reagent, under the catalytic action of visible light and a photosensitive reagent; under the assistance of an additive, when a large-polarity proton-containing additive such as an acid and an alcohol or a solvent or an additive with excellent electron donating ability is used, a sulfoxide compound (II) is selectively generated; and when a small-polarity aprotic additive or a solvent is used, a sulfone compound (III) is selectively generated. The synthesis method has the advantages of easily available and cheap raw materials, simple reaction operation, mild reaction conditions, high yield and excellent functional group tolerance. According to the invention, synthesis and modification of some medicines are realized, and an efficient method for selectively constructing sulfoxide and sulfone compounds is provided for medicinal chemistry research.
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Paragraph 0049-0052; 0065-0068
(2019/12/02)
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- Visible-Light-Photosensitized Aryl and Alkyl Decarboxylative Functionalization Reactions
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Despite significant progress in aliphatic decarboxylation, an efficient and general protocol for radical aromatic decarboxylation has lagged far behind. Herein, we describe a general strategy for rapid access to both aryl and alkyl radicals by photosensitized decarboxylation of the corresponding carboxylic acids esters followed by their successive use in divergent carbon–heteroatom and carbon–carbon bond-forming reactions. Identification of a suitable activator for carboxylic acids is the key to bypass a competing single-electron-transfer mechanism and “switch on” an energy-transfer-mediated homolysis of unsymmetrical σ-bonds for a concerted fragmentation/decarboxylation process.
- Patra, Tuhin,Mukherjee, Satobhisha,Ma, Jiajia,Strieth-Kalthoff, Felix,Glorius, Frank
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p. 10514 - 10520
(2019/07/12)
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- Palladium-Catalyzed β-Arylation of Amide via Primary sp3C-H Activation
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A β-arylation of primary sp3C-H bonds on simple amides such as pivalamides with aryl iodides/CF3CO2Ag has been established successfully at 120 °C in a Pd(OAc)2 (catalyst)/CF3CH2OH (solvent) system. Pivalamides including tBuCONH2, tBuCONHR, and tBuCONR2 undergo the arylations smoothly to afford β-aryl pivalamides in moderate to good yields. Various aryl iodides are available bearing either electron-donating or electron-withdrawing substituted groups in the coupling reactions.
- Zhao, Ren,Lu, Wenjun
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supporting information
p. 2188 - 2192
(2018/07/25)
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- A general electrochemical strategy for the Sandmeyer reaction
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Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl3, CH2I2, CCl4, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot fashion. Furthermore, the practicality of this process was demonstrated in the multigram scale synthesis of aryl halides using highly inexpensive graphite as the electrode. A series of detailed mechanism studies have been performed, including radical clock and radical scavenger study, cyclic voltammetry analysis and in situ electron paramagnetic resonance (EPR) analysis.
- Liu, Qianyi,Sun, Beiqi,Liu, Zheng,Kao, Yi,Dong, Bo-Wei,Jiang, Shang-Da,Li, Feng,Liu, Guoquan,Yang, Yang,Mo, Fanyang
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p. 8731 - 8737
(2018/12/10)
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- Copper-catalyzed: S -methylation of sulfonyl hydrazides with TBHP for the synthesis of methyl sulfones in water
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A copper-catalyzed S-methylation of sulfonyl hydrazides with TBHP was efficiently developed, providing a variety of methyl sulfones with good to excellent yields. The reaction can be carried out in water smoothly without any ligand or additive under mild conditions and this catalyst-in-water can be recycled several times.
- Yang, Yu,Bao, Yajie,Guan, Qianqian,Sun, Qi,Zha, Zhenggen,Wang, Zhiyong
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p. 112 - 116
(2017/08/15)
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- A urea biphenyl compound and its composition and use thereof
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The invention relates to biphenyl derivatives, a preparation method, pharmaceutical compositions, and medicinal applications thereof. Specifically, the invention relates to novel carbamide substituted biphenyl compounds, pharmaceutical compositions and a
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Paragraph 0165-0169
(2017/01/02)
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- Easy Access to Difluoromethylene-Containing Arene Analogues through Palladium-Catalysed C–H Olefination
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An efficient palladium-catalysed ortho-C–H olefination of α,α-difluorophenylacetic acid derivatives using 8-aminoquinoline as a bidentate directing group has been developed. A range of olefinated arenes can thus be synthesized in a concise way. This reaction provides an easy and straightforward route to a panel of difluoromethylated arene analogues in moderate to good yields, with a satisfactory tolerance of common functional groups. Transformation of the products into a variety of other difluoromethylene-containing compounds demonstrates the utility of this method.
- Shao, Changdong,Shi, Guangfa,Zhang, Yanghui
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supporting information
p. 5529 - 5538
(2016/11/25)
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- Hypervalent Activation as a Key Step for Dehydrogenative ortho C-C Coupling of Iodoarenes
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Building on earlier results, a direct metal-free α- arylation of substituted cyclic 1,3-diones using ArI(O2CCF3)2 reagents has been developed; unlike other arylative approaches, the arylated products retain the iodine substituent ortho to the newly formed C-C bond. The mechanism is explored by using DFT calculations, which show a vanishingly small activation barrier for the C-C bond-forming step. In fact, taking advantage of an efficient in situ hypervalent activation, the iodoarenes are shown to undergo a cross- dehydrogenative C-C coupling at the C-H ortho to the iodine. When Oxone is used as terminal oxidant, the process is found to benefit from a rapid initial formation of the hypervalent ArI(OR)2 species and the sulfate-accelerated final coupling with a ketone. This method complements the ipso selectivity obtained in the metal-catalyzed α-arylation of carbonyl compounds.
- Wu, Yichen,Arenas, Ismael,Broomfield, Lewis Marc,Martin, Eddy,Shafir, Alexandr
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supporting information
p. 18779 - 18784
(2016/01/25)
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- Practical and efficient ipso-iodination of arylboronic acids via KF/I2 system
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A facile and effective iododeboronation of variously substituted aryl and heteroarylboronic acids through activation and subsequent ipso-introduction of iodine is presented. The use of KF and I2 at 80 °C in 1,4-dioxane furnishes iodinated compounds in high yields.
- Tramutola, Francesco,Chiummiento, Lucia,Funicello, Maria,Lupattelli, Paolo
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p. 1122 - 1123
(2015/02/19)
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- A practical and general ipso iodination of arylboronic acids using N-iodomorpholinium iodide (NIMI) as a novel iodinating agent: mild and regioselective synthesis of aryliodides
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A mild and efficient protocol for the ipso-iodination of aryl boronic acids using N-iodomorpholinium iodide (NIMI) generated in situ from morpholine and molecular iodine as a novel iodinating agent has been developed. The addition of a catalytic amount of copper iodide found to promote rate enhancement of the iodination reaction and dramatic increase in the yield depending upon the nature of the boronic acid was observed. The mechanistic study revealed that depending upon the nature of the substrate, either the classical ipso substitution or copper catalysed iododeborylation pathway overall dominates the present iodination reaction. The features such as mild reaction conditions, operational simplicity, high to excellent yields, excellent functional group compatibility and low catalyst loading make this method potentially useful in organic synthesis.
- Tale,Toradmal,Gopula
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p. 84910 - 84919
(2015/10/28)
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- Copper-promoted reductive coupling of aryl iodides with 1,1,1-trifluoro-2-iodoethane
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An efficient Cu-promoted reductive coupling of aryl iodides with 1,1,1-trifluoro-2-iodoethane has been developed. This reaction could occur in good yields under milder conditions as compared with previous studies. The reaction tolerated nitro, formyl, ester, ether, carbonyl, sulfonyl, and even azo groups.
- Xu, Song,Chen, Huan-Huan,Dai, Jian-Jun,Xu, Hua-Jian
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supporting information
p. 2306 - 2309
(2014/05/20)
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- Synthesis of18F-labelled cyclooxygenase-2 (COX-2) inhibitors via Stille reaction with 4-[18F]fluoroiodobenzene as radiotracers for positron emission tomography (PET)
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The Stille reaction with 4-[18F]fluoroiodobenzene as a novel approach for the synthesis of radiotracers for monitoring COX-2 expression by means of PET has been developed. Optimized reaction conditions were elaborated by screening of various ca
- Wuest, Frank R.,Hoehne, Aileen,Metz, Peter
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p. 503 - 507
(2007/10/03)
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