- Visible Light Generation of a Microsecond Long-Lived Potent Reducing Agent
-
Photoexcitation of molecular radicals can produce strong reducing agents; however, the limited lifetimes of the doublet excited states preclude many applications. Herein, we propose and demonstrate a general strategy to translate a highly energetic electron from a doublet excited state to a ZrO2insulator, thereby increasing the lifetime by about 6 orders of magnitude while maintaining a reducing potential less than -2.4 V vs SCE. Specifically, red light excitation of a salicylic acid modified perylene diimide radical anion PDI?-anchored to a ZrO2insulator yields a ZrO2(e-)|PDI charge separated state with an ~10 μs lifetime in 23% yield. The ZrO2(e-)s were shown to drive CO2→ CO reduction with a Re catalyst present in micromolar concentrations. More broadly, this strategy provides new opportunities to reduce important reagents and catalysts at low concentrations through diffusional electron transfer.
- Hu, Ke,Li, Pengju,Meyer, Gerald J.,Niu, Fushuang,Wang, Hanqi,Zhang, Zhenghao,Zhao, Zijian
-
supporting information
(2022/03/27)
-
- Method for efficiently synthesizing fluorine-containing compound
-
The invention discloses a method for efficiently synthesizing a fluorine-containing compound, and relates to the field of fluorine-containing compound synthesis. The method is a method for generating a corresponding fluorine atom substituted fluorine-containing compound by reacting aromatic chloride or activated chloride serving as a raw material with potassium fluoride under the action of a novel catalyst. The method disclosed by the invention has the advantages of good product selectivity, high efficiency, mild reaction conditions, simplicity and convenience in operation, convenience in application and the like.
- -
-
Paragraph 0036-0054
(2021/06/26)
-
- Tetramethylammonium Fluoride Alcohol Adducts for SNAr Fluorination
-
Nucleophilic aromatic fluorination (SNAr) is among the most common methods for the formation of C(sp2)-F bonds. Despite many recent advances, a long-standing limitation of these transformations is the requirement for rigorously dry, aprotic conditions to maintain the nucleophilicity of fluoride and suppress the generation of side products. This report addresses this challenge by leveraging tetramethylammonium fluoride alcohol adducts (Me4NF·ROH) as fluoride sources for SNAr fluorination. Through systematic tuning of the alcohol substituent (R), tetramethylammonium fluoride tert-amyl alcohol (Me4NF·t-AmylOH) was identified as an inexpensive, practical, and bench-stable reagent for SNAr fluorination under mild and convenient conditions (80 °C in DMSO, without the requirement for drying of reagents or solvent). A substrate scope of more than 50 (hetero) aryl halides and nitroarene electrophiles is demonstrated.
- Bland, Douglas C.,Lee, So Jeong,Morales-Colón, Mariá T.,Sanford, Melanie S.,Scott, Peter J. H.,See, Yi Yang
-
supporting information
p. 4493 - 4498
(2021/06/28)
-
- Sensitization-initiated electron transferviaupconversion: mechanism and photocatalytic applications
-
Sensitization-initiated electron transfer (SenI-ET) describes a recently discovered photoredox strategy that relies on two consecutive light absorption events, triggering a sequence of energy and electron transfer steps. The cumulative energy input from two visible photons gives access to thermodynamically demanding reactions, which would be unattainable by single excitation with visible light. For this reason, SenI-ET has become a very useful strategy in synthetic photochemistry, but the mechanism has been difficult to clarify due to its complexity. We demonstrate that SenI-ET can operateviasensitized triplet-triplet annihilation upconversion, and we provide the first direct spectroscopic evidence for the catalytically active species. In our system comprised offac-[Ir(ppy)3] as a light absorber, 2,7-di-tert-butylpyrene as an annihilator, andN,N-dimethylaniline as a sacrificial reductant, all photochemical reaction steps proceed with remarkable rates and efficiencies, and this system is furthermore suitable for photocatalytic aryl dehalogenations, pinacol couplings and detosylation reactions. The insights presented here are relevant for the further rational development of photoredox processes based on multi-photon excitation, and they could have important implications in the greater contexts of synthetic photochemistry and solar energy conversion.
- Glaser, Felix,Kerzig, Christoph,Wenger, Oliver S.
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p. 9922 - 9933
(2021/08/04)
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- Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
-
We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
- Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
-
p. 3723 - 3728
(2021/04/07)
-
- Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile
-
A copper-promoted cyanation of aryl iodides has been successfully developed by using N,N-dimethyl aminomalononitrile as the cyanide source with moderate toxicity and better stability. This reaction features broad substrate scope, excellent reaction yields, readily available catalyst, and simple reaction conditions.
- Liu, Si-Zhan,Li, Jing,Xue, Cao-Gen,Xu, Xue-Tao,Lei, Lin-Sheng,Huo, Chen-Yu,Wang, Zhen,Wang, Shao-Hua
-
supporting information
(2021/02/01)
-
- Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
-
Cyanation of aryl iodides is still challenging work for chemical researchers because of harsh reaction conditions and toxic cyanide sources. Herein, we have developed a new protocol based on the combination of the catalyst Pd@CeO2, nontoxic cyanide source K4[Fe (CN)6]·3H2O, and driving force visible light irradiation. The reaction is operated at relatively moderate temperature (55°C) and exhibits good catalytic efficiency of product aryl nitriles (yields of 89.4%). Moreover, the catalyst Pd@CeO2 possesses good reusability with a slight loss of photocatalytic activity after five consecutive runs. The reaction system based on the above combination shows a wide range of functional group tolerance under the same conditions. Reaction conditions such as temperature, time, the component of catalyst, and solutions are optimized by studying cyanation of 1-iodo-4-nitrobenzene as model reaction. According to these results, the possible mechanism of Pd@CeO2-catalyzed cyanation of aryl iodides under visible light irradiation is proposed based on the influence of visible light on the catalyst and reactant compounds. In all, we provided an environmental and economic method for preparation of aryl nitriles from cyanation of aryl iodides based on the goal of green chemistry for sustainable development.
- Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
-
-
- Method for catalyzing oxidation of amines to generate nitrile by using nonmetal mesoporous nitrogen-doped carbon material
-
The invention discloses a method for preparing nitrile by catalyzing amine oxidation with a non-metal mesoporous nitrogen-doped carbon material catalyst, which is applied to the field of synthesis, the material is prepared by using a nitrogen-containing organic ligand as a precursor and silica sol as a template agent, calcining in the atmosphere of inert gases such as N2 or Ar and then removing the template agent; oxygen or air is used as an oxygen source, the reaction is performed at 80-130 DEG C under the action of ammonia water in the presence of a solvent, the effect is good, and the product still keeps higher activity after being recycled for more than 8 times, and has a wide industrial application prospect. The invention provides a heterogeneous non-metal catalytic system for catalyzing amine oxidation to prepare nitrile for the first time, and compared with a reported metal catalyst, the heterogeneous non-metal catalytic system does not bring metal pollution to a product to influence the effect of cyano drugs.
- -
-
Paragraph 0019; 0037
(2021/05/08)
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- One pot synthesis of aryl nitriles from aromatic aldehydes in a water environment
-
In this study, we found a green method to obtain aryl nitriles from aromatic aldehyde in water. This simple process was modified from a conventional method. Compared with those approaches, we used water as the solvent instead of harmful chemical reagents. In this one-pot conversion, we got twenty-five aryl nitriles conveniently with pollution to the environment being minimized. Furthermore, we confirmed the reaction mechanism by capturing the intermediates, aldoximes.
- Chen, Qingqing,Han, Hongwei,Lin, Hongyan,Ma, Xiaopeng,Qi, Jinliang,Wang, Xiaoming,Yang, Yonghua,Zhou, Ziling
-
p. 24232 - 24237
(2021/07/29)
-
- NHC-catalyzed silylative dehydration of primary amides to nitriles at room temperature
-
Herein we report an abnormal N-heterocyclic carbene catalyzed dehydration of primary amides in the presence of a silane. This process bypasses the energy demanding 1,2-siloxane elimination step usually required for metal/silane catalyzed reactions. A detailed mechanistic cycle of this process has been proposed based on experimental evidence along with computational study.
- Ahmed, Jasimuddin,Hota, Pradip Kumar,Maji, Subir,Mandal, Swadhin K.,Rajendran, N. M.
-
supporting information
p. 575 - 578
(2020/01/29)
-
- Method for continuous preparation of nitriles by amides (by machine translation)
-
The method comprises the following steps: preparing a lead salt supported by a molecular sieve by a lead salt and a molecular sieve through an impregnation method; and filling a molecular sieve-loaded lead catalyst into a fixed bed reactor. The amide or amide solution is sent into a fixed bed reactor from the top of the fixed bed to be subjected to catalytic dehydration, and the obtained reaction product is led out from the bottom of the fixed bed. The reaction product is separated to obtain the crude product of the nitrile corresponding to the amide. A fixed bed continuous production process is adopted, the reaction process is simple, the production efficiency is high, the product post-treatment is simple, and industrial production is easy to realize. (by machine translation)
- -
-
Paragraph 0033-0054; 0061-0065
(2020/12/15)
-
- Palladium-Catalyzed Cyanation under Mild Conditions: A Case Study to Discover Appropriate Substrates among Halides and Pseudohalides
-
A case study has been effectively carried out to identify a suitable substrate among halides and pseudohalides for the palladium-catalyzed cyanation reactions under mild conditions. Among the various substrates considered for evaluation, aryl pentafluorobenzenesulfonates and nonaflates were identified to be the best substrates when compared to corresponding halides and pseudohalides. The substoichiometric use of nontoxic, environmentally benign potassium hexacyanoferrate as a cyanide source and exceptionally milder conditions further highlights the significance of the protocol developed. A wide range of electronically biased and sterically challenging substrates provided the corresponding the nitriles in good to excellent yields.
- Rajendra, Merla Arjuna,Sunil,Sajith, Ayyiliath Meleveetil,Joy, Muthipeedika Nibin,Bakulev, Vasiliy A.,Haridas, Karickal Raman
-
supporting information
p. 1629 - 1633
(2020/09/15)
-
- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
-
We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
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p. 378 - 385
(2020/10/02)
-
- HCl·DMPU-assisted one-pot and metal-free conversion of aldehydes to nitriles
-
We report an efficient HCl·DMPU assisted one-pot conversion of aldehydes into nitriles. The use of HCl·DMPU as both an acidic source as well as a non-nucleophilic base constitutes an environmentally mild alternative for the preparation of nitriles. Our protocol proceeds smoothly without the use of toxic reagents and metal catalysts. Diverse functionalized aromatic, aliphatic and allylic aldehydes incorporating various functional groups were successfully converted to nitriles in excellent to quantitative yields. This protocol is characterized by a broad substrate scope, mild reaction conditions, and high scalability. This journal is
- Hammond, Gerald B.,Mudshinge, Sagar R.,Potnis, Chinmay S.,Xu, Bo
-
supporting information
p. 4161 - 4164
(2020/07/14)
-
- Method for continuous preparation of nitriles in a pipelined reactor (by machine translation)
-
The method comprises the following steps that a tin catalyst is coated on the inner wall of the pipeline reactor; and the method comprises the following steps: coating a tin catalyst on the inner wall of the pipeline reactor. The amide solution and the catalytic auxiliary agent are mixed and then sent to a pipeline reactor, and the amide is dehydrated to generate nitrile at the reaction pressure of 0.1 - 2.0 mpa and 100 - 200 °C reaction temperature. The resulting reaction product was separated to give the crude product of the nitrile to which the amide corresponded. In the pipeline reactor, the corresponding nitrile is continuously prepared under the action of the tin catalyst, a dehydrating agent is not needed, byproducts only are water, and three wastes are reduced. (by machine translation)
- -
-
Paragraph 0036-0047; 0056-0057
(2020/12/14)
-
- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
-
The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
- -
-
Paragraph 0034-0039; 0160-0165
(2020/09/16)
-
- The Tandem Photoredox Catalysis Mechanism of [Ir(ppy)2(dtb-bpy)]+ Enabling Access to Energy Demanding Organic Substrates
-
We report the discovery of a tandem catalytic process to reduce energy demanding substrates, using the [Ir(ppy)2(dtb-bpy)]+ (1+) photocatalyst. The immediate products of photoinitiated electron transfer (PET) between 1+ and triethylamine (TEA) undergo subsequent reactions to generate a previously unknown, highly reducing species (2). Formation of 2 occurs via reduction and semisaturation of the ancillary dtb-bpy ligand, where the TEA radical cation serves as an effective hydrogen atom donor, confirmed by nuclear magnetic resonance, mass spectrometry, and deuterium labeling experiments. Steady-state and time-resolved luminescence and absorption studies reveal that upon irradiation, 2 undergoes electron transfer or proton-coupled electron transfer (PCET) with a representative acceptor (N-(diphenylmethylene)-1-phenylmethanamine; S). Turnover of this new photocatalytic cycle occurs along with the reformation of 1+. We rationalize our observations by proposing the first example of a mechanistic pathway where two distinct yet interconnected photoredox cycles provide access to an extended reduction potential window capable of engaging a wide range of energy demanding and synthetically relevant organic substrates including aryl halides.
- Connell, Timothy U.,Fraser, Catherine L.,Czyz, Milena L.,Smith, Zoe M.,Hayne, David J.,Doeven, Egan H.,Agugiaro, Johnny,Wilson, David J. D.,Adcock, Jacqui L.,Scully, Andrew D.,Gómez, Daniel E.,Barnett, Neil W.,Polyzos, Anastasios,Francis, Paul S.
-
p. 17646 - 17658
(2019/11/11)
-
- Selectivity-tunable amine aerobic oxidation catalysed by metal-free N,O-doped carbons
-
Herein, we present a series of N,O-doped mesoporous carbons obtained at different pyrolysis temperatures as the first metal-free catalysts which successfully switch between imine and nitrile products for amine oxidation. Systematic characterization studies and control experiments revealed that the C-O group on the surface could function as a catalytically active site for nitrile synthesis and the N-doping environment was essential.
- Li, Yingguang,Shang, Sensen,Wang, Lianyue,Lv, Ying,Niu, Jingyang,Gao, Shuang
-
supporting information
p. 12251 - 12254
(2019/10/21)
-
- Cyanation of Anilines to Aryl Nitriles Using tert-Butyl Isocyanide: A Simple and Copper-free Procedure
-
In this manuscript, a simple and copper-free procedure for the synthesis of aryl nitrile derivatives from anilines is described. Under the improved protocol, the anilines were reacted with tert-butyl isocyanide under a mild reaction condition without the use of solvents and copper catalyst to synthesize benzonitriles. This copper-free Sandmeyer-type reaction could tolerate a range of anilines bearing different functional groups and also can be conducted even without the exclusion of air. In addition, this method has afforded the aryl nitriles in moderate to good yields (52–81%). The obtained results in this study reveal that the tert-butyl isocyanide as a potential cyanide source for the cyanation reaction.
- Chia, Poh Wai,Yong, Fu Siong Julius,Mohamad, Habsah,Kan, Su-Yin
-
supporting information
p. 939 - 942
(2019/08/21)
-
- Palladium-Catalyzed Late-Stage Direct Arene Cyanation
-
Methods for direct benzonitrile synthesis are sparse, despite the versatility of cyano groups in organic synthesis and the importance of benzonitriles for the dye, agrochemical, and pharmaceutical industries. We report the first general late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance. The reaction is enabled by a dual-ligand combination of quinoxaline and an amino acid-derived ligand. The method is applicable to direct cyanation of several marketed small-molecule drugs, common pharmacophores, and organic dyes. Benzonitriles are some of the most versatile building blocks for organic synthesis, in particular in the pharmaceutical industry, but general methods to make them by direct C–H functionalization are unknown. In this issue of Chem, Ritter and coworkers describe a late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance, enabled by a palladium-dual-ligand catalyst system. The reaction may serve for the late-stage modification of drug candidates. Aryl nitriles constitute an important class of organic compounds that are widely found in natural products, pharmaceuticals, agricultural chemicals, dyes, and materials. Moreover, nitriles are versatile building blocks to access numerous other important molecular structure groups. However, no general method for direct aromatic C–H cyanation is known. All approaches to date require either an appropriate directing group or reactive electron-rich substrates, such as indoles, which limit their synthetic applications. Here we describe an undirected, palladium-catalyzed late-stage aryl C–H cyanation reaction for the synthesis of complex aryl nitriles that would otherwise be more challenging to produce. The wide substrate scope and good functional-group tolerance of this reaction provide direct and quick access to structural diversity for pharmaceutical and agrochemical development.
- Zhao, Da,Xu, Peng,Ritter, Tobias
-
supporting information
p. 97 - 107
(2019/01/21)
-
- Visible light-induced direct conversion of aldehydes into nitriles in aqueous medium using Co@g-C3N4 as photocatalyst
-
Unprecedented Co@g-C3N4 catalyzed visible light driven efficient conversion of a variety of aldehydes into corresponding nitriles is reported. Operational simplicity, excellent yield of pure products (87–94%), ambient reaction condition, using aqueous methanol as solvent, visible-light photocatalysis are the salient features of envisaged methodology for direct conversion of aldehydes into nitriles. Furthermore, reusability of Co@g-C3N4 was checked up to five runs and it was noticed that there was no substantial change in morphology as well as the catalytic efficiency of catalyst.
- Verma, Fooleswar,Shukla, Prashant,Bhardiya, Smita R.,Singh, Manorama,Rai, Ankita,Rai, Vijai K.
-
-
- Catalytic oxidative conversion of aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8: A practical approach to febuxostat
-
A novel approach to convert aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8 has been developed. Both alkyl and aryl nitriles were obtained in good to excellent yields. Electron-withdrawing and electron-donating groups, such as fluoro, chloro, bromo, nitro, ester, cyano, trifluoromethyl and alkoxy were tolerated. Notably, febuxostat and its intermediate, ethyl 2-[3-cyano-4-(2-methylpropoxy)phenyl]-4-methyl-5-thiazolecarboxylate, were obtained in excellent yields.
- Chen, Han,Sun, Sijia,Xi, Haoying,Hu, Kaifang,Zhang, Ning,Qu, Jingping,Zhou, Yuhan
-
supporting information
p. 1434 - 1436
(2019/05/01)
-
- Copper-Catalyzed Unstrained C-C Single Bond Cleavage of Acyclic Oxime Acetates Using Air: An Internal Oxidant-Triggered Strategy toward Nitriles and Ketones
-
A copper-catalyzed aerobic oxidative C-C single bond cleavage of acyclic unstrained oxime acetates is reported, providing various aryl nitriles and ketones in good yields. Mechanistic studies indicate a radical procedure is involved in this transformation, and the oxygen atom in the ketone products is originated from O2 in the air. Oxime acetates as an internal oxidant have been proved to be an initiator, which may promote the discovery of novel protocol for C-C bond cleavage and dioxygen activation.
- Zhu, Chuanle,Chen, Fulin,Liu, Chi,Zeng, Hao,Yang, Zhiyi,Wu, Wanqing,Jiang, Huanfeng
-
p. 14713 - 14722
(2018/12/14)
-
- Catalytic Promiscuity of Galactose Oxidase: A Mild Synthesis of Nitriles from Alcohols, Air, and Ammonia
-
We report an unprecedented catalytically promiscuous activity of the copper-dependent enzyme galactose oxidase. The enzyme catalyses the one-pot conversion of alcohols into the related nitriles under mild reaction conditions in ammonium buffer, consuming ammonia as the source of nitrogen and dioxygen (from air at atmospheric pressure) as the only oxidant. Thus, this green method does not require either cyanide salts, toxic metals, or undesired oxidants in stoichiometric amounts. The substrate scope of the reaction includes benzyl and cinnamyl alcohols as well as 4- and 3-pyridylmethanol, giving access to valuable chemical compounds. The oxidation proceeds through oxidation from alcohol to aldehyde, in situ imine formation, and final direct oxidation to nitrile.
- Vilím, Jan,Knaus, Tanja,Mutti, Francesco G.
-
supporting information
p. 14240 - 14244
(2018/10/15)
-
- PROCESS FOR FLUORINATING COMPOUNDS
-
Disclosed are mild temperature (e.g., from 0 to 80°C) SNAr fluorinations of a variety of halide and sulfonate substituted aryl and heteroaryl substrates using NMe4F.
- -
-
Page/Page column 22-23; 36
(2017/02/28)
-
- Direct synthesis of nitriles by Cu/DMEDA/TEMPO-catalyzed aerobic oxidation of primary amines with air
-
By screening the copper catalysts, ligands, and the reaction conditions, a simple CuCl/DMEDA/TEMPO catalyst system readily available from commercial sources is developed for a direct and selective synthesis of the useful nitriles by an aerobic oxidation reaction of primary amines using air as an advantageous oxidant under mild conditions.
- Ma, Xian-Tao,Xu, Hao,Xiao, Ying-Lin,Su, Chen-Liang,Liu, Jian-Ping,Xu, Qing
-
p. 1336 - 1339
(2017/06/21)
-
- Decarbonylative Cyanation of Amides by Palladium Catalysis
-
Transition-metal-catalyzed cyanation of aryl halides is a process of significant importance in the preparation pharmaceuticals, organic materials and agrochemicals. Here, we demonstrate a palladium-catalyzed decarbonylative cyanation of amides by highly selective carbon-nitrogen bond cleavage for the synthesis of a wide range of aryl nitriles. The utility of this technology is demonstrated by the synthesis of isotopically labeled aryl nitriles and orthogonal cross-coupling reactions of bench-stable amides to establish cross-coupling synthons with opposite polarity.
- Shi, Shicheng,Szostak, Michal
-
supporting information
p. 3095 - 3098
(2017/06/23)
-
- Nucleophilic deoxyfluorination of phenols via aryl fluorosulfonate intermediates
-
This report describes a method for the deoxyfluorination of phenols with sulfuryl fluoride (SO2F2) and tetramethylammonium fluoride (NMe4F) via aryl fluorosulfonate (ArOFs) intermediates. We first demonstrate that the reaction of ArOFs with NMe4F proceeds under mild conditions (often at room temperature) to afford a broad range of electronically diverse and functional group-rich aryl fluoride products. This transformation was then translated to a one-pot conversion of phenols to aryl fluorides using the combination of SO2F2 and NMe4F. Ab initio calculations suggest that carbon-fluorine bond formation proceeds via a concerted transition state rather than a discrete Meisenheimer intermediate.
- Schimler, Sydonie D.,Cismesia, Megan A.,Hanley, Patrick S.,Froese, Robert D.J.,Jansma, Matthew J.,Bland, Douglas C.,Sanford, Melanie S.
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p. 1452 - 1455
(2017/02/10)
-
- METHOD FOR AROMATIC FLUORINATION
-
Disclosed is a fluorination method comprising providing an aryl fluorosuifonate and a fluorinating reagent to a reaction mixture; and reacting the aryl fluorosuifonate and the fluorinating reagent to provide a fluorinated aryl species. Also disclosed is a fluorination method comprising providing, a salt comprising a cation and an aryloxyiate, and SO2F2 to a reaction mixture; reacting the SO2F2 and the ammonium salt to provide a fluorinated aryl species. Further disclosed a fluorination method comprising providing a compound having the structure Ar-OH to a reaction mixture; where A is an aryl or heteroaryl; providing SO2F2 to the reaction mixture; providing a fluorinating reagent to the reaction mixture; reacting the SO2F2, the fluorinating reagent and the compound having the structure Ar-OH to provide a fluorinated aryl species having the structure Ar-F.
- -
-
Paragraph 0047-0049
(2017/12/18)
-
- Synthesis of nitriles from aerobic oxidation of amines catalyzed by ruthenium supported on activated carbon
-
Nitriles were synthesized from the aerobic oxidation of amines over commercially available catalysts, which were activated carbon-supported ruthenium catalysts (Ru/AC). The 5%Ru/AC catalyst can tolerate a wide range of substrates, such as aromatic, aliphatic, and heterocyclic amines, and afford the target nitriles in good-to-excellent yields. The 5%Ru/AC catalyst was easily recovered and no ruthenium leaking took place in the catalytic run.
- Niu, Baoqiang,Lu, Fei,Zhang, Hong-Yu,Zhang, Yuecheng,Zhao, Jiquan
-
supporting information
p. 330 - 333
(2017/02/23)
-
- Heterogeneous cobalt catalysts for selective oxygenation of alcohols to aldehydes, esters and nitriles
-
Efficient and green oxygenation of alcohols to the corresponding aldehydes, esters and nitriles was developed with high selectivity. Functional alcohols, including some heterocyclic and allylic alcohols can be oxygenated to the corresponding aldehydes, esters and nitriles respectively. Moreover, the catalyst can be recycled and reused without significant deactivation. Noteworthy, the Co@NC (800-2h) catalyzed oxygenation of alcohols can be regulated easily by changing the reaction conditions, and then the corresponding aldehydes, esters and nitriles can be obtained in high yields respectively.
- Mao, Fei,Qi, Zhengliang,Fan, Haipeng,Sui, Dejun,Chen, Rizhi,Huang, Jun
-
p. 1498 - 1503
(2017/01/18)
-
- Electrocatalytic synthesis of nitriles from aldehydes with ammonium acetate as the nitrogen source
-
A simple synthesis method of nitriles from corresponding aldehydes by electrochemical oxidation was developed with ammonium acetate as the nitrogen source and 4-acetamido- 2,2,6,6-tetramethylpiperidinyl-l-oxy (4-AcNH-TEMPO) as the catalyst. Cyclic voltammetry was performed to investigate the electrocatalytic activity of 4-AcNH-TEMPO for the conversion of benzaldehyde to benzonitrile. On the basis of in situ FTIR data and cyclic voltammetry experiments, a reaction mechanism, involving the redox of 4-AcNH-TEMPO and the generation of intermediate imine during the reaction, was proposed. This electrocatalytic reaction system provided an efficient protocol for synthesis of aromatic nitriles at room temperature with moderate to high yields.
- Yang, Xianjing,Fan, Zhongquan,Shen, Zhenlu,Li, Meichao
-
-
- Copper Iodide Mediated Cyanation of Arylboronic Acids and Aryl Iodides with Ethyl (Ethoxymethylene)cyanoacetate as Cyanating Agent
-
An efficient copper iodide mediated cyanation of arylboronic acids and aryl iodides with ethyl (ethoxymethylene)cyanoacetate as cyanating agent has been developed. The reaction involves a C(sp2)-CN bond cleavage and tolerates a wide range of functional groups, affording the corresponding aryl nitriles in moderate to excellent yields.
- Qi, Chaorong,Hu, Xiaohan,He, Haitao
-
p. 1979 - 1982
(2016/08/09)
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- Visible light catalysis synthesis method of aryl cyanide
-
The invention discloses a visible light catalysis synthesis method of aryl cyanide. The method comprises the following steps: putting aryl halide, potassium ferrocyanide and alkali in an organic solvent; in the condition of magnetic stirring, starting a visible light source with power of 100-500W; irradiating with light intensity of 0.2-0.8W/cm until the reaction is over while controlling the reaction temperature at 25-85 DEG C; and carrying out a catalytic reaction for 1-12h by using a nano precious metal supported photocatalyst to synthesize the aryl cyanide. The photocatalysis cyaniding process can be shown by a general formula (I), wherein the X group is Br or I; and the R group is selected from electron attracting groups such as nitryl, acetyl and carboxyl and electron donating groups such as methoxy and methyl. In the invention, nontoxic green potassium ferrocyanide is used as a cyanogen source for synthesizing aryl cyanide, the highly toxic cyanides widely used in original methods are replaced, and thus the problem of environmental pollution in the aryl cyanide synthesis is reduced. The photocatalysis cyaniding reaction has the advantages of mild reaction conditions, stability and high efficiency, simplicity in operation, environmental friendliness, high product conversion rate and good selectivity.
- -
-
Paragraph 0042; 0043
(2017/02/28)
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- Electrochemical synthesis of nitriles from aldehydes using TEMPO as a mediator
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A novel electrochemical route to generate nitriles from aldehydes under mild conditions using a catalytic amount of TEMPO (2,2,6,6-tetramethylpiperidinyl-l-oxy) as the mediator and hexamethyldisilazane as the nitrogen source in the presence of acetic acid has been developed. A variety of aromatic, heteroaromatic and aliphatic aldehydes have been converted to their corresponding nitriles in good to excellent yields. A plausible reaction mechanism is proposed based on the cyclic voltammetry, in situ FTIR and the identification of intermediates.
- Chen, Qiguo,Fang, Chaojie,Shen, Zhenlu,Li, Meichao
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- A method for preparing of the benzonitrile derivatives
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The invention discloses a preparation method of a cyanobenzene derivative. The cyanobenzene derivative is prepared by taking phenylacetic acid or the derivative thereof as well as urea as raw materials, copper salt as a catalyst and oxygen as an oxidizing agent. According to the preparation method disclosed by the invention, by adopting copper salt as the catalyst and oxygen as the oxidizing agent without an extra cocatalyst, the raw materials phenylacetic acid or the derivative thereof are easy to purchase in the market, low in cost and various in type, and urea as the source of cyanogen is low in toxicity, low in price, mild in reaction condition and environmentally friendly, and has a good functional group compatibility.
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Paragraph 0021; 0022; 0023; 0054; 0055; 0056; 0057
(2016/10/17)
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- Acyl azolium fluorides for room temperature nucleophilic aromatic fluorination of chloro- and nitroarenes
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The reaction of acid fluorides with N-heterocyclic carbenes (NHCs) produces anhydrous acyl azolium fluorides. With appropriate selection of acid fluoride and NHC, these salts can be used for the room temperature SNAr fluorination of a variety of aryl chlorides and nitroarenes.
- Ryan, Sarah J.,Schimler, Sydonie D.,Bland, Douglas C.,Sanford, Melanie S.
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supporting information
p. 1866 - 1869
(2015/04/27)
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- Anhydrous Tetramethylammonium Fluoride for Room-Temperature SNAr Fluorination
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This paper describes the room-temperature SNAr fluorination of aryl halides and nitroarenes using anhydrous tetramethylammonium fluoride (NMe4F). This reagent effectively converts aryl-X (X = Cl, Br, I, NO2, OTf) to aryl-F under mild conditions (often room temperature). Substrates for this reaction include electron-deficient heteroaromatics (22 examples) and arenes (5 examples). The relative rates of the reactions vary with X as well as with the structure of the substrate. However, in general, substrates bearing X = NO2 or Br react fastest. In all cases examined, the yields of these reactions are comparable to or better than those obtained with CsF at elevated temperatures (i.e., more traditional halex fluorination conditions). The reactions also afford comparable yields on scales ranging from 100 mg to 10 g. A cost analysis is presented, which shows that fluorination with NMe4F is generally more cost-effective than fluorination with CsF.
- Schimler, Sydonie D.,Ryan, Sarah J.,Bland, Douglas C.,Anderson, John E.,Sanford, Melanie S.
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p. 12137 - 12145
(2016/01/09)
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- Palladium/N-Heterocyclic carbene catalyzed mono- and double-cyanation of aryl halides using potassium ferrocyanide trihydrate under aerobic conditions
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Abstract A practical palladium/N-heterocyclic carbene catalyzed procedure for the mono- and double-cyanation of aryl halides is described using inexpensive, easy-to-handle and nontoxic potassium ferrocyanide trihydrate {K4[Fe(CN)6]·3H2O} as the cyanating agent. The reaction does not require an anhydrous solvent, or the exclusion of air or moisture. A variety of electron-rich and electron-deficient aryl halides are efficiently converted into their corresponding nitriles and dicarbonitriles.
- Xu, Zhicheng,Xiao, Yunqing,Ding, Hong,Cao, Changsheng,Li, Haitao,Pang, Guangsheng,Shi, Yanhui
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p. 1560 - 1566
(2015/06/02)
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- Synthesis of aryl dihydrothiazol acyl shikonin ester derivatives as anticancer agents through microtubule stabilization
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The high incidence of cancer and the side effects of traditional anticancer drugs motivate the search for new and more effective anticancer drugs. In this study, we synthesized 17 kinds of aryl dihydrothiazol acyl shikonin ester derivatives and evaluated their anticancer activity through MTT assay. Among them, C13 showed better antiproliferation activity with IC50 = 3.14 ± 0.21 μM against HeLa cells than shikonin (IC50 = 5.75 ± 0.47 μM). We then performed PI staining assay, cell cycle distribution, and cell apoptosis analysis for C13 and found that it can cause cell arrest in G2/M phase, which leads to cell apoptosis. This derivative can also reduce the adhesive ability of HeLa cells. Docking simulation and confocal microscopy assay results further indicated that C13 could bind well to the tubulin at paclitaxel binding site, leading to tubulin polymerization and mitotic disruption.
- Lin, Hong-Yan,Li, Zi-Kang,Bai, Li-Fei,Baloch, Shahla Karim,Wang, Fang,Qiu, Han-Yue,Wang, Xue,Qi, Jin-Liang,Yang, Raong-Wu,Wang, Xiao-Ming,Yang, Yong-Hua
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- A highly efficient, ligand-free and recyclable SBA-15 supported Cu 2O catalyzed cyanation of aryl iodides with potassium hexacyanoferrate(ii)
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SBA-15 supported Cu2O nanoparticles (Cu2O/SBA-15) have been fabricated and characterized. The as-prepared Cu2O/SBA-15 is a highly effective catalyst for cyanation of aryl iodides using non-toxic K4[Fe(CN)6] as a cyanide source in dimethylformamide (DMF). The approach achieves a high selectivity and an excellent yield without using any ligands and base additives. Moreover, the Cu2O/SBA-15 catalyst shows wide functional group tolerance and reusability with a slight loss of activity. the Partner Organisations 2014.
- Yin, Wenzhu,Liu, Rui,He, Guangke,Lv, Wangjie,Zhu, Hongjun
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p. 37773 - 37778
(2014/11/07)
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- Copper-catalyzed decarboxylative C≡N triple bond formation: Direct synthesis of benzonitriles from phenylacetic acids under O2 atmosphere
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A copper-catalyzed reaction of phenylacetic acids with urea was found to afford benzonitriles under an oxygen atmosphere. This reaction proceeds smoothly by a sequence of decarboxylation, dioxygen activation, C-H bond functionalization, and nitrile formation with urea as the nitrogen source. Molecular oxygen was found to play a crucial role in this transformation. This reaction represents a novel protocol for the formation of benzonitriles in an environmental friendly way and with good functional group tolerability.
- Feng, Qiang,Song, Qiuling
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supporting information
p. 1697 - 1702
(2014/06/09)
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- Heterogeneous catalytic method for the conversion of aldoximes into nitriles using molecular sieve modified with Copper(II)
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A simple heterogeneous metal-catalyzed method was developed for the transformation of aldoximes into nitriles. Molecular sieve (4 A) modified with copper(II) proved to be an efficient catalyst for the conversion. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.
- Kiss, Arpad,Hell, Zoltan
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supporting information
p. 1778 - 1786
(2013/05/22)
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- Ruthenium-catalyzed one-pot synthesis of primary amides from aldehydes in water
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The readily available arene-ruthenium(ii) complex [RuCl2(η 6-C6Me6){P(NMe2)3}] (5 mol%) proved to be an efficient catalyst for the direct synthesis of primary amides from aldehydes and hydroxylamine hydrochloride (NH2OH· HCl) in water at 100 °C. The process, which requires the presence of NaHCO3 to catch the HCl released during the formation of the key aldoxime intermediates, was operative with both aromatic, heteroaromatic, α,β-unsaturated and aliphatic aldehydes, and tolerated several functional groups. A greener approach using commercially available NH 2OH solution (50 wt.% in water) is also presented.
- Garcia-Alvarez, Rocio,Diaz-Alvarez, Alba E.,Crochet, Pascale,Cadierno, Victorio
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p. 5889 - 5894
(2013/05/09)
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- Synthesis of functionalized aryl fluorides using organolithium reagents in flow microreactors
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Flow on: Flow microreactors enable the generation of aryl lithium compounds and subsequent electrophilic fluorination with NFSI and N-fluorosultam. The reaction can be successfully accomplished to synthesize various aryl fluorides involving an electron-withdrawing, an electron-donating, and a sterically hindered functional group in good yields. Copyright
- Nagaki, Aiichiro,Uesugi, Yuki,Kim, Heejin,Yoshida, Jun-Ichi
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supporting information
p. 705 - 708
(2013/05/08)
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- Schmidt reaction in ionic liquids: Highly efficient and selective conversion of aromatic and heteroaromatic aldehydes to nitriles with [BMIM(SO3H)][OTf] as catalyst and [BMIM][PF6] as solvent
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A mild and selective method is presented for the conversion of aromatic and heteroaromatic aldehydes to nitriles via the Schmidt reaction with TMSN 3 by using [BMIM(SO3H)][OTf] as catalyst and [BMIM][PF6] as solvent. The method offers high yields and simple product isolation, and avoids the use of liquid superacids or corrosive Lewis acids commonly employed for this transformation. It also offers some potential for recycling/reuse of the IL solvent.
- Nandi, Ganesh C.,Laali, Kenneth K.
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p. 2177 - 2179
(2013/04/24)
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- Palladium(II)-catalyzed cyclization reaction of 2-(Alk-2'-ynyloxy) benzonitriles or 2-(Alk-2'-ynylamino)benzonitriles: A facile way to 2H-chromene and 1,2-dihydroquinoline derivatives
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An efficient synthesis of 2H-chromenes and 1,2-dihydroquinolines from palladium(II)-catalyzed tandem reactions of 2-(alk-2'-ynyloxy)benzonitriles or 2-(alk-2'-ynylamino)benzonitriles was developed. This tandem reaction involves an intermolecular trans-acetoxypalladation of an alkyne followed by an addition to the nitrile group to quench the carbon-palladium bond and complete the catalytic cycle without the necessity of a redox system.
- Xi, Guoqin,Han, Xiuling,Lu, Xiyan
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supporting information
p. 2701 - 2705,5
(2012/12/12)
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- Straightforward zinc-catalyzed transformation of aldehydes and hydroxylamine hydrochloride to nitriles
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In the present study, the zinc-catalyzed dehydration of a range of in situ generated aldoximes, available by the reaction of aldehydes and hydroxylamine hydrochloride, has been explored. After investigating various reaction parameters, with Zn(OTf)2 an excellent and easily accessible pre-catalyst was obtained. The system was highly active and dehydrated a broad range of aldoximes selectively to the corresponding nitriles under mild reaction conditions.
- Enthaler, Stephan,Weidauer, Maik,Schr?der, Fanny
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experimental part
p. 882 - 885
(2012/03/26)
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- SUBSTITUTED NAPHTHYRIDINES AND THEIR USE AS SYK KINASE INHIBITORS
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The invention relates to new substituted naphthyridines of formula (1), as well as pharmacologically acceptable salts, diastereomers, enantiomers, racemates, hydrates or solvates thereof, wherein R1 is selected from among -O-R3 or -NR3R4, R3 is C1-6-alkyl which is substituted by R5 and R6 R5 is selected from hydrogen, branched or linear C1-6-alkyl, C2-6-alkenyl, -C1-6-alkylen-O-C1-3-alkyl, C1-3-haloalkyl, R6 is ring X wherein n is either 0 or 1, and Formula (I) is a either a single or a double bond and wherein A, B, D and E are each independently from one another selected from CH2, CH, C, N, NH, O or S and wherein ring X is attached to the molecule either via position A, B, D or E, wherein said ring X may optionally be further substituted by one, two or three residues each selected individually from the group consisting of -oxo, hydroxy, -C1-3-alkyl, -C1-3-haloalkyl, -O-C1-3-alkyl, -C1-3-alkanol and halogen, and wherein R4, R2, R7, R8, R9, R10, R11 and Q may have the meanings as given in claim 1, as well as pharmaceutical compositions containing these compounds.
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Page/Page column 45
(2011/08/21)
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- A mild and efficient method for nucleophilic aromatic fluorination using tetrabutylammonium fluoride as fluorinating reagent
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Anhydrous tetrabutylammonium fluoride (TBAFanh.) has been found to be a highly efficient fluorinating reagent for nucleophilic aromatic fluorinations such as fluorodenitration or halogen exchange (Halex) reaction. The products were formed in high to excellent yields under surprisingly mild reaction conditions and no phenol or ether side-products were detected in these reactions.
- Hu, Yu Feng,Luo, Jun,Lü, Chun Xu
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experimental part
p. 151 - 154
(2010/11/18)
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