- Nitrile Synthesis via Desulfonylative-Smiles Rearrangement
-
Herein, we designed a simple nitrile synthesis from N-[(2-nitrophenyl)sulfonyl]benzamides via base-promoted intramolecular nucleophilic aromatic substitution. The process features redox-neutral conditions as well as no requirement of toxic cyanide species and transition metals. Our process shows broad scope and various functional group compatibility, affording a variety of (hetero)aromatic nitriles in good to excellent yields.
- Abe, Masahiro,Nitta, Sayasa,Miura, Erina,Kimachi, Tetsutaro,Inamoto, Kiyofumi
-
p. 4460 - 4467
(2022/03/15)
-
- Oxalohydrazide Ligands for Copper-Catalyzed C?O Coupling Reactions with High Turnover Numbers
-
Here, we report a class of ligands based on oxalohydrazide cores and N-amino pyrrole and N-amino indole units that generates long-lived copper catalysts for couplings that form the C?O bonds in biaryl ethers. These Cu-catalyzed coupling of phenols with aryl bromides occurred with turnovers up to 8000, a value which is nearly two orders of magnitude higher than those of prior couplings to form biaryl ethers and nearly an order of magnitude higher than those of any prior copper-catalyzed coupling of aryl bromides and chlorides. This ligand also led to copper systems that catalyze the coupling of aryl chlorides with phenols and the coupling of aryl bromides and iodides with primary benzylic and aliphatic alcohols. A wide variety of functional groups including nitriles, halides, ethers, ketones, amines, esters, amides, vinylarenes, alcohols and boronic acid esters were tolerated, and reactions occurred with aryl bromides in pharmaceutically related structures.
- Ray, Ritwika,Hartwig, John F.
-
supporting information
p. 8203 - 8211
(2021/03/08)
-
- 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)
-
- CuO-catalyzed conversion of arylacetic acids into aromatic nitriles with K4Fe(CN)6 as the nitrogen source
-
Readily available CuO was demonstrated to be effective as the catalyst for the conversion of arylacetic acids to aromatic nitriles with non-toxic and inexpensive K4Fe(CN)6 as the nitrogen source via the complete cleavage of the C[tbnd]N triple bond. The present method allowed a series of arylacetic acids including phenylacetic acids, naphthaleneacetic acids, 2-thiopheneacetic acid and 2-furanacetic acid to be converted into the targeted products in low to high yields.
- Ren, Yun-Lai,Shen, Zhenpeng,Tian, Xinzhe,Xing, Ai-Ping,Zhao, Zhe
-
-
- Selective oxidation of alcohols to nitriles with high-efficient Co-[Bmim]Br/C catalyst system
-
An efficient method for catalyzing the ammoxidation of aromatic alcohols to aromatic nitriles was developed, in which a new heterogeneous catalyst based on transition metal elements was employed, the new catalyst was named Co-[Bmim]Br/C-700 and then characterized by X-ray photo-electronic spectroscopy, transmission electron microscope and X-ray diffraction. The reaction was carried out by two consecutive dehydrogenations under the catalysis of Co-[Bmim]Br/C-700, which catalytically oxidized the alcohol to the aldehyde, and then the aldehyde was subjected to ammoxidation to the nitrile. The catalyst system was suitable for a wide range of substrates and nitriles obtained in high yields, especially, the conversion rate of benzyl alcohol, 4-methoxybenzyl alcohol, 4-chlorobenzyl alcohol and 4-nitrobenzyl alcohol reached 100%. The substitution of ammonia and oxygen for toxic cyanide to participate in the reaction accords with the theory of green chemistry.
- Xia, Yu-Yan,Lv, Qing-Yang,Yuan, Hua,Wang, Jia-Yi
-
p. 3957 - 3964
(2021/04/09)
-
- Preparation method of nitrile compound
-
The present invention belongs to the field of organic synthesis technology, specifically relates to a method for preparing a nitrile compound, aldehyde oxime derivatives as raw materials, adding DPPA and DBU, reacting in an organic solvent, one step to pr
- -
-
Paragraph 0054-0056
(2022/01/08)
-
- Photocatalytic Reductive C-O Bond Cleavage of Alkyl Aryl Ethers by Using Carbazole Catalysts with Cesium Carbonate
-
Methods to activate the relatively stable ether C-O bonds and convert them to other functional groups are desirable. One-electron reduction of ethers is a potentially promising route to cleave the C-O bond. However, owing to the highly negative redox potential of alkyl aryl ethers (Ered -2.6 V vs SCE), this mode of ether C-O bond activation is challenging. Herein, we report the visible-light-induced photocatalytic cleavage of the alkyl aryl ether C-O bond using a carbazole-based organic photocatalyst (PC). Both benzylic and non-benzylic aryl ethers underwent C-O bond cleavage to form the corresponding phenol products. Addition of Cs2CO3 was beneficial, especially in reactions using a N-H carbazole PC. The reaction was proposed to occur via single-electron transfer (SET) from the excited-state carbazole to the substrate ether. Interaction of the N-H carbazole PC with Cs2CO3 via hydrogen bonding exists, which enables a deprotonation-assisted electron-transfer mechanism to operate. In addition, the Lewis acidic Cs cation interacts with the substrate alkyl aryl ether to activate it as an electron acceptor. The high reducing ability of the carbazole combined with the beneficial effects of Cs2CO3 made this otherwise formidable SET event possible.
- Yabuta, Tatsushi,Hayashi, Masahiko,Matsubara, Ryosuke
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p. 2545 - 2555
(2021/02/01)
-
- EIF4E INHIBITORS AND USES THEREOF
-
The present invention provides compounds inhibiting elF4E activity and compositions and methods of using thereof.
- -
-
Paragraph 00337; 00358
(2021/09/11)
-
- Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C-CN Bond Cleavage and Cyano Transfer
-
We report nickel-catalyzed cyanation and hydrocyanation methods to prepare aryl nitriles and vinyl nitriles from aryl halides and alkynes, respectively. Using inexpensive and nontoxic 4-cyanopyridine N-oxide as the cyano shuttle, the methods provide an efficient approach to prepare aryl cyanides and vinyl nitriles under mild and operationally simple reaction conditions with a broad range of functional group tolerances. In hydrocyanation of alkynes, the method demonstrated good regioselectivity, producing predominantly E- or Z-alkenyl nitriles in a controlled manner and exclusively Markovnikov vinyl nitriles when internal diaryl alkynes and terminal alkynes were applied as the substrates, respectively. The preliminary mechanistic investigation indicated that the C-CN bond cleavage process is promoted by oxidative addition to the nickel(I) complex in the cyanation of aryl halides, and further studies via a series of deuterium exchange experiments indicated that water serves as the hydrogen source for the hydrocyanation of alkynes.
- Chen, Hui,Sun, Shuhao,Liu, Yahu A.,Liao, Xuebin
-
p. 1397 - 1405
(2020/02/04)
-
- Method for converting aromatic aldehyde into aromatic nitrile by using sulfur powder promoted inorganic ammonium as nitrogen source (by machine translation)
-
The invention discloses a method for converting aromatic aldehyde into aromatic nitrile. The method is conversion of high yield of aromatic aldehyde one-pot reaction of sulfur powder promoted inorganic ammonium as a nitrogen source into aromatic nitrile. The method has the advantages of no need of metal participation, no need of strong oxide, compatibility of reaction to air, easiness in amplification to a gram scale and the like, and overcomes the problems of harsh reaction conditions, complex operation, low functional group compatibility and the like in the prior art. (by machine translation)
- -
-
Paragraph 0050; 0051
(2020/09/12)
-
- ANALOGUES OF PENTAMIDINE AND USES THEREFOR
-
The present disclosure provides a group of aromatic (e.g., pyridinyl, pyrimidinyl, pyrazinyl, or phenyl) diamidine analogs and pharmaceutically acceptable salts that are useful for treating a proliferative disease. The proliferative disease may include solid cancer or blood cancer. Compositions, methods of synthesizing the same and methods for treating various cancer using the analogs are disclosed herein. The present disclosure also provides pharmaceutical formulations comprising at least one of the compounds with a pharmaceutically acceptable carrier, diluent or excipient therefor.
- -
-
Paragraph 0239
(2020/07/14)
-
- Difluorocarbene-Based Cyanation of Aryl Iodides
-
A large number of efficient cyanation methods have been developed because of the wide range of applications of nitriles, but conventional methods usually suffer from the need for a toxic cyanation reagent. Although difluorocarbene chemistry has received increasing attention, the use of difluorocarbene as a sources of the nitrile carbon for nitrile groups remains largely unexplored. We describe a difluorocarbene-based cyanation of aryl iodides promoted by a cheap copper source, Cu(NO 3) 2 ·2.5H 2 O, under an air atmosphere. Ph 3 P + CF 2 CO 2-, an easily available and shelf-stable difluorocarbene reagent, and NaNH 2 are used as the carbon source and the nitrogen source for the nitrile group, respectively. The cyanation protocol is attractive because no toxic reagent is used and performing the reactions under an air atmosphere is operationally convenient.
- Cao, Yu-Cai,Du, Ruo-Bing,Fu, Zhi-Hong,Guo, Yu,Lin, Jin-Hong,Xiao, Ji-Chang,Xiao, Xuan,Yao, Xu,Zhang, Yin-Xiang,Zheng, Xing
-
supporting information
p. 713 - 717
(2020/04/08)
-
- Atomically Dispersed Ru on Manganese Oxide Catalyst Boosts Oxidative Cyanation
-
There is a strong incentive for environmentally benign and sustainable production of organic nitriles to avoid the use of toxic cyanides. Here we report that manganese oxide nanorod-supported single-site Ru catalysts are active, selective, and stable for oxidative cyanation of various alcohols to give the corresponding nitriles with molecular oxygen and ammonia as the reactants. The very low amount of Ru (0.1 wt %) with atomic dispersion boosts the catalytic performance of manganese oxides. Experimental and theoretical results show how the Ru sites enhance the ammonia resistance of the catalyst, bolstering its performance in alcohol dehydrogenation and oxygen activation, the key steps in the oxidative cyanation. This investigation demonstrates the high efficiency of a single-site Ru catalyst for nitrile production.
- Gates, Bruce C.,Guan, Erjia,Meng, Xiangju,Wang, Chengtao,Wang, Hai,Wang, Liang,Wang, Sai,Xiao, Feng-Shou,Xu, Dongyang,Xu, Hua,Yang, Bo,Zhang, Jian
-
p. 6299 - 6308
(2020/07/21)
-
- Choline Hydroxide as a Versatile Medium for Catalyst-Free O-Functionalization of Phenols
-
A versatile synthetic protocol for benzyl phenyl ether preparation via O-alkylation of phenolic oxygen with readily available benzyl derivatives was demonstrated. The newly designed procedure was carried out using an eco-friendly medium, room-temperature ionic liquid (choline hydroxide), under metal- and base-catalyst-free aerobic conditions. The reaction platform was also successfully applied to phenol protection strategy.
- Joo, Seong-Ryu,Kim, Seung-Hoi,Kwon, Gyu-Tae,Park, Soo-Youl
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p. 1200 - 1205
(2020/11/30)
-
- SSAO INHIBITOR
-
The present invention provides an SSAO inhibitor and an application thereof in preparing a drug for treating a disease related to SSAO. In particular, the present invention provides a compound shown in formula (IV) and a pharmaceutically acceptable salt thereof.
- -
-
Paragraph 0150-0152
(2020/04/02)
-
- Practical heterogeneous photoredox/nickel dual catalysis for C-N and C-O coupling reactions
-
Efficient C-N and C-O coupling reactions of aryl halides with amines and alcohols have been developed by using the strategy of heterogeneous visible light photoredox and nickel dual catalysis. Obviously, the joint use of inexpensive and bench-stable CdS and nickel salts, together with mild reaction conditions, makes these two transformations attractive for the synthetic community. This heterogeneous dual catalysis system also proved to be successful in the ligand-free catalytic hydroxylation of aryl bromide with water as a nucleophile. The practicality of this protocol is further emphasized by the scaled-up reaction and the reusability of heterogeneous photocatalysts.
- Liu, Yi-Yin,Liang, Dong,Lu, Liang-Qiu,Xiao, Wen-Jing
-
supporting information
p. 4853 - 4856
(2019/05/02)
-
- Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
-
A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.
- Fang, Wan-Yin,Qin, Hua-Li
-
p. 5803 - 5812
(2019/05/14)
-
- SO 2 F 2 -Promoted Dehydration of Aldoximes: A Rapid and Simple Access to Nitriles
-
A rapid, simple and mild process for the dehydration of aldoximes to give the corresponding nitriles, which utilizes SO 2 F 2 as an efficient reagent, has been developed. A variety of (hetero)arene, alkene, alkyne and aliphatic aldoximes proceeded with high efficiency to afford nitriles in excellent to quantitative yields with great functional group compatibilities in acetonitrile under ambient conditions. Furthermore, an eco-friendly synthetic protocol to access nitriles from aldehydes with ortho -, meta - and para -nitrile groups was also described in aqueous methanol by using inorganic base Na 2 CO 3, and a one-pot synthetic strategy to generate nitriles from aldehydes was proved to be feasible.
- Ding, Chengrong,Mei, Guangyao,Wang, Haibo,Zhang, Guofu,Zhao, Yiyong
-
p. 1484 - 1488
(2019/07/15)
-
- Nickel-Catalyzed Decarbonylative Cyanation of Acyl Chlorides
-
Ni-catalyzed decarbonylative cyanation of acyl chlorides with trimethylsilyl cyanide has been achieved. This transformation is applicable to the synthesis of an array of nitrile compounds bearing a wide range of functional groups under neutral conditions. The step-by-step experimental studies revealed that the reaction sequences of the present catalytic reaction are oxidative addition, transmetalation, decarbonylation, and reductive elimination.
- Wang, Zhenhua,Wang, Xiu,Ura, Yasuyuki,Nishihara, Yasushi
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p. 6779 - 6784
(2019/08/26)
-
- Ambident Reactivity of Phenolate Anions Revisited: A Quantitative Approach to Phenolate Reactivities
-
Prompted by the observation that the regioselectivities of phenolate reactions (C versus O attack) are opposite to the predictions by the principle of hard and soft acids and bases, we performed a comprehensive experimental and computational investigation of phenolate reactivities. Rate and equilibrium constants for the reactions of various phenolate ions with benzhydrylium ions (Aryl2CH+) and structurally related quinone methides have been determined photometrically in polar aprotic solvents. Quantum chemical calculations at the SMD(MeCN)/M06-2X/6-31+G(d,p) level confirmed that O attack is generally favored under kinetically controlled conditions, whereas C attack is favored under thermodynamically controlled conditions. Exceptions are diffusion-limited reactions with strong electrophiles, which give mixtures of products arising from O and C attack, as well as reactions with metal alkoxides in nonpolar solvents, where oxygen attack is blocked by strong ion pairing. The Lewis basicity (LB) and nucleophilicity (N, sN) parameters of phenolates determined in this work can be used to predict whether their reactions with electrophiles are kinetically or thermodynamically controlled and whether the rates are activation- or diffusion-limited. Comparison of the measured rate constants for the reactions of phenolates with carbocations with the Gibbs energies for single-electron transfer manifests that these reactions proceed via polar mechanisms.
- Mayer, Robert J.,Breugst, Martin,Hampel, Nathalie,Ofial, Armin R.,Mayr, Herbert
-
p. 8837 - 8858
(2019/07/08)
-
- Phosphazene Base tBu-P4 Catalyzed Methoxy–Alkoxy Exchange Reaction on (Hetero)Arenes
-
The organic superbase tBu-P4 catalyzes methoxy-alkoxy exchange reactions on (hetero)arenes with alcohols. The catalytic reaction proceeded efficiently with electron-deficient methoxy(hetero)arenes as well as with a variety of alcohols, including 3-amino-1-propanol, β-citronellol, menthol, and cholesterol. An intramolecular version of this reaction furnished six- and seven-membered ring compounds.
- Shigeno, Masanori,Hayashi, Kazutoshi,Nozawa-Kumada, Kanako,Kondo, Yoshinori
-
supporting information
p. 6077 - 6081
(2019/03/26)
-
- Nickel-catalyzed cyanation of aryl halides and triflates using acetonitrile: Via C-CN bond cleavage assisted by 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine
-
We developed a non-toxic cyanation reaction of various aryl halides and triflates in acetonitrile using a catalyst system of [Ni(MeCN)6](BF4)2, 1,10-phenanthroline, and 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine (Si-Me4-DHP). Si-Me4-DHP was found to function as a reductant for generating nickel(0) species and a silylation reagent to achieve the catalytic cyanation via C-CN bond cleavage.
- Ueda, Yohei,Tsujimoto, Nagataka,Yurino, Taiga,Tsurugi, Hayato,Mashima, Kazushi
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p. 994 - 999
(2019/02/03)
-
- Oxidative cyanide-free cyanation on arylboronic acid derivatives using aryl/heteroaryl thiocyanate using novel IL-PdCl4 catalyst under mild condition
-
An efficient and simple method is reported for the cyanation on arylboronic acid using various simple/indole thiocyanates using a new IL-PdCl4 catalyst. The cascade process involves a coupling reaction without any additive to give a wide range of cyanide derivatives. Cyanation on various arylboronic acids underwent smoothly affording the corresponding arylnitriles in good to high yields.
- Vaghasiya, Beena K.,Satasia, Shailesh P.,Thummar, Rahul P.,Kamani, Ronak D.,Avalani, Jemin R.,Sapariya, Nirav H.,Raval, Dipak K.
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p. 507 - 515
(2018/05/15)
-
- From Anilines to Aryl Ethers: A Facile, Efficient, and Versatile Synthetic Method Employing Mild Conditions
-
We have developed a simple and direct method for the synthesis of aryl ethers by reacting alcohols/phenols (ROH) with aryl ammonium salts (ArNMe3+), which are readily prepared from anilines (ArNR′2, R′=H or Me). This reaction proceeds smoothly and rapidly (within a few hours) at room temperature in the presence of a commercially available base, such as KOtBu or KHMDS, and has a broad substrate scope with respect to both ROH and ArNR′2. It is scalable and compatible with a wide range of functional groups.
- Wang, Dong-Yu,Yang, Ze-Kun,Wang, Chao,Zhang, Ao,Uchiyama, Masanobu
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p. 3641 - 3645
(2018/03/13)
-
- NH3?H2O: The Simplest Nitrogen-Containing Ligand for Selective Aerobic Alcohol Oxidation to Aldehydes or Nitriles in Neat Water
-
Aqueous ammonia (NH3?H2O) has been shown to serve as the simplest nitrogen-containing ligand to effectively promote copper-catalyzed selective alcohol oxidation under air in water. A series of alcohols with varying electronic and steric properties were selectively oxidized to aldehydes with up to 95 % yield. Notably, by increasing the amount of aqueous ammonia in neat water, the exclusive formation of aryl nitriles was also accomplished with good-to-excellent yields. Additionally, the catalytic system exhibits a high level of functional group tolerance with ?OH, ?NO2, esters, and heteroaryl groups all being amenable to the reaction conditions. This one-pot and green oxidation protocol provides an important synthetic route for the selective preparation of either aldehydes or nitriles from commercially available alcohols.
- Zhang, Guofu,Ma, Danting,Zhao, Yiyong,Zhang, Guihua,Mei, Guangyao,Lyu, Jinghui,Ding, Chengrong,Shan, Shang
-
p. 885 - 889
(2018/12/10)
-
- Challenging clinically unresponsive medullary thyroid cancer: Discovery and pharmacological activity of novel RET inhibitors
-
It is now known that “gain of function” mutations of RET (REarranged during Transfection) kinase are specific and key oncogenic events in the onset of thyroid gland cancers such as the Medullary Thyroid Carcinoma (MTC). Although a number of RET inhibitors exist and are capable of inhibiting RET variants, in which mutations are outside the enzyme active site, the majority becomes dramatically ineffective when mutations are within the protein active site (V804L and V804M). Pursuing a receptor-based virtual screening against the kinase domain of RET, we found that compound 5 is able to inhibit efficiently both wild type and V804L mutant RET. Compound 5 was able to significantly reduce proliferation of both commercially available TT cell lines and surgical thyroid tissues obtained from patients with MTC and displayed a suitable drug-like profile, thus standing out as a promising candidate for further development towards the treatment of clinically unresponsive MTC.
- La Pietra, Valeria,Sartini, Stefania,Botta, Lorenzo,Antonelli, Alessandro,Ferrari, Silvia Martina,Fallahi, Poupak,Moriconi, Alessio,Coviello, Vito,Quattrini, Luca,Ke, Yi-Yu,Hsing-Pang, Hsieh,Da Settimo, Federico,Novellino, Ettore,La Motta, Concettina,Marinelli, Luciana
-
supporting information
p. 491 - 505
(2018/03/21)
-
- Synthesis and evaluation of biaryl derivatives for structural characterization of selective monoamine oxidase B inhibitors toward Parkinson's disease therapy
-
Benzyloxyphenyl moiety is a common structure of highly potent, selective and reversible inhibitors of monoamine oxidase B (MAO-B), safinamide and sembragiline. We synthesized 4-(benzyloxy)phenyl and biphenyl-4-yl derivatives including halogen substituents on the terminal aryl unit. In addition, we modified the carbon linker between amine group and the biaryl linked unit. Among synthesized compounds, 12c exhibited the most potent and selective MAO-B inhibitory effect (hMAO-B IC50: 8.9 nM; >10,000-fold selectivity over MAO-A) as a competitive inhibitor. In addition, 12c showed greater MAO-B inhibitory activity and selectivity compared to well-known MAO-B inhibitors such as selegiline, safinamide and sembragiline. In the MPTP-induced mouse model of Parkinson's disease (PD), 12c significantly protected the tyrosine hydroxylase (TH)-immunopositive DAergic neurons and attenuated the PD-associated behavioral deficits. This study suggests characteristic structures as a MAO-B inhibitor that may provide a good insight for the development of therapeutic agents for PD.
- Yeon, Seul Ki,Choi, Ji Won,Park, Jong-Hyun,Lee, Ye Rim,Kim, Hyeon Jeong,Shin, Su Jeong,Jang, Bo Ko,Kim, Siwon,Bahn, Yong-Sun,Han, Gyoonhee,Lee, Yong Sup,Pae, Ae Nim,Park, Ki Duk
-
supporting information
p. 232 - 244
(2017/12/08)
-
- Direct C-H Cyanation of Arenes via Organic Photoredox Catalysis
-
Methods for the direct C-H functionalization of aromatic compounds are in demand for a variety of applications, including the synthesis of agrochemicals, pharmaceuticals, and materials. Herein, we disclose the construction of aromatic nitriles via direct C-H functionalization using an acridinium photoredox catalyst and trimethylsilyl cyanide under an aerobic atmosphere. The reaction proceeds at room temperature under mild conditions and has proven to be compatible with a variety of electron-donating and -withdrawing groups, halogens, and nitrogen- and oxygen-containing heterocycles, as well as aromatic-containing pharmaceutical agents.
- McManus, Joshua B.,Nicewicz, David A.
-
p. 2880 - 2883
(2017/03/11)
-
- A synthetic method of the compound aryl residue nitrile
-
The invention relates to a preparation method of a medicinal chemical engineering intermediate, and relates to a synthetic method of nitrile compounds. The nitrile compounds are an important part of many drugs and bioactive molecules, have important applications in the fields of organic synthesis and medicinal chemistry, and have a broad market prospect. The synthetic method of the nitrile compounds is characterized in that the nitrile compounds are synthesized from chloromethyl naphthalene and sodium azide in the presence of a ligand with acetone as a hydrogen acceptor. The method has the advantages of simple operation, easily obtained raw materials, mild reaction conditions, great use values, and great social and economic benefits.
- -
-
Paragraph 0054; 0055; 0056
(2017/08/25)
-
- A primary alcohol nitrile method (by machine translation)
-
The invention discloses a catalytic oxidation of primary alcohol nitrile method, said method comprising the following steps: formula (I) or formula (III) as shown in the primary alcohol as the raw material, in order to copper salt as catalyst, in order to air as the oxidizing agent, in order to TEMPO (2, 2, 6, 6 - tetramethyl piperidine nitrogen oxide) and help the oxidizing agent, ammonia as cocatalyst and solvent, for 80 - 120 °C reaction under 15 - 30h, after the reaction, the resulting reaction solution by the following formula (II) after treatment of the formula (IV) is shown in the nitriles; the reaction of the invention conversion, high yield, easy operation, low cost, safe reaction, the whole process is friendly to the environment, pollution-free. (by machine translation)
- -
-
Paragraph 0070; 0071; 0072; 0073; 0074
(2017/07/22)
-
- N-Heterocyclic carbene-mediated redox condensation of alcohols
-
N-Heterocyclic carbenes (NHCs) with a variety of oxidants promote the Mitsunobu-type coupling reactions of alcohols with phenols, carboxylic acids, and phthalimide. Experiments using a chiral alcohol indicate that these reactions proceed via SN1 or SN2 pathways depending on the polarity of the used solvents. The NHCs are consumed as reducing reagents to form their oxides as readily separable byproducts.
- Kato, Terumasa,Matsuoka, Shin-Ichi,Suzuki, Masato
-
supporting information
p. 8569 - 8572
(2016/07/13)
-
- Improved schmidt conversion of aldehydes to nitriles using azidotrimethylsilane in 1,1,1,3,3,3-Hexafluoro-2-Propanol
-
The Schmidt reaction of aromatic aldehydes using a substoichiometric amount (40 mol %) of triflic acid is described. Low catalyst loading was enabled by a strong hydrogen-bond-donating solvent hexafluoro-2-propanol (HFIP). This improved protocol tolerates a broad scope of aldehydes with diverse functional groups and the corresponding nitriles were obtained in good to high yields without the need for aqueous work up.
- Motiwala, Hashim F.,Yin, Qin,Aubé, Jeffrey
-
-
- Aerobic Copper-Promoted Radical-Type Cleavage of Coordinated Cyanide Anion: Nitrogen Transfer to Aldehydes to Form Nitriles
-
We have disclosed for the first time the copper-promoted C≡N triple bond cleavage of coordinated cyanide anion under a dioxygen atmosphere, which enables a nitrogen transfer to various aldehydes. Mechanistic study of this unprecedented transformation suggests that the single electron-transfer process could be involved in the overall course. This protocol provides a new cleavage pattern for the cyanide ion and would eventually lead to a more useful synthetic pathway to nitriles from aldehydes.
- Wu, Qian,Luo, Yi,Lei, Aiwen,You, Jingsong
-
supporting information
p. 2885 - 2888
(2016/03/19)
-
- Transnitrilation from Dimethylmalononitrile to Aryl Grignard and Lithium Reagents: A Practical Method for Aryl Nitrile Synthesis
-
An electrophilic cyanation of aryl Grignard or lithium reagents, generated in situ from the corresponding aryl bromides or iodides, by a transnitrilation with dimethylmalononitrile (DMMN) was developed. DMMN is a commercially available, bench-stable solid. The transnitrilation with DMMN avoids the use of toxic reagents and transition metals and occurs under mild reaction conditions, even for extremely sterically hindered substrates. The transnitrilation of aryllithium species generated by directed ortho-lithiation enabled a net C-H cyanation. The intermediacy of a Thorpe-type imine adduct in the reaction was supported by isolation of the corresponding ketone from the quenched reaction. Computational studies supported the energetic favorability of retro-Thorpe fragmentation of the imine adduct. (Chemical Equation Presented).
- Reeves, Jonathan T.,Malapit, Christian A.,Buono, Frederic G.,Sidhu, Kanwar P.,Marsini, Maurice A.,Sader, C. Avery,Fandrick, Keith R.,Busacca, Carl A.,Senanayake, Chris H.
-
supporting information
p. 9481 - 9488
(2015/08/11)
-
- Cu-Catalyzed Cyanation of Arylboronic Acids with Acetonitrile: A Dual Role of TEMPO
-
The cyanation of arylboronic acids by using acetonitrile as the "CN" source has been achieved under a Cu(cat.)/TEMPO system (TEMPO=2,2,6,6-tetramethylpiperidine N-oxide). The broad substrate scope includes a variety of electron-rich and electron-poor arylboronic acids, which react well to give the cyanated products in high to excellent yields. Mechanistic studies reveal that TEMPO-CH2CN, generated in situ, is an active cyanating reagent, and shows high reactivity for the formation of the CN- moiety. Moreover, TEMPO acts as a cheap oxidant to enable the reaction to be catalytic in copper. The cyanation of arylboronic acids by using acetonitrile as the "CN" source has been achieved under a Cu(cat.)/TEMPO system. Electron-rich and electron-poor arylboronic acids react well to give the cyanated products in high to excellent yields. Mechanistic studies reveal that TEMPO-CH2CN, generated in situ, is an active cyanating reagent. Moreover, TEMPO, a cheap oxidant, enables the reaction to be catalytic in copper (see scheme; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide).
- Zhu, Yamin,Li, Linyi,Shen, Zengming
-
supporting information
p. 13246 - 13252
(2015/09/15)
-
- An efficient transformation of primary halides into nitriles through palladium-catalyzed hydrogen transfer reaction
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Two-step one-pot transformation of primary halides into corresponding nitriles is successfully achieved. Nucleophilic substitution of primary halides with sodium azide and subsequent palladium-catalyzed hydrogen transfer proceeds smoothly in the presence of sterically bulky ligand dicyclohexyl(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine (XPhos) in acetone to produce nitriles in satisfactory to good yields. This journal is
- Zou, Tao,Yu, Xiaoqiang,Feng, Xiujuan,Bao, Ming
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supporting information
p. 10714 - 10717
(2015/06/30)
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- "Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles
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Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2O3)-based catalysts applying molecular oxygen.
- Jagadeesh, Rajenahally V.,Junge, Henrik,Beller, Matthias
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- Glucosylceramide synthase inhibitors
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The invention relates to inhibitors of glucosylceramide synthase (GCS) useful for the treatment metabolic diseases, such as lysosomal storage diseases, either alone or in combination with enzyme replacement therapy, and for the treatment of cancer.
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Page/Page column 94
(2015/09/28)
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- TRIAZINE COMPOUNDS AND COMPOSITIONS THEREOF AND METHODS FOR TREATING MALARIA AND CHEMOPROPHYLAXIS
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Disclosed herein are triazine compounds and methods of making and using thereof to treat malaria, provide chemoprophylaxis, and/or treat or inhibit infection by one or more Plasmodium spp.
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Paragraph 0104; 0105
(2014/10/15)
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- Catalytic cyanation of aryl iodides using DMF and ammonium bicarbonate as the combined source of cyanide: A dual role of copper catalysts
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Cu(ii)-catalyzed cyanation of aryl iodides has been developed using DMF and ammonium bicarbonate as the combined source of cyanide. It is assumed that copper is involved both in the generation of CN units from DMF-ammonia and in the cyanation of aryl halides. A range of electron-rich and fused (hetero)aryl iodides underwent cyanation resulting in moderate to good yields.
- Pawar, Amit B.,Chang, Sukbok
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supporting information
p. 448 - 450
(2014/01/06)
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- Tetrabutyl ammonium bromide-mediated benzylation of phenols in water under mild condition
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Benzylation of phenol was successfully achieved in water under room temperature mediated by tetrabutylammonium bromide (TBAB) for only 2 h affording the corresponding benzyl phenyl ether with good to excellent yields. This protocol is very efficient, simple, avoiding catalysts, easy to work-up after reaction, and especially 'green'.
- Wang, Hailei,Ma, Yuping,Tian, Heng,Yu, Ajuan,Chang, Junbiao,Wu, Yangjie
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p. 2669 - 2673
(2014/04/03)
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- Cu2O-mediated room temperature cyanation of aryl boronic acids/esters and TMSCN
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A method for the efficient and reliable synthesis of aryl nitriles via the Cu2O-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich and deficient, sterically very congested, and labile functionalities were tolerated. Moreover, the reaction can proceed under mild conditions at room temperature. These advantages paired with the use of cheap, readily available, and halogen-free Cu2O as catalysts make the protocol an appealing option for aryl cyanations. A method for the efficient and reliable synthesis of aryl nitriles via the Cu2O-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. The room temperature operation paired with the use of cheap, readily available, and halogen-free Cu2O as catalysts makes the protocol an appealing option for aryl cyanations. Copyright
- Ye, Yong,Wang, Yanhua,Liu, Pengtang,Han, Fushe
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supporting information
p. 27 - 30
(2013/08/24)
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- Copper-mediated transformation of organosilanes to nitriles with DMF and ammonium iodide
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Cyanation of aryl-, diaryldimethyl-, and styrylsilanes was developed for the first time under copper-mediated oxidative conditions using ammonium iodide and DMF as the combined source of nitrogen and carbon atom of the introduced cyano unit, respectively. The reaction was observed to proceed in a two-step process: initial conversion of organosilanes to their iodo intermediates and then cyanation. This method has a broad substrate scope with high functional group tolerance.
- Wang, Zhen,Chang, Sukbok
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supporting information
p. 1990 - 1993
(2013/06/04)
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- Copper- and silver-mediated cyanation of aryl iodides using ddq as cyanide source
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A new copper and silver-mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved, providing nitriles with good yields. This new approach represents a safe method leading to aryl nitriles. A new copper and silver-mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved.
- Zheng, Kui,Yu, Peng,Chen, Shuyou,Chen, Fen,Cheng, Jiang
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supporting information
p. 449 - 452
(2013/08/25)
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- Copper-catalyzed cyanation of aryl iodide with the combined cyanide source of urea and DMSO
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A simple copper-catalyzed cyanation of aryl iodide with the combination of urea and dimethyl sulfoxide as a cyanide source is achieved, providing nitriles in moderate to good yields. This new approach represents an exceedingly practical and safe method for the synthesis of aryl nitriles.
- Zheng, Kui,Liu, Bin,Chen, Shuyou,Chen, Fan
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supporting information
p. 5250 - 5252
(2013/09/02)
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- Silver-catalyzed nitrogenation of alkynes: A direct approach to nitriles through C≡C bond cleavage
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Three in one blow! A novel direct transformation of alkynes into nitriles by a silver-catalyzed nitrogenation reaction through C≡C bond cleavage has been developed. This research provides both a new application for alkynes in organic synthesis, and valuable mechanistic insights into nitrogenation chemistry. Copyright
- Shen, Tao,Wang, Teng,Qin, Chong,Jiao, Ning
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supporting information
p. 6677 - 6680
(2013/07/25)
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- Copper-catalyzed N- and O-alkylation of amines and phenols using alkylborane reagents
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By the reaction of amines with alkylborane reagents in the presence of a catalytic amount of copper(II) acetate Cu(OAc)2 and di-tert-butyl peroxide, a cross-coupling reaction proceeded and alkylated amines were obtained in good to excellent yields. Phenols are also applicable for this reaction, and the corresponding alkyl aryl ethers were produced.
- Sueki, Shunsuke,Kuninobu, Yoichiro
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supporting information
p. 1544 - 1547
(2013/06/26)
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- Palladium-catalyzed cyanation of aryl halides with CuSCN
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A palladium-catalyzed cyanation of aryl halides and borons has been developed by employing cuprous thiocyanate as a safe cyanide source. This protocol avoids the use of a highly toxic cyanide source, providing aromatic nitriles in moderate to good yields with good functional tolerance.
- Zhang, Guo-Ying,Yu, Jin-Tao,Hu, Mao-Lin,Cheng, Jiang
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p. 2710 - 2714
(2013/05/08)
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- Benzyloxybenzylammonium chlorides: Simple amine salts that display anticonvulsant activity
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Several antiepileptic drugs exert their activities by inhibiting Na + currents. Recent studies demonstrated that compounds containing a biaryl-linked motif (Ar-X-Ar′) modulate Na+ currents. We, and others, have reported that compound
- Lee, Hyosung,Gold, Alexander S.,Yang, Xiao-Fang,Khanna, Rajesh,Kohn, Harold
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supporting information
p. 7655 - 7662
(2014/01/06)
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- NiCl2·6H2O/NaBH4 in methanol: A mild and efficient strategy for chemoselective deallylation/debenzylation of aryl ethers
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Deprotection of allyl/benzyl aryl ethers was achieved chemoselectively. The mild and inexpensive reagent combination of NiCl2·6H 2O/NaBH4 in methanol afforded the products in high yields, within a reaction time of 5-10 min.
- Chouhan, Mangilal,Kumar, Kapil,Sharma, Ratnesh,Grover, Vikas,Nair, Vipin A.
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supporting information
p. 4540 - 4543
(2013/08/23)
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