cas 21382-98-9, 4-(METHYLTHIO)BENZONITRILE

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Diaryl-substituted (Dihydro)pyrrolo[3,2,1- hi ]indoles, a class of potent COX-2 inhibitors with tricyclic core structure
A new compound class of diaryl-substituted heterocycles with tricyclic dihydropyrrolo[3,2,1-hi]indole and pyrrolo[3,2,1-hi]indole core structures has been designed and was synthesized by a modular sequence of Friedel-Crafts acylation, amide formation, and
Laube, Markus,Gassner, Cemena,Sharma, Sai Kiran,Günther, Robert,Pigorsch, Arne,K?nig, Jonas,K?ckerling, Martin,Wuest, Frank,Pietzsch, Jens,Kniess, Torsten
p. 5611 - 5624
(2015)
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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)

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
supporting information
p. 3723 - 3728
(2021/04/07)

t-BuOK-promoted methylthiolation of aryl fluorides with dimethyldisulfide under transition-metal-free and mild conditions
In the presence of potassium tert-butoxide (t-BuOK), the cross-coupling reaction between aryl fluorides and dimethyldisulfide was developed. A series of aryl methyl sulfides were obtained in moderate to good yields under transition-metal-free and mild conditions.
Huang, Dayun,Wu, Xiangmei
(2021/03/24)

N-bromosuccinimide/HCl mediated reduction of sulfoxides to sulfides
An efficient reduction of sulfoxides to sulfides mediated by N-bromosuccinimide (NBS)/HCl system has been developed. This protocol shows good functional group compatibility as well as broad substrates scope with operational simplicity.
Wang, Jianqiang,Shi, Fangmin,Dai, Dongyan,Xiong, Liping,Yang, Yongpo
supporting information
p. 439 - 443
(2021/02/03)

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)
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Paragraph 0052; 0053

(2020/09/12)

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)

Palladium-catalyzed intermolecular transthioetherification of aryl halides with thioethers and thioesters
Functional group transfer reactions are an important synthetic tool in modern organic synthesis. Herein, we developed a new palladium-catalyzed intermolecular transthioetherification reaction of aryl halides with thioethers and thioesters. The synthetic utility and practicality of this catalytic protocol are demonstrated in a wide range of successful transformations (>70 examples). This catalytic protocol is applicable in carbonylative coupling processes as well, and the first example of carbonylative methylthioesterification of aryl halides has been achieved. Notably, this work also provides an approach to using natural products, such as methionine and selenomethionine, as the functional group sources.
Li, Yahui,Bao, Gao,Wu, Xiao-Feng
p. 2187 - 2192
(2020/03/11)

Copper-Catalyzed Methylthiolation of Aryl Iodides and Bromides with Dimethyl Disulfide in Water
An efficient route to aryl methyl sulfides through the copper-catalyzed coupling reaction of aryl iodides or bromides with dimethyl disulfide in water is described. Electron-donating and electron-withdrawing functional groups in the substrates were tolerated, and the corresponding products were obtained in moderate to good yields.
Wang, Ying-Yu,Wu, Xiang-Mei,Yang, Ming-Hua
supporting information

(2020/07/20)

An aerobic and green C-H cyanation of terminal alkynes
This study describes a benign C-H cyanation of terminal alkynes with α-cyanoesters serving as a nontoxic cyanide source. In situ generation of the key copper cyanide intermediate is proposed by a sequence of α-C-H oxidation and copper-mediated β-carbon elimination of α-cyanoesters, releasing the α-ketoester byproduct observed experimentally. The ensuing reaction of copper cyanide with terminal alkynes delivers preferentially cyanoalkynes and surpasses the possible Glaser type dimerization of terminal alkynes or the undesired accumulation of HCN under protic conditions. The presence of the co-oxidant K2S2O8 is crucial to this selectivity, probably by promoting oxidative transmetalation and the resulting formation of the Cu(iii)(acetylide)(CN) intermediate. All the reagents and salts used are commercially available, cheap and nontoxic, avoiding the use of highly toxic cyanide salts typically required in cyanation studies. The scope of this reaction is demonstrated with a set of alkynes and α-cyanoesters. The application of this method to late-stage functionalization of the terminal alkyne group in an estrone derivative is also feasible, showing its practical value for drug design.
Si, Yi-Xin,Zhang, Song-Lin,Zhu, Peng-Fei
supporting information
p. 9216 - 9220
(2020/12/03)

A convenient reagent for the conversion of aldoximes into nitriles and isonitriles
For the dehydroxylation of aldoximes with 4-nitro-1-((trifluoromethyl)sulfonyl)-imidazole (NTSI), slight modifications of reaction conditions resulted in significantly different reaction paths to provide either nitriles or isonitriles. The challenging conversion of aldoximes into isonitriles was achieved under mild conditions.
Zhang, Wei,Lin, Jin-Hong,Zhang, Pengfei,Xiao, Ji-Chang
supporting information
p. 6221 - 6224
(2020/06/29)

B2cat2-Mediated Reduction of Sulfoxides to Sulfides
An efficient and operationally simple method for the reduction of sulfoxides to sulfides has been developed using bis(catecholato)diboron (B2cat2) as a reducing agent. The present method accommodates various functional groups which are generally prone to reduction: halides, alkynes, carbonyls, nitriles, and heterocycles are totally intact, and only sulfoxide moieties undergo reduction chemoselectively. Moreover, the remaining diboron and the resulting boron-containing wastes are readily removable, the practicality of this protocol being thus demonstrated.
Takahashi, Fumiya,Nogi, Keisuke,Yorimitsu, Hideki
supporting information
p. 3009 - 3012
(2020/03/25)

Visible-light-driven catalytic oxidation of aldehydes and alcohols to nitriles by 4-acetamido-tempo using ammonium carbamate as a nitrogen source
A mild and efficient route to prepare nitriles from aldehydes by combining photoredox catalysis with oxoammonium cations is reported. The reaction is performed using ammonium carbamate as the nitrogen source. The practicality of the method is increased by the extension of the dual catalytic system to one-pot two-step conversion of alcohols to nitriles.
Nandi, Jyoti,Leadbeater, Nicholas E.
supporting information
p. 9182 - 9186
(2019/11/05)

A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
p. 3190 - 3194
(2019/05/21)

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)

Transition-Metal-Free Aryl-Heteroatom Bond Formation via C-S Bond Cleavage
Aryl-heteroatom bonds (C-Het) are almost ubiquitously present in chemical molecules. However, methods for diverse C-Het bond formations from a simple substrate are limited. Herein, we report a convenient and efficient C-S bond transformation of aryl sulfoniums to various C-Het bonds (C-O, C-S, C-Sn, C-Si, C-Se) in the absence of any transition-metal catalyst. These reactions proceeded in mild conditions with a wide substrate scope.
Zhao, Jian-Nan,Kayumov, Muzaffar,Wang, Dong-Yu,Zhang, Ao
supporting information
p. 7303 - 7306
(2019/10/02)

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
p. 6779 - 6784
(2019/08/26)

Visible light-promoted formation of C-B and C-S bonds under metal- A nd photocatalyst-free conditions
A green, efficient, photoinduced synthesis of arylboronic esters and aryl sulfides has been developed. Bench stable arylazo sulfones were used as radical precursors for a photocatalyst- A nd additive-free carbon-heteroatom bond formation under visible light. The protocols are applicable to a wide range of substrates, providing products in good yields.
Blank, Lena,Fagnoni, Maurizio,Protti, Stefano,Rueping, Magnus
p. 1243 - 1252
(2019/02/26)

A Manganese N-Heterocyclic Carbene Catalyst for Reduction of Sulfoxides with Silanes
The first reduction of sulfoxides catalysed by a well-defined manganese complex is described. A variety of sulfoxides are reduced to the corresponding sulfides in high yields using phenylsilane, diphenylsilane, and the economically feasible 1,1,3,3-tetramethyldisiloxane (TMDS) as reducing agents in the presence of a Mn-NHC complex. The reaction is performed under air and without the need of any additive. The involvement of radicals in the catalytic reaction is probed by spin-trap experiments.
Sousa, Sara C. A.,Carrasco, Carlos J.,Pinto, Mara F.,Royo, Beatriz
p. 3839 - 3843
(2019/06/24)

Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides
The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O2 or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.
Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Sharif, Muhammad,Kalevaru, Narayana V.,Jagadeesh, Rajenahally V.
supporting information
p. 266 - 273
(2018/01/12)

Cesium carbonate-promoted synthesis of aryl methyl sulfides using: S -methylisothiourea sulfate under transition-metal-free conditions
In the presence of cesium carbonate, an efficient synthesis of aryl methyl sulfides by the reactions of aryl halides with commercially available S-methylisothiourea sulfate is developed. This odourless and highly crystalline solid can be used as the subst
Zhang, Caiyang,Zhou, You,Huang, Jintao,Tu, Canhui,Zhou, Xiaoai,Yin, Guodong
p. 6316 - 6321
(2018/09/10)

Nucleophilic Amination and Etherification of Aryl Alkyl Thioethers
A transition-metal-free protocol capable of synthesizing diarylated aniline derivatives is reported. This method could be further employed to prepare aryl alkyl ethers. A wide range of thioethers, anilines, as well as alcohols were tolerated thanks to the mild reaction conditions. The strength of our method was demonstrated by performing a gram-scale reaction (20 mmol) followed by conversion of the nitrile group into synthetically useful aldehyde, ketone, and carboxylic acid.
Wang, Xia,Tang, Yue,Long, Cheng-Yu,Dong, Wen-Ke,Li, Chenchen,Xu, Xinhua,Zhao, Wanxiang,Wang, Xue-Qiang
supporting information
p. 4749 - 4753
(2018/08/23)

Chemoenzymatic Deracemization of Chiral Sulfoxides
The highly enantioselective enzyme methionine sulfoxide reductase A was combined with an oxaziridine-type oxidant in a biphasic setup for the deracemization of chiral sulfoxides. Remarkably, high ee values were observed with a wide range of substrates, thus providing a practical route for the synthesis of enantiomerically pure sulfoxides.
Nosek, Vladimír,Mí?ek, Ji?í
supporting information
p. 9849 - 9852
(2018/07/31)

Nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine
A nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine (TCT) using aminoacetonitrile as the cyanating agent is described. This catalytic system delivered the desired products in moderate to good yields with good substrate compatibility. The readily available starting materials, cost-effective nickel catalyst and metal-free cyanating agent are the major features of the present method.
Wang, Liang,Wang, Yaoyao,Shen, Jun,Chen, Qun,He, Ming-Yang
supporting information
p. 4816 - 4820
(2018/07/13)

Corresponding amine nitrile and method of manufacturing thereof
The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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(2018/05/07)

A visible-light photocatalytic thiolation of aryl, heteroaryl and vinyl iodides
The general catalytic synthesis of aryl and vinyl thioethers from readily available halides remains a challenge. Herein we report a unified method for the thiolation of aryl and vinyl iodides with dialkyl disulfides using visible light photoredox catalysis. A range of thioether products bearing diverse functional groups can be accessed in high yield and with excellent chemoselectivity. We demonstrate the versatility of this method through the expedient synthesis of a family of thioether-rich natural products. A detailed investigation of the photocatalytic mechanism is presented from both steady-state and time-resolved luminescent quenching as well as transient absorption spectroscopy experiments.
Czyz,Weragoda,Monaghan,Connell,Brzozowski,Scully,Burton,Lupton,Polyzos
supporting information
p. 1543 - 1551
(2018/03/08)

Dichromatic Photocatalytic Substitutions of Aryl Halides with a Small Organic Dye
Photocatalytic bond activations are generally limited by the photon energy and the efficiency of energy and electron transfer processes. Direct two-photon processes provide sufficient energy but the ultra-short lifetimes of the excited states prohibit chemical reactions. The commercial dye 9,10-dicyanoanthracene enabled photocatalytic aromatic substitutions of non-activated aryl halides. This reaction operates under VIS-irradiation via sequential photonic, electronic, and photonic activation of the simple organic dye. The resultant highly reducing excited photocatalyst anion readily effected C?H, C?C, C?P, C?S, and C?B bond formations. Detailed synthetic, spectroscopic, and theoretical studies support a biphotonic catalytic mechanism.
Neumeier, Michael,Sampedro, Diego,Májek, Michal,de la Pe?a O'Shea, Víctor A.,Jacobi von Wangelin, Axel,Pérez-Ruiz, Raúl
supporting information
p. 105 - 108
(2017/12/04)

Palladium-Catalyzed Thiomethylation via a Three-Component Cross-Coupling Strategy
In this report, the combination of masked inorganic sulfur and dimethyl carbonate was designed to achieve thiomethylated cross coupling of aryl chlorides. Remarkably, this powerful strategy realized thiomethylation of nucleosides bearing unprotected ribose, chloride-containing pharmaceuticals with late-stage coupling, and herbicides possessing multiple heteroatoms and steric hindrance. Moreover, this protocol is practically amenable to multigram-scale synthesis with a lower catalysis loading and a higher yield.
Wang, Ming,Qiao, Zongjun,Zhao, Jiaoyan,Jiang, Xuefeng
supporting information
p. 6193 - 6197
(2018/09/25)

Practical CuCl/DABCO/4-HO-TEMPO-catalyzed oxidative synthesis of nitriles from alcohols with air as oxidant
A mild and efficient methodology for the direct oxidative synthesis of nitriles from easily available alcohols and aqueous ammonia by employing CuCl/DABCO/4-HO-TEMPO as the catalysts is described. This protocol uses the air as a green oxidant and aqueous ammonia as the nitrogen source at room temperature. A variety of aryl, heterocyclic and allylic alcohols are smoothly converted into the corresponding nitriles in good to excellent yields.
Hu, Yongke,Chen, Lei,Li, Bindong
supporting information
p. 464 - 466
(2017/11/13)

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)

HETEROGENEOUS COPPER-CATALYZED AEROBIC OXIDATIVE CONVERSION OF AROMATIC ALDEHYDES TO CORRESPONDING NITRILES
The present invention relates to a method of aerobic oxidative converting aromatic aldehyde to nitrile. More specifically, the present invention relates to a method of aerobic oxidative conversion of an aromatic aldehyde to nitrile using a heterogeneous copper catalyst, and optimization of reaction conditions applied thereto. The method can obtain nitrile at high yield with respect to various substrates by synthesizing nitrile, e.g., benzonitrile from aromatic aldehyde, e.g., benzaldehyde and an ammonia source, e.g., ammonia water under an oxygen condition by using TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) and a heterogeneous copper catalyst (Cu@C) obtained by pyrolyzing HKUST-1, i.e., a type of a metal-organic framework, and enables the heterogeneous copper catalyst to be reused at least three or more times without significant loss of catalytic activities since the heterogeneous copper catalyst maintains structure thereof even under the presence of the ammonia source.COPYRIGHT KIPO 2018
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Paragraph 0090-0110; 0134; 0135

(2018/07/31)

HETEROGENEOUS COPPER-CATALYZED AEROBIC OXIDATIVE CONVERSION OF ALCOHOLS TO CORRESPONDING NITRILES
The present invention refers to a method relates to knight reel aerobic oxidation conversion to alcohol (Aerobic oxidative conversion), metal - organic framework is provided electromagnetic wave is pyrolytically cracking using non-uniform copper catalyst (Cu ? C) and TEMPO HKUST-a 1, alcohol (e.g., benzyl alcohol) aromatic aldehyde (e.g., benzaldehyde) aromatic 1 difference after conversion into ammonia source (e.g., ammonia) manner won - port (One-a pot) aromatic aldehydes (e.g., benzo knight reel) added into knight reel by switching, high yield various substrate results in obtaining uniform copper catalyst in the presence of ammonia source knight reel and said holding structure even a significant catalyst activity may be reused without loss to at least 3 or more times, using alcohol knight reel aerobic to non-uniform copper catalyzed oxidative cycle, and applied to the optimization of the reaction conditions are disclosed. (by machine translation)
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Paragraph 0115-0124; 0155; 0181

(2018/10/03)

A practical iodine-catalyzed oxidative conversion of aldehydes to nitriles
A simple and efficient method for the direct synthesis of nitriles from aldehydes using ammonium acetate as the nitrogen source has been developed. The reactions were performed with iodine as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant under mild conditions. A variety of aromatic, heteroaromatic, aliphatic and allylic aldehydes could be converted into their corresponding nitriles in good to excellent yields.
Fang, Chaojie,Li, Meichao,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Jin, Liqun,Shen, Zhenlu
p. 1484 - 1489
(2017/01/21)

Catalytic and oxidizing synthetic method of nitriles compound
The invention discloses a catalytic and oxidizing synthetic method of a nitriles compound. The catalytic and oxidizing synthetic method comprises the following steps: adding reaction substrate aldehyde, NH4OAc, alkaline additives, I2 and TBHP (tert-butyl hydroperoxide) into an ethanol solvent, facilitating the reaction for 3 to 17 h at 40 to 60 DEG C, adding a sodium thiosulfate solution into a reaction solution, stirring, extracting with diethyl ether, separating to obtain an organic layer, decompressing and steaming to remove the solvent, performing the column chromatography isolation, adopting a mixed solution of ethyl acetate/petroleum ether in a volume ratio of 1: 100 as an eluent, collecting an elution solution containing a target compound, and steaming to remove the solvent, thus obtaining the product nitriles, wherein a weight ratio of the reaction substrate aldehyde to the alkaline additives to NH4OAc to I2 to TBHP is 100: (100 to 120): (120 to 160): (2 to 3): (100 to 120). The synthetic method has the beneficial effects that the operation is simple and safe, and the reaction condition is relatively moderate; and the reaction substrate is wide in application range.
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Paragraph 0046; 0047

(2017/07/23)

Oxoammonium salt-mediated oxidative nitriles synthesis from aldehydes with ammonium acetate
An efficient and scalable route for the synthesis of nitriles was developed by oxoammonium salt (4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) mediated oxidative conversion of aldehydes with NH4OAc. A variety of aliphatic aldehydes as well as benzaldehydes were converted into the corresponding nitriles in high yields. The nitroxyl radical which is the reduced species of the used oxoammonium salt was recovered by simple acid-base extraction for the recycling.
Kim, Myeong Jin,Mun, Junyoung,Kim, Jinho
supporting information
p. 4695 - 4698
(2017/11/17)

Cyanation of aromatic/vinylic boronic acids with α-cyanoacetates
A friendly protocol is reported to achieve cyanation of aromatic and vinylic boronic acids using nontoxic and readily available α-cyanoacetates as a cyano source under aerobic conditions. Many aryl/vinyl boronic acids (as well as some iodides and bromides) are amenable substrates to give aryl nitriles and acrylonitriles. This cyanation method provides a safe and operationally convenient alternative to traditional ones requiring toxic cyanide salts.
Wang, Xian-Jin,Zhang, Song-Lin
supporting information
p. 14826 - 14830
(2017/12/15)

Copper-catalyzed cyanation of aryl iodides using nitromethane
The copper-catalyzed cyanation of aryl iodides is described using nitromethane as a CN source. In situ generation of a “CN” species from nitromethane is plausible. This strategy is an advantageous synthetic method for the construction of an aromatic CCN bond, because nitromethane is a common and easily handled compound that is readily available as a cyanation reagent, and its use allows the avoidance of using toxic metal cyanides.
Ogiwara, Yohei,Morishita, Hiromitsu,Sasaki, Minoru,Imai, Hiroki,Sakai, Norio
supporting information
p. 1736 - 1739
(2017/11/23)

Methyl aryl thioether compound, and synthetic method and applications thereof
The invention discloses a methyl aryl thioether compound represented by formula 2, and a synthetic method and applications thereof. According to the synthetic method, in a reaction solvent, an aryl halide or an aromatic halide, dimethyl carbonate, and potassium thioacetate are taken as reaction raw materials, reaction is carried out in the presence of metal palladium catalyst under the action of a ligand and an alkali so as to obtain the methyl aryl thioether compound. The reaction conditions of the synthetic method are mild; the raw materials are cheap and easily available; reaction operation is simple; yield is relatively high. The methyl aryl thioether compound can be used for providing skeleton structures for the synthesis of a plurality of natural products and medicines, and can be widely applied in industrialized large-scale production.
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Paragraph 0083; 0084; 0085

(2017/07/21)

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)
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Paragraph 0065; 0066; 0067; 0068; 0069

(2017/07/22)

A Mild TEMPO-Catalyzed Aerobic Oxidative Conversion of Aldehydes into Nitriles
An efficient method to prepare nitriles from aldehydes using hexamethyldisilazane (HMDS) as the nitrogen source has been developed. The reactions were performed with 2,2,6,6-tetramethylpiperidine l-oxyl (TEMPO) as the catalyst, NaNO2 or TBN as the co-catalyst, and molecular oxygen as the terminal oxidant under mild conditions. A variety of aromatic, heteroaromatic, aliphatic and allylic aldehydes could be converted into their corresponding nitriles in good to excellent yields.
Fang, Chaojie,Li, Meichao,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Jin, Liqun,Shen, Zhenlu
p. 1157 - 1163
(2016/04/19)

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
(2016/02/05)

Homolytic Cleavage of a B-B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification
Density functional theory (DFT) investigations revealed that 4-cyanopyridine was capable of homolytically cleaving the B-B σ bond of diborane via the cooperative coordination to the two boron atoms of the diborane to generate pyridine boryl radicals. Our experimental verification provides supportive evidence for this new B-B activation mode. With this novel activation strategy, we have experimentally realized the catalytic reduction of azo-compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones with B2(pin)2 at mild conditions. Breaking good: The diborane B-B bond can be homolytically cleaved via the cooperative catalysis of two 4-cyanopyridine molecules. Using this combination of a diborane (B2(pin)2) and 4-cyanopyridine also allows the catalytic reduction of the N=N double bond of azo-compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones under mild conditions.
Wang, Guoqiang,Zhang, Honglin,Zhao, Jiyang,Li, Wei,Cao, Jia,Zhu, Chengjian,Li, Shuhua
supporting information
p. 5985 - 5989
(2016/05/19)

Half-Sandwich Guanidinate-Osmium(II) Complexes: Synthesis and Application in the Selective Dehydration of Aldoximes
The novel guanidinate-osmium(II) complexes [OsCl{κ2-(N,N′)-C(NR)(NiPr)NHiPr}(η6-p-cymene)] [R = Ph (3a), 4-C6H4F (3b), 4-C6H4Cl (3c), 4-C6H4CF3 (3d), 3-C6H4CF3 (3e), 3,5-C6H3(CF3)2 (3f), 4-C6H4CN (3g), 4-C6H4Me (3h), 3-C6H4Me (3i), 2-C6H4Me (3j), 4-C6H4tBu (3k), 2,6-C6H3iPr2 (3l), 2,4,6-C6H2Me3 (3m)] have been synthesized in high yields (70-88 %) by treatment of THF solutions of the dimeric precursor [{OsCl(μ-Cl)(η6-p-cymene)}2] (1) with 4 equivalents of the corresponding guanidine (iPrHN)2C=NR (2a-m) at room temperature. The easily separable guanidinium chloride salts [(iPrHN)2C(NHR)]Cl (4a-m) were also formed in these reactions. The structures of 3a, 3d, and 3h were unequivocally confirmed by X-ray diffraction methods. Complexes 3a-m proved to be active in the catalytic dehydration of aldoximes. The best results were obtained with [OsCl{κ2-(N,N′)-C(N-4-C6H4CF3)(NiPr)NHiPr}(η6-p-cymene)] (3d; 5 mol-%), which, in acetonitrile at 80C, was able to convert selectively a large variety of aromatic, heteroaromatic, α,β-unsaturated, and aliphatic aldoximes into the corresponding nitriles in high yields and short reaction times. Novel osmium(II)-guanidinate complexes of general composition [OsCl{κ2-(N,N′)-C(NR)(NiPr)NHiPr}(η6-p-cymene)] (R = Ar) have been synthesized and successfully employed as catalysts for the selective conversion of aldoximes into nitriles.
Francos, Javier,González-Liste, Pedro J.,Menéndez-Rodríguez, Lucía,Crochet, Pascale,Cadierno, Victorio,Borge, Javier,Anti?olo, Antonio,Fernández-Galán, Rafael,Carrillo-Hermosilla, Fernando
p. 393 - 402
(2016/02/03)

Synthesis of nitriles from amines using nanoscale Co3O4-based catalysts via sustainable aerobic oxidation
The selective oxidation of amines for the benign synthesis of nitriles under mild conditions is described. Key to success for this transformation is the application of reusable cobalt oxide-based nanocatalysts. The resulting nitriles constitute key precursors and central intermediates in organic synthesis.
Natte, Kishore,Jagadeesh, Rajenahally V.,Sharif, Muhammad,Neumann, Helfried,Beller, Matthias
supporting information
p. 3356 - 3359
(2016/04/09)

A practical and chemoselective Mo-catalysed sulfoxide reduction protocol using a 3-mercaptopropyl-functionalized silica gel (MPS)
A convenient sulfoxide deoxygenation procedure using a mercaptopropyl-functionalized silica gel as the reducing agent is described. This new protocol based on a heterogeneous reagent displays broad scope and tolerance to reducible functional groups and, from an experimental point of view, enhances previous methods by simplifying the isolation of the sulfide to a simple filtration.
García, Nuria,Fernández-Rodríguez, Manuel A.,García-García, Patricia,Pedrosa, María R.,Arnáiz, Francisco J.,Sanz, Roberto
p. 27083 - 27086
(2016/03/25)

Method for preparing nitrile by alcohol oxidation
The invention provides a method for preparing nitrile by alcohol oxidation. The method comprises the following steps: mixing substrate alcohol which is shown as formula (I), a catalyst, a cocatalyst TEMPO, a ligand, an alkaline matter, 25 weight percent to 28 weight percent of ammonium hydroxide and a solvent; reacting for 2 to 24 hours with stirring in an oxygen atmosphere at 25 to 100 DEG C, and performing aftertreatment on reaction liquid to obtain a product nitrile which is shown in a formula (II). The method provided by the invention is environment friendly, wide in substrate application range, high in yield and mild in reaction conditions, has the preparation scale from grams to over hundreds of grams, and also has relatively high practical application value.
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Paragraph 0043; 0052; 0053

(2017/01/23)

Cobalt-Catalyzed Electrophilic Cyanation of Arylzinc Halides with N-Cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS)
The cobalt-catalyzed cross-coupling of organozinc bromides with N-cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS) is described. The same cobalt catalyst, cobalt(II) bromide, was used for both the synthesis of the organozinc species and the cross-coupling reaction. However in this case, a catalytic amount of zinc dust is necessary in the second step to release the low-valent cobalt. Under these mild conditions, moderate to excellent yields of different benzonitriles were obtained.
Cai, Yingxiao,Qian, Xin,Rrat, Alice,Auffrant, Audrey,Gosmini, Corinne
supporting information
p. 3419 - 3423
(2016/01/25)

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)

Palladium(II) complexes with a phosphino-oxime ligand: Synthesis, structure and applications to the catalytic rearrangement and dehydration of aldoximes
The treatment of [PdCl2(COD)] (COD = 1,5-cyclooctadiene) with 1 and 2 equivalents of 2-(diphenylphosphino)benzaldehyde oxime in dichloromethane at room temperature led to the selective formation of [PdCl2{κ2-(P,N)-2-Ph2PC6H4CHNOH}] (1) and [Pd{κ2-(P,N)-2-Ph2PC6H4CHNOH}2][Cl]2 (2), respectively, which represent the first examples of Pd(II) complexes containing a phosphino-oxime ligand. These compounds, whose structures were fully confirmed by X-ray diffraction methods, were active in the catalytic rearrangement of aldoximes. In particular, using 5 mol% complex 1, a large variety of aldoximes could be cleanly converted into the corresponding primary amides at 100 °C, employing water as solvent and without the assistance of any cocatalyst. Palladium nanoparticles are the active species in the rearrangement process. In addition, when the same reactions were performed employing acetonitrile as solvent, selective dehydration of the aldoximes to form the respective nitriles was observed. For comparative purposes, the catalytic behaviour of an oxime-derived palladacyclic complex has also been briefly evaluated.
Menéndez-Rodríguez, Lucía,Tomás-Mendivil, Eder,Francos, Javier,Nájera, Carmen,Crochet, Pascale,Cadierno, Victorio
p. 3754 - 3761
(2015/07/01)

"Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles
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
p. 92 - 96
(2015/02/19)