- Nitrile Synthesis via Desulfonylative-Smiles Rearrangement
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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
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p. 4460 - 4467
(2022/03/15)
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- Desulfurative Ni-Catalyzed Reductive Cross-Coupling of Benzyl Mercaptans/Mercaptoacetates with Aryl Halides
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The C-S activation and sulfur removal from native thiols is challenging, which limits their application as feedstock materials in organic synthesis despite their natural abundance. Herein, we introduce a per-/polyfluoroaryl moiety, which serves as a redox-active scaffold, into sp3-hybridized thiols to activate the C-S bond. Using a Ni catalyst with MgBr2 as an additive, the S group can be removed to yield an aliphatic radical that can react with an aryl halide in a reductive cross-coupling.
- Chan, Cheng-Lin,Hsu, Che-Ming,Lee, Shao-Chi,Li, Li-Yun,Liao, Hsuan-Hung,Mi?oza, Shinje,Tsai, Hao-En,Tsai, Zong-Nan,Tsao, Yong-Ting
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- Photo-Ni-Dual-Catalytic C(sp2)-C(sp3) Cross-Coupling Reactions with Mesoporous Graphitic Carbon Nitride as a Heterogeneous Organic Semiconductor Photocatalyst
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The synergistic combination of a heterogeneous organic semiconductor mesoporous graphitic carbon nitride (mpg-CN) and a homogeneous nickel catalyst with visible-light irradiation at room temperature affords the C(sp2)-C(sp3) cross-co
- Antonietti, Markus,Ghosh, Indrajit,K?nig, Burkhard,Khamrai, Jagadish,Savateev, Aleksandr
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p. 3526 - 3532
(2020/04/09)
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- Preparation method of o-amino diphenylmethane
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The invention relates to a preparation method of o-amino diphenylmethane, and belongs to the technical field of pharmaceutical synthesis. The preparation method comprises steps as follows: o-cyano-diphenylmethane is prepared from o-cyanobenzyl chloride and benzene through a reaction, then o-cyano-diphenylmethane is hydrolyzed in an aqueous solution of ethanediol, o-amide-diphenylmethane is obtained and is subjected to a rearrangement reaction with sodium hypochlorite, reduced-pressure distillation is performed, and o-amino diphenylmethane is obtained. O-amino diphenylmethane prepared with themethod is high in yield, the yield can reach 89% or above, meanwhile, a finished o-amino diphenylmethane product is high in purity, the purity can reach 99% or above, product quality is good, and defects of low purity and low yield of the product prepared with a traditional method are overcome. Besides, the preparation method is simple to operate and needs few steps, impurities in the product areeasy to separate and remove, and large-scale industrial production is facilitated.
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Paragraph 0017; 0028; 0030; 0034; 0036; 0040; 0042; 0046
(2019/09/17)
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- Cobalt-Catalyzed Formation of Functionalized Diarylmethanes from Benzylmesylates and Aryl Halides
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A simple cobalt-catalyzed reductive coupling protocol allowing the synthesis of functionalized diarylmethanes from benzyl mesylate is described. The possibility to directly use the benzyl alcohol as a result of a two-step reaction is also presented. This method tolerates a variety of functional groups. A benzyl radical is likely involved. (Figure presented.).
- Reddy, Bhoomireddy Rajendra Prasad,Chowdhury, Sushobhan,Auffrant, Audrey,Gosmini, Corinne
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p. 3026 - 3029
(2018/08/24)
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- Synthesis of bench-stable solid triorganoindium reagents and reactivity in palladium-catalyzed cross-coupling reactions
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Bench-stable solid triorganoindium compounds have been prepared by coordination with 4-(dimethylamino)pyridine (DMAP). The solid R3In(DMAP) complexes are obtained from the corresponding solution of R3In in quantitative yield and can
- Gil-Negrete, José M.,Pérez Sestelo, José,Sarandeses, Luis A.
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supporting information
p. 1453 - 1456
(2018/02/19)
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- Radical-Based C?C Bond-Forming Processes Enabled by the Photoexcitation of 4-Alkyl-1,4-dihydropyridines
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We report herein that 4-alkyl-1,4-dihydropyridines (alkyl-DHPs) can directly reach an electronically excited state upon light absorption and trigger the generation of C(sp3)-centered radicals without the need for an external photocatalyst. Selective excitation with a violet-light-emitting diode turns alkyl-DHPs into strong reducing agents that can activate reagents through single-electron transfer manifolds while undergoing homolytic cleavage to generate radicals. We used this photochemical dual-reactivity profile to trigger radical-based carbon–carbon bond-forming processes, including nickel-catalyzed cross-coupling reactions.
- Buzzetti, Luca,Prieto, Alexis,Roy, Sudipta Raha,Melchiorre, Paolo
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supporting information
p. 15039 - 15043
(2017/11/20)
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- Cobalt-Catalyzed Reductive Cross-Coupling Between Benzyl Chlorides and Aryl Halides
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A new protocol for the direct reductive cobalt-catalyzed arylation of benzyl chlorides has been developed in order to form functionalized diarylmethanes. A variety of reactive groups either on the aryl or the benzyl halide was employed. This represents the first cobalt-catalyzed reductive cross-coupling which does not require any ligand and pyridine. A reaction pathway is proposed involving a radical benzyl species. (Figure presented.).
- Pal, Suman,Chowdhury, Sushobhan,Rozwadowski, Elodie,Auffrant, Audrey,Gosmini, Corinne
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supporting information
p. 2431 - 2435
(2016/08/16)
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- Visible-Light-Mediated Aromatic Substitution Reactions of Cyanoarenes with 4-Alkyl-1,4-dihydropyridines through Double Carbon-Carbon Bond Cleavage
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Novel aromatic substitution reactions of cyanoarenes with 4-alkyl-1,4-dihydropyridines as alkylating reagents in the presence of a catalytic amount of a photoredox catalyst proceed smoothly to give the corresponding alkyl-substituted arenes in good to high yields. The present reaction system realizes a novel C-C bond-forming reaction between two fragments generated from the C-C bond-cleavage reactions of two independent substrates.
- Nakajima, Kazunari,Nojima, Sunao,Sakata, Ken,Nishibayashi, Yoshiaki
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p. 1028 - 1032
(2016/04/05)
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- Efficient synthesis of diarylmethane derivatives by PdCl2 catalyzed cross-coupling reactions of benzyl chlorides with aryl boronic acids in aqueous medium
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The research provides a simple and efficient method for preparing diarylmethane derivatives using the cross-coupling reaction of benzyl chlorides and aryl boronic acids catalyzed by palladium chloride in DMF aqueous solution without additional ligand.
- Zhao, Guangkuan,Zhang, Kena,Wang, Liang,Li, Jingya,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
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supporting information
p. 6700 - 6703
(2016/02/03)
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- A highly efficient catalyst for Suzuki-Miyaura coupling reaction of benzyl chloride under mild conditions
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Diarylmethane derivatives, essential building blocks in organic synthesis, are usually synthesized through the traditional electrophilic substitution reaction i.e., Friedel-Crafts reaction, which suffers from the rearrangement and weak reactivity of aromatic compounds with deactivating/electron-withdrawing groups. The Suzuki-Miyaura coupling reaction of low-cost benzyl chloride as an alternative method overcomes these defects. Pd(ii) organometallic catalysts immobilized on the triphenylphosphine-functionalized microporous knitting aryl polymer (KAPs(Ph-PPh3)-Pd) as a novel heterogeneous catalyst was employed in Suzuki-Miyaura coupling reaction of benzyl chloride and exhibited excellent catalytic activity under mild conditions with a turnover frequency (TOF) up to 76 min-1 (4569 h-1). This work reveals that the microporous structure of the catalyst can rapidly adsorb substrates, consequently facilitating their interaction, and eventually promoting the catalytic efficiency. the Partner Organisations 2014.
- Guan, Zhenhong,Li, Buyi,Hai, Guoliang,Yang, Xinjia,Li, Tao,Tan, Bien
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p. 36437 - 36443
(2014/11/08)
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- Cucurbit[7]uril promoting PdCl2-catalyzed cross-coupling reaction of benzyl halides and arylboronic acids in aqueous media
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The research provides a novel approach for producing diarylmethane derivatives using CB[7]-NaCl-PdCl2catalyzed Suzuki cross-coupling reaction of benzyl chloride derivatives and arylboronic acids in ethanol aqueous solution.
- Zhao, Guangkuan,Wang, Zhen,Wang, Ruixin,Li, Jingya,Zou, Dapeng,Wu, Yangjie
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supporting information
p. 5319 - 5322
(2015/01/16)
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- Copper-catalyzed benzylic C-H oxygenation under an oxygen atmosphere via N-H imines as an intramolecular directing group
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Copper-catalyzed benzylic C-H oxygenation under an oxygen atmosphere was developed starting from carbonitriles and Grignard reagents via N-H imine intermediates. The present process is characterized by the following two-step sequence in a one-pot manner: (1) addition of Grignard reagents to carbonitriles to form N-H imines and (2) benzylic C-H oxygenation (C=O bond formation) triggered by 1,5-hydrogen atom transfer with transient iminyl copper species.
- Zhang, Line,Ang, Gim Yean,Chiba, Shunsuke
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supporting information; experimental part
p. 1622 - 1625
(2011/05/05)
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- Direct method for carbon-carbon bond formation: The functional group tolerant cobalt-catalyzed alkylation of aryl halides
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(Figure Presented). A new protocol for the direct cobaltcatalyzed alkylation of aryl halides has been developed that proceeds smoothly in the presence of phosphanes or bipyridines as ligands with a variety of alkyl halides, including challenging alkyl electrophiles bearing β hydrogen atoms (see scheme). Sensitive functional groups are tolerated on both coupling partners, thus, significantly extending the general scope of transition-metal-catalyzed alkylation of aryl halides.
- Amatore, Muriel,Gosmini, Corinne
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supporting information; experimental part
p. 5848 - 5852
(2010/09/03)
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- Palladium nanoparticle catalyzed hiyama coupling reaction of benzyl halides
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An efficient Hiyama coupling reaction between benzylic halide and aryltrialkoxysilane using Pd nanoparticles has been developed. This procedure accommodates various functional groups to yield a diverse range of diarylmethanes which are ubiquitous units of natural products and pharmaceuticals.
- Srimani, Dipankar,Bej, Ansuman,Sarkar, Amitabha
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supporting information; experimental part
p. 4296 - 4299
(2010/09/04)
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- Simple mixed Fe-Zn catalysts for the Suzuki couplings of tetraarylborates with benzyl halides and 2-halopyridines
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Employing co-catalytic zinc reagents facilitates the iron-catalysed Suzuki cross-coupling of tetraarylborates with both benzyl and 2-heteroaryl halides.
- Bedford, Robin B.,Hall, Mark A.,Hodges, George R.,Huwe, Michael,Wilkinson, Mark C.
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supporting information; experimental part
p. 6430 - 6432
(2010/03/03)
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- Decarboxylative photosubstitution of dicyanobenzenes with aliphatic carboxylate ions
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The photoreaction of dicyanobenzenes with aliphatic carboxylate ions afforded alkylcyanobenzenes and alkyldicyanobenzenes via decarboxylative substitution. The redox-photosensitized reaction system was effective in improving the product yield. The efficie
- Itou, Tatsuya,Yoshimi, Yasuharu,Morita, Toshio,Tokunaga, Yuji,Hatanaka, Minoru
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experimental part
p. 263 - 269
(2009/04/07)
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- Synthesis of functionalised diarylmethanes via a cobalt-catalysed cross-coupling of arylzinc species with benzyl chlorides
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A new cobalt-catalysed reductive coupling of aryl halides with benzyl chlorides is reported; a variety of diarylmethanes can be prepared in good to excellent yields under mild reaction conditions using CoBr2 as catalyst and Zn dust; this new cobalt-catalysed coupling represents a practical and interesting alternative to previously known methods for the synthesis diarylmethanes. The Royal Society of Chemistry.
- Amatore, Muriel,Gosmini, Corinne
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supporting information; body text
p. 5019 - 5021
(2009/06/05)
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- Facile one-pot synthesis of 2-aryl-substituted nitriles and 2-aryl-3-keto nitriles via benzyne reaction
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2-Aryl-substituted nitriles were prepared in good to excellent yields in a one-pot reaction by the reaction of benzyne, generated using neutral conditions from (phenyl)[o-(trimethylsilyl)-phenyl]iodonium triflate, and 2-lithionitriles. 3-Keto nitriles substituted at the 2-position were obtained in good yields when these reactions were trapped with acid chlorides. The mechanism of the benzyne reaction in terms of a N-lithiobenzocyclobutanimine intermediate is discussed. Copyright Taylor & Francis Group, LLC.
- Kamila, Sukanta,Koh, Benjamin,Biehl, Edward R.
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p. 3493 - 3507
(2007/10/03)
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- Flow-vacuum pyrolysis of 2,5-diphenyl-4-methyloxazole
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The flow-vacuum pyrolysis of 2,5-diphenyl-4-methyloxazole (4) at 1000°C and 0.5 Torr afforded a complex reaction mixture containing: benzonitrile, diphenylmethane, 9,10-dimethylphenantrene, 9,10-dimethylantracene, fluorene, o-benzylbenzonitrile (major product, 20-22%), phenanthrene, anthracene, o,o′-dicyanodiphenyl, 9,10-anthraquinone, 2-methyl-4,5-diphenyloxazole and 1,1,2,2-tetraphenylethane. A radical- and carbene mechanism is suggested in order to rationalize the formation of the reaction products.
- Banciu, Mircea D.,Istrati, Daniela,Schiketanz, Iosif,Mihǎiescu, Dan,Drǎghici, Constantin,Malacea, Raluca
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p. 493 - 499
(2007/10/03)
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- Flash vacuum pyrolysis of 2,5-diphenyloxazole
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FVP of the title oxazole (1) at 1000°C and 0.5 mm Hg afforded a complex reaction mixture containing benzonitrile, phenylacetonitrile, biphenyl, diphenylmethane, fluorene, o-benzylbenzonitrile (major product, 22%), phenanthrene, anthracene, 9,10-anthraquinone, 2-phenylindole and 3-phenylindole. A radical and carbene mechanism was suggested in order to rationalize the formation of the reaction products.
- Banciu, Mircea D.,Istrati, Daniela,Mihaiescu, Dan,Draghici, Constantin
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p. 1004 - 1010
(2007/10/03)
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- Iodine ate complexes and N-lithiobenzocyclobutenamine intermediates in the reactions of α-lithionitriles with benzyne
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α-Lithionitriles add to benzynes to give N-lithiobenzocyclobutenamines in a two-step process. The intermediate aryllithiums can be trapped prior to cyclization with iodobenzene or 2,6-dimethoxyiodobenzene to form iodine-ate complex intermediates which fragment preferentially to 2-(α-cyanobenzyl)-iodobenzenes. The N-lithiobenzocyclobutenamines undergo ring opening to yield either 2-substituted benzonitriles or α-substituted benzylcyanides depending on the substitution pattern on the aryl and cyclobutene rings. (C) 2000 Published by Elsevier Science Ltd.
- Tripathy,Hussain,Durst
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p. 8401 - 8405
(2007/10/03)
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- Intramolecular Trapping of a Ketenimine Carbene Formed on Flash Vacuum Pyrolysis of 3-Phenylimino-3H-indazole and 3-Phenyliminoisobenzofuran-1-one
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Flash vacuum pyrolysis of 3-phenylimino-3H-indazole yielded biphenylene, benzonitrile and, by loss of dinitrogen followed by intramolecular trapping of a ketenimine carbene intermediate, the isomers fluorenimine, phenanthridine and 2-phenylbenzonitrile.Pyrolysis of 3-phenyliminoisobenzofuran-1-one gave the same five products together with N-phenylphthalimide.It is proposed that the same ketenimine carbene intermediate is involved in the two reactions.Pyrolysis of 3-o-tolylimino- and 3-benzylimino-isobenzofuran-1-one led to fragmentation without intramolecular trapping.Pyrolysis of 3-t-butyliminoisobenzofuran-1-one gave o-cyanobenzoic acid.
- Brown, Roger F. C.,Coulston, Karen J.,Eastwood, Frank W.
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- PHOTOSUBSTITUTION OF DICYANOBENZENES BY GROUP 14 ORGANOMETALLIC COMPOUNDS VIA PHOTOINDUCED ELECTRON-TRANSFER. ADDITIVE AND MEDIUM EFFECTS ON PHOTOINDUCED ELECTRON TRANSFER REACTION
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The phenanthrene-sensitized photoreaction of 1,2- and 1,4-dicyanobenzenes with group 14 organometallic compounds containing allylic and benzylic groups in CH3CN afforded the corresponding 1- and 4-allylated benzonitriles in high yields.These photoreactions were accelerated by the addition of Mg(ClO4)2 and benzene derivatives.
- Mizuno, Kazuhiko,Nakanishi, Kazuhisa,Otsuji, Yoshio
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p. 1833 - 1836
(2007/10/02)
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- Preparation of Aryl, Alkynyl, and Vinyl Organocopper Compounds by the Oxidative Addition of Zerovalent Copper to Carbon-Halogen Bonds
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A highly reactive copper slurry can be prepared by the reduction of CuI*PEt3 with 1 equiv of lithium naphthalide.The highly reactive copper is found to undergo rapid oxidative addition to alkyl, aryl, alknyl, and vinyl halides under mild conditions.The aryl, alkynyl, and vinyl organocopper compounds are stable at room temperature.These organocopper compounds can bee prepared with variety of functional groups such nitro, nitrile, ester, and ketone.The arylcopper compounds can be cross-coupled in moderate to high yields with acid chlorides and with alkyl-halides.A comparison of different methods for producing activated copper is presented, and the scope and limitations are discussed.
- Ebert, Greg W.,Rieke, Reuben D.
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p. 4482 - 4488
(2007/10/02)
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- A NOVEL PHOTOSUBSTITUTION OF DICYANOBENZENES BY ALLYLIC AND BENZYLIC SILANES
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The photosubstitution of o- and p-dicyanobenzenes by allylic and benzylic silanes in acetonitrile occurred efficiently, giving the corresponding mono-allylated and benzylated cyanobenzenes.
- Mizuno, Kazuhiko,Ikeda, Munehiro,Otsuji, Yoshio
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p. 461 - 464
(2007/10/02)
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- Direct Formation of Organocopper Compounds by Oxidative Addition of Zerovalent Copper to Organic Halides
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Mixing a solution of CuI*P(Et)3 with a stoichiometric amount of lithium naphthalide in THF affords a zerovalent copper species that is sufficiently reactive to add to organic halides to give the corresponding organocopper compounds.
- Ebert, Greg W.,Rieke, Reuben D.
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p. 5280 - 5282
(2007/10/02)
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