- Heteroannulation enabled by a bimetallic Rh(III)/Ag(i) relay catalysis: Application in the total synthesis of aristolactam BII
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A redox-neutral bimetallic Rh(iii)/Ag(i) relay catalysis allowed the efficient construction of 3-alkylidene isoindolinones and 3-alkylidene isobenzofuranones. The Rh(iii) catalyst was responsible for the C-H monofluoroalkenylation reaction, whereas the Ag(i) salt was an activator for the follow-up cyclization. The methodology developed was applied as a key step in the rapid total synthesis of the natural product aristolactam BII.
- Ji, Wei-Wei,Lin,Li, Qingjiang,Wang, Honggen
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- Unexpected C-C bond cleavage of α-nitroketone in the presence of TsNBr2: A new pathway for C-N bond formation
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A new catalyst-free protocol for C-N bond formation via the cleavage of α-nitroketone has been developed. When α-nitroketones are treated with TsNBr2 in the presence of potassium carbonate, unexpected cleavage of C(O)-CHNO2 bond of α-nitroketone was observed followed by the formation of corresponding amide. Various nitroketones could be converted to corresponding amide using this procedure.
- Sarma, Manas Jyoti,Phukan, Prodeep
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- N-Sulfonyl acetylketenimine as a highly reactive intermediate for synthesis of N-Aroylsulfonamides
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A highly reactive intermediate N-sulfonyl acetylketenimine was generated from an ynone-participated CuAAC/ring-opening method. Its unique structure allowed it to react with aryl carboxylic acids to give N-aroylsulfonamides via a novel Mumm-type rearrangement.
- Yang, Weiguang,Huang, Dayun,Zeng, Xiaobao,Zhang, Jianlan,Wang, Xinyan,Hu, Yuefei
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Read Online
- Chemoselective Cleavage of Acylsulfonamides and Sulfonamides by Aluminum Halides
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The chemoselective cleavage of C-N bonds of amides, sulfonamides, and acylsulfonamides by aluminum halides is described. AlCl3and AlI3display complementary reactivities toward N-alkyl and N-acyl moieties. N-Alkylacylsulfonamides, sec
- Sang, Dayong,Dong, Bingqian,Liu, Yunfeng,Tian, Juan
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p. 3586 - 3595
(2022/02/25)
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- Traceless selenocarboxylates for the one-pot synthesis of amides and derivatives
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We have recently reported a one-pot procedure for glycosyl amides synthesis using selenocarboxylate as traceless reagent. Herein, we present a further application of selenocarboxylate-azide reaction for amide bond formation on a broader range of substrates, including heterocyclic systems and fatty acid. This method proved to be highly efficient for the synthesis of primary and secondary amides, sulfonamides, imides, phosphoramide and also carbamate.
- Silva, Luana,Rosário, Alisson R.,Machado, Bianca M.,Lüdtke, Diogo S.
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supporting information
(2020/12/25)
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- Ru(ii)-catalyzed allenylation and sequential annulation of: N -tosylbenzamides with propargyl alcohols
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We hereby report Ru(ii)-catalyzed C(sp2)-H allenylation of N-tosylbenzamides to access multi-substituted allenylamides. Furthermore, the allenylamides were converted to the corresponding isoquinolone derivatives via base mediated annulation. The current protocol features low catalyst loading, mild reaction conditions, high functional group compatibility and desired scalability. The unique functionality of the afforded allenes allowed further transformations to expand the practicality of the protocol. This journal is
- Kumar, Shreemoyee,Nair, Akshay M.,Volla, Chandra M. R.
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p. 6280 - 6283
(2021/07/02)
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- Metal-free C-H Activation over Graphene Oxide toward Direct Syntheses of Structurally Different Amines and Amides in Water
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Unprecedented metal-free synthesis of a variety of amines and amides is reported via amination of C(sp3)-H and C(sp2)-H bonds. The strategy involves graphene-oxide/I2-catalyzed nitrene insertion using PhINTs as a nitrene (NT) source in water at room temperature. A wide range of structurally different substrates, viz., cyclohexane, cyclic ethers, arenes, alkyl aromatic systems, and aldehydes/ketones, having an α-phenyl ring have been employed successfully to afford the corresponding nitrene insertion product in good yield, albeit low in few cases. The envisaged method has superiority over others in terms of its operational simplicity, metal-free catalysis, use of water as a solvent, ambient reaction conditions, and reusability of the catalyst.
- Shukla, Prashant,Asati, Ambika,Bhardiya, Smita R.,Singh, Manorama,Rai, Vijai K.,Rai, Ankita
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p. 15552 - 15561
(2020/12/02)
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- Efficient synthesis of carbon-11 labelled acylsulfonamides using [11C]CO carbonylation chemistry
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Herein, a novel method for carbon-11 labeling of acyl sulfonamides by a one-step insertive [11C]CO carbonylative cross-coupling reaction between aryl halides and sulfonamides is presented. Various model compounds as well as drug molecules LY573636 (tasisulam) and ABT-199 were obtained in excellent yields. This method provides a valuable and widely applicable contribution to the continuously expanding radiochemical toolbox for PET research.
- Van Der Wildt, Berend,Shen, Bin,Chin, Frederick T.
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supporting information
p. 3124 - 3127
(2019/03/28)
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- Controllable construction of isoquinolinedione and isocoumarin scaffolds: Via RhIII-catalyzed C-H annulation of N -tosylbenzamides with diazo compounds
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A highly efficient protocol for the synthesis of isoquinolinediones by RhIII-catalyzed C-H activation/annulation/decarboxylation of N-tosylbenzamides with diazo compounds is reported. The switchable synthesis of isocoumarins was also achieved successfully via C-H activation/annulation with slight modification of the reaction conditions. Importantly, the synthetic utility of this new reaction was further demonstrated in an atom-economical and operationally convenient total synthesis of a TDP2 inhibitor derivative from commercially available starting materials.
- Liu, Yanfei,Wu, Jiaping,Qian, Baiyang,Shang, Yongjia
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p. 8768 - 8777
(2019/10/16)
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- Ruthenium-Catalyzed Synthesis of Isoindolinones via Amide-Directed Addition of Aromatic C-H Bonds to Aldimines
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Ruthenium-catalyzed addition of aromatic C-H bonds to aldimines is described. [RuCl2(p-cymene)]2 functions as an efficient catalyst to promote the coupling of aryl amides with aldimines in the presence of a catalytic amount of base to give the corresponding isoindolinone derivatives. The nature of the substituent at the N-atom of the amides is crucial for the efficient conversion of the substrates, and a p-toluenesulfonyl group is the functionality of choice. A variety of amides and aldimines participated in the present Ru-catalyzed reaction to furnish the corresponding isoindolinones in moderate to high yield.
- Miura, Hiroki,Kimura, Yuriko,Terajima, Sachie,Shishido, Tetsuya
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supporting information
p. 2807 - 2811
(2019/02/01)
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- Formation of esters and amides via metal-free Csp2-Csp3 bond cleavage of α-nitro ketone: Mechanistic insight to the reaction pathway
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A catalyst free protocol for hucleophilic Csp2-Csp3 bond cleavage of a-nitroketone has been achieved for the formation of C-O and C-N bond. A series of differently substituted a-nitroketones could be selectively cleaved and converted into corresponding esters and tosylamides in presence of alcohols and bromamine-T respectively. Mechanism of the C-C bond cleavage has been proposed by identifying different reaction intermediates using IR and NMR spectroscopic methods.
- Sarma, Manas Jyoti,Phukan, Prodeep
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p. 523 - 533
(2019/05/21)
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- Co-Catalyzed Synthesis of N-Sulfonylcarboxamides from Carboxylic Acids and Sulfonyl Azides
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A Co-catalyzed effective synthesis of N-sulfonylcarboxamides from the reaction of carboxylic acids and organic azides in the presence of isocyanide has been developed. The protocol has the advantages of short time, low temperature, and being oxidant-free, which provides a new and simple approach for the synthesis of N-sulfonylcarboxamides in good to excellent yields with a broad substrate scope.
- Fang, Yue,Gu, Zheng-Yang,Wang, Shun-Yi,Yang, Jin-Ming,Ji, Shun-Jun
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p. 9364 - 9369
(2018/07/09)
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- Pd(II)/Cu(II)-Catalyzed Regio- and Stereoselective Synthesis of (E)-3-Arylmethyleneisoindolin-1-ones Using Air as the Terminal Oxidant
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Regio- and stereoselective synthesis of (E)-3-arylmethyleneisoindolin-1-ones via Pd(II)/Cu(II)-catalyzed one-pot C-C/C-N bond forming sequence between amides and styrenes is reported. This method provides facile and rapid access to a diverse range of such compounds using readily available starting materials under mild aerobic conditions with good functional group tolerance and high selectivity and efficiency. Further elaboration of the products obtained from this process enabled very short and efficient syntheses of aristolactam and indoloisoquinolinone alkaloids.
- Youn, So Won,Ko, Tae Yun,Kim, Young Ho,Kim, Yun Ah
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supporting information
p. 7869 - 7874
(2019/01/14)
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- Carbodiimide insertion into sulfonimides: one-step route to azepine derivatives via a two-atom saccharin ring expansion
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A previously unknown insertion of carbodiimides into sulfonimides enables the first one-step, two-atom expansion of the saccharin 5-membered ring into a 7-membered benzo[1,2,4]thiadiazepine, and a two-atom chain extension of a non-cyclic sulfonimide. This reaction is enhanced by copper salts, which allow it to be conducted mechanochemically, in a solvent-free manner.
- Tan, Davin,Fri??i?, Tomislav
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p. 901 - 904
(2017/01/17)
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- N-Sulfonylcarboxamide as an Oxidizing Directing Group for Ruthenium-Catalyzed C–H Activation/Annulation
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N-Sulfonylcarboxamides can act as both a directing group for C–H activation and an internal oxidant in the Ru-catalyzed annulation reaction with alkynes to give isoquinolones. Of all of the N-sulfonylcarboxamides that were studied, the N-(2,6-difluorophenyl)sulfonamide derivatives were found to be the most efficient and led to the formation of an unstable sulfinate byproduct that decomposed into 1,3-difluorobenzene under the reaction conditions. The described isoquinolone synthesis provides an alternative to the currently known traceless annulations of hydroxamic acid and sulfoximine derivatives.
- Petrova, Elina,Rasina, Dace,Jirgensons, Aigars
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supporting information
p. 1773 - 1779
(2017/04/13)
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- Metal-catalyzed formal amidation of alkenes under CO-free condition
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An effective procedure for synthesis of amides from alkenes and [Formula presented] via Pd and Fe catalysts under mild conditions is described. A series of benzamides containing various functional groups can be obtained in reasonable yield and the possible reaction pathway is proposed in this Letter.
- Zhang, Yuanyuan,Ye, Wenjing,Leng, Xue,He, Ying,Zhang, Hui,Xiao, Xiao
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p. 4203 - 4206
(2016/08/24)
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- Reactant cum solvent water: Generation of transient λ3-hypervalent iodine, its reactivity, mechanism and broad application
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An outstanding amidation/imidation process is demonstrated under metal-free benign reaction conditions by grafting terminal alkynes with varied amines and reactant cum solvent water. We explored diverse substrate scope in the nonconventional approach for synthesis of several classes of valuable compounds bearing amide linkages such as N-tosyl, N-aminotosyl, N-oxobenzyl, N-alkylated sugar-based secondary and tertiary chiral amides and also exploiting it for synthesis of valuable cyclic imides through simultaneous activation of triple bond and sp2C-H of aldehyde. The in situ-generated powerful reagent PhI(OH)2 enables selective cleavage and functionalization of terminal C-C triple bonds through simultaneous construction of C-N and C=O bonds. A measurable breakthrough in time-resolved ATR-MIR spectroscopy of the ongoing λ3-hypervalent iodine controlled reaction revealed formation of the unknown intermediates. The ATR-MIR technology is used for identifying infrared (IR) spectra of the individual intermediate/component present in the reaction mixture, which contains several compounds. The structures of the intermediates and their IR spectra were determined by DFT study. This unprecedented combination of experimental results and theoretical prediction provided useful information regarding the reaction insights such as the cleavage of triple bond, amination and amidation in the complex reaction process involving λ3-hypervalent iodine-bearing labile intermediates to the desired amide. The NMR and labelling (2H and 18O) studies supported the DFT-IR predicted reaction pathway.
- Khamarui, Saikat,Maiti, Rituparna,Mondal, Ramij R.,Maiti, Dilip K.
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p. 106633 - 106643
(2016/01/08)
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- Room-temperature ortho-alkoxylation and -halogenation of N-tosylbenzamides by using palladium(II)-catalyzed C-H activation
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The N-tosylcarboxamide group can direct the room-temperature palladium-catalyzed C-H alkoxylation and halogenation of substituted arenes in a simple and mild procedure. The room-temperature stoichiometric cyclopalladation of N-tosylbenzamide was first studied, and the ability of the palladacycle to react with oxidants to form C-X and C-O bonds under mild conditions was demonstrated. The reaction conditions were then adapted to promote room-temperature ortho-alkoxylations and ortho-halogenations of N-tosylbenzamides using palladium as catalyst. The scope and limitation of both alkoxylations and halogenations was studied and the subsequent functional transformation of the N-tosylcarboxamide group through nucleophilic additions was evaluated. This methodology offers a simple and mild route to diversely functionalized arenes.
- Peron, Florent,Fossey, Christine,Sopkova-Deoliveirasantos, Jana,Cailly, Thomas,Fabis, Frederic
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supporting information
p. 7507 - 7513
(2014/06/23)
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- A highly efficient catalyst-free protocol for C-H bond activation: Sulfamidation of alkyl aromatics and aldehydes
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A catalyst-free protocol has been developed for amidation of alkyl aromatics and aldehydes using TsNBr2via a nitrene transfer process in the presence of a base in excellent yield within a short time. The reaction was found to be selective for secondary and tertiary benzylic C-H bonds and C-H bonds of aldehydic groups.
- Borah, Arun Jyoti,Phukan, Prodeep
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p. 5491 - 5493
(2012/06/30)
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- Iron(II)-catalyzed amidation of aldehydes with iminoiodinanes at room temperature and under microwave-assisted conditions
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A method for the amidation of aldehydes with PhI=NTs/PhI=NNs as the nitrogen source and an inexpensive iron(II) chloride + pyridine as the in situ formed precatalyst under mild conditions at room temperature or microwave assisted conditions is described. The reaction was operationally straightforward and accomplished in moderate to excellent product yields (20-99%) and with complete chemoselectivity with the new C-N bond forming only at the formylic C-H bond in substrates containing other reactive functional groups. By utilizing microwave irradiation, comparable product yields and short reaction times of 1 h could be accomplished. The mechanism is suggested to involve insertion of a putative iron-nitrene/imido group to the formylic C-H bond of the substrate via a H-atom abstraction/radical rebound pathway mediated by the precatalyst [Fe(py)4Cl2] generated in situ from reaction of FeCl 2 with pyridine.
- Ton, Thi My Uyen,Tejo, Ciputra,Tania, Stefani,Chang, Joyce Wei Wei,Chan, Philip Wai Hong
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experimental part
p. 4894 - 4904
(2011/08/03)
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- N -acylsulfonamide assisted tandem C-H olefination/annulation: Synthesis of isoindolinones
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A tandem C-H olefination/annulation sequence directed by N-acylsulfonamides affords a variety of isoindolinones. This transformation is compatible with aliphatic alkenes as well as conjugated alkenes. Notably, molecular oxygen can be used as the sole, eco-friendly oxidant.(Figure Presented)
- Zhu, Chen,Falck
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supporting information; experimental part
p. 1214 - 1217
(2011/05/02)
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- TiCl4-promoted direct N-acylation of sulfonamide with carboxylic ester
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Several Lewis acids were investigated as promoters in the intermolecular or intramolecular direct N-acylation reaction of sulfonamides using carboxylic ester as an acylating agent. TiCl4 was found to possess the highest activity and enhanced efficiently sulfonamide to form N-acylsulfonamides under optimized conditions. This method provides a novel approach to make N-acylsulfonamides from ester via an easy work-up procedure.
- Fu, Shaomin,Lian, Xiaoyan,Ma, Tongmei,Chen, Wenhua,Zheng, Meifang,Zeng, Wei
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supporting information; experimental part
p. 5834 - 5837
(2010/11/04)
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- Practical copper(I)-catalysed amidation of aldehydes
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The direct synthesis of amides by insertion into the C-H bond of aldehydes is shown to be a practical procedure through application of cheap, readily available catalysts generated in situ from copper(i) halides and pyridine. The Royal Society of Chemistry 2010.
- Chang, Joyce Wei Wei,Ton, Thi My Uyen,Tania, Stefani,Taylor, Paul C.,Chan, Philip Wai Hong
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supporting information; experimental part
p. 922 - 924
(2010/06/12)
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- Highly efficient ruthenium(II) porphyrin catalyzed amidation of aldehydes
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H to N: The first example of a mild, highly efficient C-H bond amidation catalyzed by ruthenium(II) porphyrin complexes uses PhI=NTs as the nitrogen source for installing the amide bond functionality in a wide variety of aldehydes (see scheme). The protocol is chemoselective, with the new C-N bond forming only at the acyl C-H bond, even in aldehyde substrates containing other functional groups.
- Chang, Joyce Wei Wei,Chan, Philip Wai Hong
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p. 1138 - 1140
(2008/09/21)
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- Acylation of aromatic compounds with isocyanates catalyzed by ytterbium(III) triflate: Environmentally friendly
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Aromatic compounds can be acylated by isocyanates in the presence of catalytic amount of ytterbium(III) triflate [Yb(0Tf)3] to obtain the corresponding N-substituted benzamides in good yields under neutral conditions. The catalyst can easily be recovered and reused without any loss of activity.
- Su,Li,Yang
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p. 885 - 887
(2007/10/03)
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- Unconventional Regiospecific Syntheses of Aromatic Carbonamides and Thiocarbonamides by Means of Tin-Mediated Friedel-Crafts Reactions
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Friedel-Crafts reactions of stannylarenes 1 with tosyl isocyanate (TsNCO, 2) give N-tosylcarbonamides 3 via ipso substitution of the stannyl group.Thus, unconventionally substituted aromatic carbonamides can be obtained.The combination of the reaction of 1 and 2 with that of 1 and chlorosulfonyl isocyanate (14) allows one-pot syntheses of N-(arylsulfonyl)-substituted aromatic carbonamides with optional substitution patterns on both aromatic rings.The known ipso-specific substitutions of stannylarenes with 14 are extended to bi- and tricyclic arenes as well as to thiophenes 6 and 22.One stannyl group can serve as a leaving group for two aromatic systems, as shown with diaryldialkyltins 29.Also, stannylalkanes such as 27 react with 14 to afford alkylsulfonyl isocyanates and products of further reactions, such as 28.From the reactions of 1 with ethoxycarbonyl isocyanate (32), ortho- and meta-substituted aromatic thiocarbonamides 33 which are potential precursors for further syntheses, are accessible.The scope, limitations, and mechanism of these electrophilic substitutions are outlined.
- Arnswald, Martin,Neumann, Wilhelm P.
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p. 7022 - 7028
(2007/10/02)
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- KINETICS AND MECHANISMS OF THE ACID-CATALYSED HYDROLYSES OF 4-NITROPHENYL-N-AROYL-ARENEIMINOSULPHONATES
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The acid catalysed hydrolyses of N-acetyl and a series of N-aroylsulphonimidic esters have been studied in aqueous 40percent (v/v) dioxane solutions of mineral acids.At low acidity all the esters studied are considered to hydrolyse by an A-2 mechanism.At
- Kutuk, Halil,Tillett, John
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p. 217 - 224
(2007/10/02)
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- Footprint Catalysis. II. Molecular Recognition of Footprint Catalytic Sites
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In order to investigate the molecular recognition capability of "footprint" catalytic sites, the affinities of nine "footprint" catalysts for eleven competitive inhibitors, closely related to template molecules, were estimated through the competitive inhibition constants, Ki .An examination of the affinity revealed that the recognition by "footprint" catalytic sites was so highly specific that it could recognize not only the whole, but also the partial, stuctures of the bound molecules.
- Morihara, Kensaku,Nishihata, Emiko,Kojima, Mari,Miyake, Sayoko
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p. 3999 - 4004
(2007/10/02)
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