- A more sustainable and highly practicable synthesis of aliphatic isocyanides
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Synthesis protocols to convert N-formamides into isocyanides using three different dehydration reagents (i.e. p-toluenesulfonyl chloride (p-TsCl), phosphoryl trichloride (POCl3) and the combination of triphenylphosphane (PPh3) and iodine) were investigated and optimized, while considering the principles of green chemistry. Comparison of the yield and the E-factors of the different synthesis procedures revealed that, in contrast to the typically applied POCl3 or phosgene derivatives, p-TsCl was the reagent of choice for non sterically demanding aliphatic mono- or di-N-formamides (yields up to 98% and lowest E-factor 6.45). Apart from a significantly reduced E-factor, p-TsCl is cheap, offers a simplified reaction protocol and work-up, and is less toxic compared to other dehydration reagents. Thus, this procedure offers easier and greener access to aliphatic isocyanide functionalities.
- Waibel,Nickisch,M?hl,Seim,Meier
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Read Online
- Ugi Multicomponent Reaction Based Synthesis of Medium-Sized Rings
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An Ugi multicomponent reaction based two-step strategy was applied to generate medium-sized rings. In the first linear expansion phase, a series of diamines reacted with cyclic anhydrides to produce different lengths of terminal synthetic amino acids as the starting material for the second phase. The Ugi-4-center 3-component reaction was utilized to construct complex medium-sized rings (8-11) by the addition of isocyanides and oxo components. This method features mild conditions and a broad substrate scope.
- Abdelraheem, Eman M. M.,Madhavachary, Rudrakshula,Rossetti, Arianna,Kurpiewska, Katarzyna,Kalinowska-Tlu?cik, Justyna,Shaabani, Shabnam,D?mling, Alexander
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Read Online
- Synthesis and structure–activity relationship of α-keto amides as enterovirus 71 3C protease inhibitors
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α-Keto amide derivatives as enterovirus 71 (EV71) 3C protease (3Cpro) inhibitors have been synthesized and assayed for their biochemical and antiviral activities. structure–activity relationship (SAR) study indicated that small moieties were primarily tolerated at P1' and the introduction of para-fluoro benzyl at P2 notably improved the potency of inhibitor. Inhibitors 8v, 8w and 8x exhibited satisfactory activity (IC50= 1.32 ± 0.26 μM, 1.88 ± 0.35 μM and 1.52 ± 0.31 μM, respectively) and favorable CC50values (CC50> 100 μM). α-Keto amide may represent a good choice as a warhead for EV71 3Cproinhibitor.
- Zeng, Debin,Ma, Yuying,Zhang, Rui,Nie, Quandeng,Cui, Zhengjie,Wang, Yaxin,Shang, Luqing,Yin, Zheng
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- Electrochemical generation of alkyl and aryl isocyanides
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An efficient and widely applicable reagent-free method for the synthesis of alkyl and aryl isocyanides has been established. The electrochemical reduction of alkyl and aryl carbonimidoyl dichlorides under constant cathode potential leads to the corresponding isocyanides in almost quantitative yields. The availability of the starting materials, the mildness of the reaction conditions as well as the easy isolation of products are noteworthy, advantageous features of the procedure.
- Guirado, Antonio,Zapata, Andres,Gomez, Jesus L.,Trabalon, Luis,Galvez, Jesus
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- Synthesis of isocyanides by reacting primary amines with difluorocarbene
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A general, convenient, and friendly route for preparing a versatile building block of isocyanides from primary amines is developed. Difluorocarbene, generated in situ from decarboxylation of chlorodifluoroacetate, reacts efficiently with primary amines to produce isocyanides. Various primary amines are well tolerated, including aryl, heteroaryl, benzyl, and alkyl amines, as well as amine residues in amino acids and peptides. Late-stage functionalization of biologically active amines is demonstrated, showing its practical capacity in drug design and peptide modification.
- Si, Yi-Xin,Zhu, Peng-Fei,Zhang, Song-Lin
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- ELECTROCHEMICAL REDUCTION OF CARBONIMIDOYL DICHLORIDES. A NEW METHOD FOR THE PREPARATION OF ISOCYANIDES
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The cathodic reduction of carbonimidoyl dichlorides provides a new, mild and free-reagent method for the preparation of isocyanides in almost quantitative yields.
- Guirado, Antonio,Zapata, Andres,Fenor, Manuel
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Read Online
- Multicomponent Ugi Reaction of Indole- N-carboxylic Acids: Expeditious Access to Indole Carboxamide Amino Amides
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A novel multicomponent Ugi-type reaction for the synthesis of indole carboxamide amino amides from aldehydes, amines, isocyanides, and indole-N-carboxylic acids, which were simply prepared from indoles and CO2, is described. This method provides an expeditious and practical access to indole tethered peptide units, along with the achievement of remarkable structural diversity and brevity. Gram-scale reaction was conducted to demonstrate the scalability, and the products could be transformed to new indole derivatives.
- Zeng, Linwei,Sajiki, Hironao,Cui, Sunliang
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- Formamide Synthesis through Borinic Acid Catalysed Transamidation under Mild Conditions
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A highly efficient and mild transamidation of amides with amines co-catalysed by borinic acid and acetic acid has been reported. A wide range of functionalised formamides was synthesized in excellent yields, including important chiral α-amino acid derivatives, with minor racemisation being observed. Experiments suggested that the reaction rely on a cooperative catalysis involving an enhanced boron-derived Lewis acidity rather than an improved Br?nsted acidity of acetic acid. Amide bonds are reputedly difficult to activate due to their high resonance stabilization. An unusual mild activation of dimethylformamide and formamide by borinic acid 1 (see scheme), illustrated by a general formylation of a wide range of amines, including chiral α-amino esters, has been reported.
- Mohy El Dine, Tharwat,Evans, David,Rouden, Jacques,Blanchet, Jér?me
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Read Online
- Microwave-assisted synthesis of isonitriles: A general simple methodology
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(Chemical Equation Presented) A facile conversion of formamides to isonitriles under very mild conditions and microwave irradiation is described. This simple and efficient method has been applied for the synthesis of both aliphatic and aromatic isonitriles in high yields.
- Porcheddu, Andrea,Giacomelli, Giampaolo,Salaris, Margherita
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Read Online
- Anodic Oxidation of Aminotetrazoles: A Mild and Safe Route to Isocyanides
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A new electrochemical method for the preparation of isocyanides from easily accessible aminotetrazole derivatives has been developed, which tolerates an unprecedented range of functional groups. The use of chemical, rather than electrochemical, oxidation to afford isocyanides was also demonstrated, which provides access to these compounds for those without electrosynthesis equipment. The practicality of scale-up using flow electrochemistry has been demonstrated, in addition to the possibility of using electrochemically generated isocyanides in further reactions.
- Leech, Matthew C.,Petti, Alessia,Tanbouza, Nour,Mastrodonato, Andrea,Goodall, Iain C. A.,Ollevier, Thierry,Dobbs, Adrian P.,Lam, Kevin
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p. 9371 - 9375
(2021/12/09)
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- One-Pot Synthesis of Thiocarbamates
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An efficient isocyanide-based synthesis of S-thiocarbamates was discovered and thoroughly investigated. The new reaction protocol is a one-pot procedure and allows the direct conversion of N-formamides into thiocarbamates by initial dehydration with p-toluene sulfonyl chloride to the respective isocyanide and subsequent addition of a sulfoxide component. Contrary to recent literature, which also uses isocyanides as starting material, but with other sulfur reagents than sulfoxides, in this protocol, no isolation and purification of the isocyanide component is necessary, thus significantly decreasing the environmental impact and increasing the efficiency of the synthesis. The new protocol was applied to synthesize a library of sixteen thiocarbamates, applying four N-formamides and four commercially available sulfoxides. Furthermore, experiments were conducted to investigate the reaction mechanism. Finally, four norbornene-based thiocarbamate monomers were prepared and applied in controlled ring-opening metathesis polymerization (ROMP) reactions. The polymers were characterized by size-exclusion chromatography (SEC) and their properties were investigated utilizing differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).
- Barther, Dennis,Malliaridou, Triantafillia,Meier, Michael A. R.,Moatsou, Dafni,Waibel, Kevin A.
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supporting information
p. 4508 - 4516
(2021/08/30)
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- Method for preparing isonitrile compound
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The invention discloses a method for preparing an isonitrile compound, and belongs to the field of organic synthesis. According to the method, sodium chlorodifluoroacetate or potassium bromodifluoroacetate is used as a difluoromethyl source and is condensed with primary amine under the action of alkali to obtain an isocyanide target product, so that isocyanide is generated in situ on the primary amine. The reaction raw materials, alkali and solvent used in the method are simple and easy to obtain, wide in source and convenient to operate, do not need special storage and use conditions, the method has the advantages of safety, low cost, high yield, simple process, environmental friendliness and the like, and has important application value in the fields of medicine, protein and polypeptidepreparation, pesticides, high polymer materials, dyes and the like.
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Paragraph 0056-0061
(2021/01/30)
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- Isocyanide 2.0
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The isocyanide functionality due to its dichotomy between carbenoid and triple bond characters, with a nucleophilic and electrophilic terminal carbon, exhibits unusual reactivity in organic chemistry exemplified for example in the Ugi reaction. Unfortunately, the over proportional use of only a few isocyanides hampers novel discoveries about the fascinating reactivity of this functional group. The synthesis of a broad range of isocyanides with multiple functional groups is lengthy, inefficient, and exposes the chemist to hazardous fumes. Here we present an innovative isocyanide synthesis overcoming these problems by avoiding the aqueous workup which we exemplify by parallel synthesis from a 0.2 mmol scale performed in 96-well microtiter plates up to a 0.5 mol multigram scale. The advantages of our methodology include an increased synthesis speed, very mild conditions giving access to hitherto unknown or highly reactive classes of isocyanides, rapid access to large numbers of functionalized isocyanides, increased yields, high purity, proven scalability over 5 orders of magnitude, increased safety and less reaction waste resulting in a highly reduced environmental footprint. For example, the hitherto believed to be unstable 2-isocyanopyrimidine, 2-acylphenylisocyanides and even o-isocyanobenzaldehyde could be accessed on a preparative scale and their chemistry was explored. Our new isocyanide synthesis will enable easy access to uncharted isocyanide space and will result in many discoveries about the unusual reactivity of this functional group. This journal is
- Ahmadian-Moghaddam, Maryam,D?mling, Alexander,Patil, Pravin
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supporting information
p. 6902 - 6911
(2020/11/09)
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- Rapid Discovery of Aspartyl Protease Inhibitors Using an Anchoring Approach
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Pharmacophore searches that include anchors, fragments contributing above average to receptor binding, combined with one-step syntheses are a powerful approach for the fast discovery of novel bioactive molecules. Here, we are presenting a pipeline for the rapid and efficient discovery of aspartyl protease inhibitors. First, we hypothesized that hydrazine could be a multi-valent warhead to interact with the active site Asp carboxylic acids. We incorporated the hydrazine anchor in a multicomponent reaction and created a large virtual library of hydrazine derivatives synthetically accessible in one-step. Next, we performed anchor-based pharmacophore screening of the libraries and resynthesized top-ranked compounds. The inhibitory potency of the molecules was finally assessed by an enzyme activity assay and the binding mode confirmed by several soaked crystal structures supporting the validity of the hypothesis and approach. The herein reported pipeline of tools will be of general value for the rapid generation of receptor binders beyond Asp proteases.
- ünver, M. Yagiz,Camacho, Carlos Jamie,D?mling, Alexander,Haupenthal, J?rg,Heine, Andreas,Hirsch, Anna K. H.,Jumde, Varsha R.,Klebe, Gerhard,Konstantinidou, Markella,Magari, Francesca,Sutanto, Fandi
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supporting information
(2020/04/10)
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- [3+2] Anionic Cycloaddition of Isocyanides to Acyclic Enamines and Enaminones: A New, Simple, and Convenient Method for the Synthesis of 2,4-Disubstituted Pyrroles
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We herein demonstrate a new approach for the synthesis of 2,4-disubstituted pyrroles by [3+2] cycloaddition reaction of isocyanides to the activated double bond of various enamines and enaminones. This process paved the way for the synthesis a series of 2,4-disubstituted pyrroles, which are known to be intermediates in the synthesis of biologically active compounds, in good to excellent yields from simple and commercially available starting materials. The process is carried out efficiently using a strong base, tBuOK, at low temperatures (0 °C). The described method is simple, proceeds in one step, does not require additional catalysts and hence, has a wide scope.
- Bakulev, Vasiliy A.,Efimov, Ilya V.,Luque, Rafael,Matveeva, Maria D.,Voskressensky, Leonid G.
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supporting information
(2020/02/27)
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- Thermolysis-Induced Two- or Multicomponent Tandem Reactions Involving Isocyanides and Sulfenic-Acid-Generating Sulfoxides: Access to Diverse Sulfur-Containing Functional Scaffolds
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Direct reaction of isocyanides with some sulfenic-acid-generating sulfoxides led to the effective formation of the corresponding thiocarbamic acid S-esters in good to high yields. A multicomponent reaction involving isocyanide, sulfoxide, and a suitable nucleophile has also been developed, providing ready access to a diverse range of sulfur-containing compounds, including isothioureas, carbonimidothioic acid esters, and carboximidothioic acid esters.
- Wu, Shengfeng,Lei, Xiaofang,Fan, Erkang,Sun, Zhihua
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p. 522 - 525
(2018/02/10)
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- Silver-catalyzed [3+2+1] annulation of aryl amidines with benzyl isocyanide
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A silver-catalyzed [3+2+1] annulation of amidines with benzyl isocyanide toward 2,4-diaryl-1,3,5-triazines was developed. A variety of symmetrical and unsymmetrical products were obtained in moderate to good yields. This work also features an oxidant-free approach to 2,4-disubstituted triazines.
- Lu, Xiaodong,Xin, Xiaoyi,Wan, Boshun
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supporting information
p. 361 - 364
(2018/01/08)
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- Hexafluoroisopropanol as the Acid Component in the Passerini Reaction: One-Pot Access to β-Amino Alcohols
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A new Passerini-type reaction in which hexafluoroisopropanol functions as the acid component is reported. The reaction tolerates a broad range of isocyanides and aldehydes, and the formed imidates can be reduced toward β-amino alcohols under mild and metal-free conditions. In addition, the imidate products were shown to undergo an unprecedented retro-Passerini-type reaction under microwave conditions, providing valuable mechanistic information about the Passerini reaction and its variations.
- Saya, Jordy M.,Berabez, Rayan,Broersen, Pim,Schuringa, Imme,Kruithof, Art,Orru, Romano V. A.,Ruijter, Eelco
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supporting information
p. 3988 - 3991
(2018/07/15)
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- Synthesis of Isoselenocyanates
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Isoselenocyanates were synthesized by two methods under phase-transfer conditions (50% aq NaOH, CH2Cl2, Aliquat 336); the first started from isocyanides and selenium and gave isoselenocyanates in 61-89% yields, while the second started from amines and used chloroform and selenium, by applying sequentially the Hofmann isonitrile synthesis and the addition of selenium, in 4-70% yields.
- Zakrzewski, Jerzy,Huras, Bogumi?a,Kie?czewska, Anna
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- Development of Scalable Conditions for the Ugi Reaction-Application to the Synthesis of (R)-Lacosamide
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The Ugi reaction is applied for the preparation of (R)-lacosamide, an important drug for the treatment of epilepsy. To this end, key issues associated with the Ugi reaction, such as a practical preparation of the foul-smelling isocyanide as well as the efficient introduction of chirality via a cheap and easily removable chiral directing group, were solved. Enantiomerically pure (>99.9% ee) drug substance meeting all required purity specifications is prepared in operationally simple four steps in 40% overall yield from the commodity chemical benzylamine.
- Wehlan, Hermut,Oehme, Jan,Sch?fer, Alexander,Rossen, Kai
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p. 1980 - 1986
(2016/01/09)
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- MULTICYCLIC COMPOUND HAVING NITROGEN AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME
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The present invention relates to a nitrogen-containing polycyclic compound employing a novel structure and an organic light emitting device using the same. According to the present invention, the nitrogen-containing polycyclic compound can be used to form an organic layer in the organic light emitting device.COPYRIGHT KIPO 2015
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Paragraph 0180-0183
(2016/10/09)
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- Synthesis of isocyanides through dehydration of formamides using XtalFluor-E
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The formation of isocyanides from formamides using XtalFluor-E, [Et2NSF2]BF4, is presented. A wide range of formamides can be used to produce the corresponding isocyanides in up to 99% yield. In a number of cases, the crude products showed good purity (generally >80% by NMR) allowing to be used directly in multi-component reactions.
- Keita, Massaba,Vandamme, Mathilde,Mahé, Olivier,Paquin, Jean-Fran?ois
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supporting information
p. 461 - 464
(2015/03/05)
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- Efficient isocyanide-less isocyanide-based multicomponent reactions
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Isocyanides are the Jekyll and Hyde of organic chemistry allowing for extremely interesting transformations that are not only extremely odorous but also noxious. Therefore, an isocyanide-less isocyanide-based multicomponent reaction (IMCR) has been developed, and this protocol is expected to replace many of the old procedures in the future not only in IMCR but in other areas of organic chemistry as well.
- Neochoritis, Constantinos G.,Stotani, Silvia,Mishra, Bhupendra,D?mling, Alexander
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supporting information
p. 2002 - 2005
(2015/04/27)
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- Synthesis of imidazo[1,2-a]pyridines in a sequential one-pot Groebke-Blackburn modification using 2-aminopyridines, aldehydes and amines
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Herein we present a novel synthetic procedure for the synthesis of imidazo[1,2-a]pyridines in a modified Groebke-Blackburn fashion. In a sequential three-step one-pot protocol the commercially hardly available isocyanide-component is formed in situ using standard reagents. Cyclization to the desired products can be afforded in the same reaction mixture. The absent need of isolation of the isocyanide in this protocol eases its handling considerably and workup is only needed to finally furnish the imidazo[1,2-a]pyridines via coloumn chromatography. This protocol is a convenient way to more diverse libraries of imidazo[1,2-a]pyridines extending the functionality of the Groebke-Blackburn synthesis.
- Flesch,Schubert-Zsilavecz
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p. 507 - 510
(2015/09/15)
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- Multicomponent cascade cycloaddition involving tropone, allenoate, and isocyanide: A rapid access to a 7,6,5-fused tricyclic skeleton
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Multicomponent cascade cycloaddition of tropone, allenoate, and isocyanide has been disclosed. This method allows for the rapid construction of a highly unusual tricyclic skeleton in an efficient manner. The proposed transformation proceeds through [8 + 2 + 1] cycloaddition, [1,5]-H shift, and cyclization followed by an alkoxy group migration process.
- Jia, Shuanglong,Su, Shikuan,Li, Chunju,Jia, Xueshun,Li, Jian
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p. 5604 - 5607
(2015/02/19)
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- Novel ultrasound-promoted parallel synthesis of trifluoroatrolactamide library via a one-pot passerini/hydrolysis reaction sequence and their fungicidal activities
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An ultrasound-promoted one-pot Passerini/hydrolysis reaction sequence has been developed for the synthesis of trifluoroatrolactamide derivatives using a diverse range of trifluoroacetophenones and isonitriles in acetic acid. Parallel synthesis in a centrifuge tube using a noncontact ultrasonic cell crusher was used in this study as an efficient method for the rapid generation of combinatorial trifluoroatrolactamide libraries, and subsequent biochemical evaluation of the resulting compounds indicated that they possessed excellent broad-spectrum fungicidal activities. N-(4-chlorophenyl)-2-(4-ethylphenyl)-3,3, 3-trifluoro-2-hydroxypropanamide and N-(4-chlorophenyl)-3,3,3-trifluoro-2- hydroxy-2-(4-methoxyphenyl)propanamide, in particular, showed significant fungicidal activities against all of the fungal species tested in the current study.
- Yu, Shu-Jing,Zhu, Cong,Bian, Qiang,Cui, Can,Du, Xiu-Jiang,Li, Zheng-Ming,Zhao, Wei-Guang
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supporting information
p. 17 - 23
(2014/02/14)
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- A general simple methodology for synthesis of isonitriles using benzene-1,3-disulfonyl dichloride
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Isonitrile derivatives have been synthesized in good to high yields by dehydration of aliphatic and aromatic formamides in the presence of benzene-1,3-disulfonyl dichloride as easy and efficient reagent.
- Ghorbani-Vaghei, Ramin,Amiri, Mostafa,Veisi, Hojat
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- Odorless isocyanide chemistry: An integrated microfluidic system for a multistep reaction sequence
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Can't smell this: An integrated continuous-flow microfluidic setup enables in situ generation, extraction, separation, and reaction of foul-smelling isocyanides with little exposure to the surroundings. Isocyanides were generated by dehydration of the corresponding N-substituted formamides, and several representative isocyanide-based organic reactions were successfully performed. DIPEA=N,N-diisopropylethylamine. Copyright
- Sharma, Siddharth,Maurya, Ram Awatar,Min, Kyoung-Ik,Jeong, Guan-Young,Kim, Dong-Pyo
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supporting information
p. 7564 - 7568
(2013/07/26)
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- Multicomponent reaction to construct spirocyclic oxindoles with a Michael (triple Michael)/cyclization cascade sequence as the key step
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Multicomponent cycloadditions with readily available isocyanides, allenoates, and isatylidene malononitriles are disclosed. This reaction, which does not require the aid of any catalyst, allows the efficient syntheses of spirocyclic oxindoles with excellent regioselectivity. Reactions with ethyl 2,3-butadienoate and various structurally diverse α- and γ-substituted allenoates are also fully explored. Remarkably, we have shown that the usual three-component process can be further developed into an unprecedented four-component cycloaddition in the presence of water, which provides a new strategy to access highly unusual tricyclic oxindoles. From a synthetic point of view, this protocol is very interesting considering the high level of complexity reached in one step. The mechanism is thought to proceed by a triple Michael/cyclization process by using allenoate as a three carbon atom component (3 C). Furthermore, multicomponent reaction with γ-substituted allenoate also results in a very interesting conversion. In such cases, the unusual cleavage of the "C=C" double bond of isatylidene malononitrile and one of the "C=C" double bonds of allenoate is always observed. Multiply your chemistry! Multicomponent reactions with readily available isocyanides, allenoates, and isatylidene malononitriles are disclosed. This protocol provides a synthetic route to an exocyclic double bond containing a spirocyclic ring in an efficient manner with excellent regioselectivity (see scheme). Copyright
- Li, Jian,Wang, Ning,Li, Chunju,Jia, Xueshun
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p. 9645 - 9650
(2012/09/07)
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- Synthesis and evaluation of inhibitors of bacterial drug efflux pumps of the major facilitator superfamily
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Inhibitors of drug efflux pumps have great potential as pharmacological agents that restore the drug susceptibility of multidrug resistant bacterial pathogens. Most attention has been focused on the discovery of small molecules that inhibit the resistance nodulation division (RND) family drug efflux pumps in Gram-negative bacteria. The prototypical inhibitor of RND-family efflux pumps in Gram-negative bacteria is MC-207,110 (Phe-Arg-β-naphthylamide), a C-capped dipeptide. Here, we report that C-capped dipeptides inhibit two chloramphenicol-specific efflux pumps in Streptomyces coelicolor, a Gram-positive bacterium that is a relative of the human pathogen Mycobacterium tuberculosis. Diversity-oriented synthesis of a library of structurally related C-capped dipeptides via an Ugi four component reaction and screening of the resulting compounds resulted in the discovery of a compound that is threefold more potent as a suppressor of chloramphenicol resistance in S. coelicolor than MC-207,110. Since chloramphenicol resistance in S. coelicolor is mediated by major facilitator superfamily drug efflux pumps, our findings provide the first evidence that C-capped dipeptides can inhibit drug efflux pumps outside of the RND superfamily.
- Okandeji, Babajide O.,Greenwald, Daniel M.,Wroten, Jessica,Sello, Jason K.
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experimental part
p. 7679 - 7689
(2012/02/05)
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- NEW BENZIMIDAZOLE DERIVATIVES
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The invention is concerned with novel benzimidazole derivatives of formula (I) wherein R1 to R6 are as defined in the description and in the claims, as well as physiologically acceptable salts and esters thereof. These compounds can be used as medicaments.
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Page/Page column 36
(2010/04/30)
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- Isocyanide-based multicomponent reaction 'without' isocyanides
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We present here a one-pot, four-component sequence that affords Ugi-type adducts starting from simple benzyl or allyl bromides. The isocyanides are prepared in situ under alkylation of silver cyanide salts and the resulting mixture is directly used in a U
- El Kaim, Laurent,Grimaud, Laurence,Schiltz, Aurélie
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experimental part
p. 1401 - 1404
(2009/10/19)
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- One-pot synthesis of oxazoles using isocyanide surrogates
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We wish to present herein a simple one-pot synthesis of 2,5-disubstituted oxazoles, starting from benzyl halides and acyl chlorides. The in situ formation of isocyanides, followed by the addition of an acyl chloride in the presence of a base leads to the
- Kaim, Laurent El,Grimaud, Laurence,Schiltz, Aurélie
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experimental part
p. 5235 - 5237
(2009/12/06)
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- NEW COMPOUNDS I/418
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There is provided compounds of formula I, wherein R1 to R7 have meanings given in the description, which are useful in the prophylaxis and in the treatment of arrhythmias, in particular atrial and ventricular arrhythmias.
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Page/Page column 30
(2008/06/13)
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- N-(4-carb-amimidophenyl)glycineamide derivatives
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N-(4-carbamimidophenylamino) phenylglycineamide derivative compounds having the formula: in which E, g1, g2, Q, R and X1 to X4 are each as defined in the description, and hydrates or solvates and physiologically acceptable salts thereof can be used as inhibitors of the formation of the coagulation factors Xa, IXa and thrombin induced by the factor VIIa and by the tissue factor. These compounds can be used as medicaments for the treatment and/or prevention of thromboses, apoplexy, cardiac infarction, inflammation and arteriosclerosis or as antitumor agents.
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- Electrochemical synthesis of isocyanides and 1,n-diisocyanides
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Some isocyanide structures have shown fungicide, antibiotic, insecticide, akarizide and other biological activities. Electrochemical reduction of substituted tosylmethylisocyanides (TosMICs) in acetonitrile/0,1 M tetraalkylammonium supporting-electrolyte at Hg-electrodes led to new alkyl-, aryl and 1,n-diisocyanides in good yields. The reaction proceeds in a two-electron C,S-cleavage, reducing exclusively the tosyl-function. The high selectivity of the corresponding ECE-mechanism is supported by quantum- chemical calculation.
- Hess, Ulrich,Brosig,Komenda,Schaefer
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p. 412 - 417
(2007/10/03)
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- Aryl chlorothionoformate: A new versatile reagent for the preparation of nitriles and isonitriles under mild conditions
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Aryl chlorothionoformate is a very useful reagent for the preparation of nitriles and isonitriles in high yields under essentially neutral conditions.
- Subhas Bose,Ravinder Goud
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p. 747 - 748
(2007/10/03)
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- 2-Chloro-1,3-dimethylimidazolinium chloride. 1. A powerful dehydrating equivalent to DCC
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2-Chloro-1,3-dimethylimidazolinium chloride (DMC) (3) can act as a powerful dehydrating agent, replacing DCC (1) under nearly neutral conditions. Its application to acylation and dehydration is described.
- Isobe, Toshio,Ishikawa, Tsutomu
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p. 6984 - 6988
(2007/10/03)
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- Solution and solid phase combinatorial synthesis of peptidomimetic library containing diversified α-methylated amino acids
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A combinatorial peptidomimetic library containing diversified α- methylated amino acids was generated by the Ugi four component condensation (4cc) reaction from acids, amines, isocyanides and ketones in both solution and solid phase synthesis procedures. This one-pot methodology overall gave fair to good yields, which compare well with multi-step syntheses.
- Kim, Sang Woong,Shin, You Seung,Ro, Seonggu
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p. 1665 - 1668
(2007/10/03)
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- Screw Sense Selective Polymerization of Achiral Isocyanides Catalysed by Optically Active Nickel(II) Complexes
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Poly(isocyanides), (RN=Cn, can be prepared from isocyanides, , by the catalytic action of nickel(II) compounds.The main chain of these polymers is a rigid helix.This helical conformation results from a restricted rotation around the single bonds that connect the main-chain carbon atoms.Polymerization of achiral isocyanides generally gives a racemic mixture of left- and right-handed helices, whereas polymerization of optically active isocyanides results in helices with an excess of one screw sense.We describe a procedure for obtaining poly(isocyanides) with predominantly one screw sense, starting from an achiral monomer.A catalyst is prepared by adding an optically active amine to a tetrakis(isocyanide)nickel(II) perchlorate complex.Polymerization of various achiral isocyanides with this catalist yields optically active polymers with an enantiomeric excess up to 83percent.
- Kamer, Paul C. J.,Nolte, Roeland J. M.,Drenth, Wiendelt
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p. 6818 - 6825
(2007/10/02)
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- Photochemical Reactivity of Aldimines from 2,2-Dimethyl-3-oxo-3-phenylpropanal
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The syntheses of some thermally labile aldimines of 2,2-dimethyl-3-oxo-3-phenylpropanal are described.The aldimines (7a-c) are photochemically reactive and undergo fission mainly into isopropyl phenyl ketone.Several other minor products are also formed.On
- Armesto, Diego,Ramos, Ana,Perez-Ossorio, Rafael,Horspool, William M.
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- DI-2-PYRIDYL SULFITE. A NEW USEFUL REAGENT FOR THE PREPARATION OF N-SULFINYLAMINES, NITRILES, ISOCYANIDES, AND CARBODIIMIDES UNDER MILD CONDITIONS
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Di-2-pyridyl sulfite is a very useful reagent for the preparation of N-sulfinylamines, nitriles, isocyanides, and carbodiimides in high yields under essentially neutral conditions.
- Kim, Sunggak,Yi, Kyu Yang
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p. 1925 - 1928
(2007/10/02)
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- Reaction of N-Nitroso-N-benzylformamide with Phenylmagnesium Bromide and Phenyllithium
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The action of aryl Grignard and lithium reagents on N-nitroso-N-benzylformamide (1) leads to products whose formation can be understood in terms of the intermediacy of benzyldiazotate ion.However, the presence of "hydrogen abstraction" products, e. g., anisole or naphthalene, coupled with the near absence of products traceable to the aldehyde moiety (expected from the attack at the formyl group) with 1 equiv of organometallics, suggests the initial formation of a complex.Possible rationalizations for the formation of the products are presented.
- Nakajima, Masayuki,Anselme, Jean-Pierre
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p. 2492 - 2496
(2007/10/02)
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- The Conversion of Aldehydes and Ketones via their 2,4,6-Tri-isopropylbenzenesulphonyl Hydrazones into Nitriles containing One Additional Carbon Atom
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2,4,6-Tri-isopropylbenzenesulphonyl hydrazones of aliphatic and alicyclic aldehydes and ketones react readily with potassium cyanide in boiling methanol solution to give the corresponding nitriles (containing one more carbon atom than the original aldehyde or ketone) in satisfactory yield. Under the same conditions, benzaldehyde 2,4,6-tri-isopropylbenzenesulphonyl hydrazone gives phenylacetonitrile in very low yield.In some cases, the arenesulphonyl hydrazones may be generated in situ, in methanol solution, from the carbonyl compounds and 2,4,6-tri-isopropylbenzenesulphonohydrazide (11a), thereby constituting a one-pot preparation or the nitriles.
- Jiricny, Josef,Orere, Daniel M.,Reese, Colin B.
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p. 1487 - 1492
(2007/10/02)
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- Tris(substituted amino) sulfonium salts
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Trisaminosulfonium salts of the formula (R1 R2 N)(R3 R4 N)(R5 R6 N)S+ X- wherein the R groups are alkyl of 1-20 carbons and each alkyl has at least 2 alpha hydrogens and X is selected from the group (CH3)3 SiF2, Cl, Br, I, CN, NCO, NCS NO2 and N3, are soluble in organic liquids. They are useful as polymerization catalysts and as reagents to replace other atoms or groups in organic compounds with F, Cl, Br, I, CN, NCO, NCS, NO2 or N3.
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