- A Titanium-Catalyzed Reductive α-Desulfonylation
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A titanium(III)-catalyzed desulfonylation gives access to functionalized alkyl nitrile building blocks from α-sulfonyl nitriles, circumventing traditional base-mediated α-alkylation conditions and strong single electron donors. The reaction tolerates numerous functional groups including free alcohols, esters, amides, and it can be applied also to the α-desulfonylation of ketones. In addition, a one-pot desulfonylative alkylation is demonstrated. Preliminary mechanistic studies indicate a catalyst-dependent mechanism involving a homolytic C?S cleavage.
- Kern, Christoph,Selau, Jan,Streuff, Jan
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p. 6178 - 6182
(2021/03/16)
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- Nickel/Cobalt-Catalyzed Reductive Hydrocyanation of Alkynes with Formamide as the Cyano Source, Dehydrant, Reductant, and Solvent
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A Ni/Co co-catalyzed reductive hydrocyanation of various alkynes was developed for the production of saturated nitriles. Hydrocyanic acid is generated in situ from safe and readily available formamide. Formamide played multiple roles as a cyano source, dehydrant, and reductant for the NiII pre-catalyst and vinyl nitriles, along with acting as the co-solvent in this reaction. Detailed mechanistic investigation supported a pathway via hydrocyanation of C≡C bond and the subsequent reduction of C=C bond. Wide substrate scope, the employment of a cheap and stable nickel salt as pre-catalyst, a safe cyano source and convenient experimental operation render this hydrocyanation practical for the laboratory synthesis of saturated nitriles. (Figure presented.).
- Zhang, Jin,Luo, Cui-Ping,Yang, Luo
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supporting information
p. 283 - 288
(2020/12/01)
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- Visible- And UV-Light-Induced Decarboxylative Radical Reactions of Benzoic Acids Using Organic Photoredox Catalysts
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Photoinduced decarboxylative radical reactions of benzoic acids with electron-deficient alkenes, diborane, and acetonitrile under organic photoredox catalysis conditions and mild heating afforded adducts, arylboronate esters, and the reduction product, respectively. The reaction is thought to involve single-electron transfer promoted the generation of aryl radicals via decarboxylation. A diverse range of benzoic acids were found to be suitable substrates for this photoreaction. Only our two-molecule organic photoredox system can work well for the direct photoinduced decarboxylation of benzoic acids.
- Kubosaki, Suzuka,Takeuchi, Haruka,Iwata, Yutaka,Tanaka, Yosuke,Osaka, Kazuyuki,Yamawaki, Mugen,Morita, Toshio,Yoshimi, Yasuharu
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p. 5362 - 5369
(2020/05/19)
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- Transition-metal-free Intramolecular C-H amination of sulfamate esters and: N -alkylsulfamides
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The transition-metal-free intramolecular C-H amination of sulfamate esters using iodine oxidants, tert-butyl hypoiodite (t-BuOI) and N-iodosuccinimide (NIS) is reported. A method using NIS was also successfully applied to the oxidative cyclization of N-alkylsulfamides.
- Kiyokawa, Kensuke,Nakamura, Shogo,Jou, Keisuke,Iwaida, Kohji,Minakata, Satoshi
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p. 11782 - 11785
(2019/10/02)
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- Synthesis of Nitriles from Aldehydes with Elongation of the Molecule with Two Carbon Atoms
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A new protocol for the synthesis of nitriles from carbonyl compounds with elongation of the molecule with two carbon atoms was developed. It involves a reaction of ethyl cyanoacetate with different aldehydes in the presence of iron pentacarbonyl as a redu
- Afanasyev, Oleg I.,Zarochintsev, Alexander,Petrushina, Tatiana,Cherkasova, Anastasia,Denisov, Gleb,Cherkashchenko, Ilia,Chusova, Olga,Jinho, Oh,Man-Seog, Chun,Usanov, Dmitry L.,Semenov, Sergei E.,Chusov, Denis
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supporting information
p. 32 - 35
(2018/12/05)
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- A strategy for generating aryl radicals from arylborates through organic photoredox catalysis: Photo-Meerwein type arylation of electron-deficient alkenes
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Photoinduced reactions of arylboronic acids with electron deficient alkenes under mild organic photoredox catalysis conditions lead to the formation of Meerwein arylation type adducts via the generation of aryl radicals.
- Iwata,Tanaka,Kubosaki,Morita,Yoshimi
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supporting information
p. 1257 - 1260
(2018/02/09)
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- Formal reductive addition of acetonitrile to aldehydes and ketones
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An efficient and highly productive rhodium-catalyzed method for the synthesis of nitriles employing aldehydes or ketones, methyl cyanoacetate, water and carbon monoxide as starting materials has been developed. Simple rhodium chloride without any ligands can be used. The fine tuning of the substrate can lead to the activity higher than 5000 TON.
- Muratov, Karim,Kuchuk, Ekaterina,Vellalath, Sreekumar,Afanasyev, Oleg I.,Moskovets, Alexei P.,Denisov, Gleb,Chusov, Denis
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supporting information
p. 7693 - 7701
(2018/11/02)
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- Tris(trimethylsilyl)silane-mediated reductive decyanation and cyano transfer reactions of malononitriles
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Reductive decyanation reactions of malononitriles were achieved with tris(trimethylsilyl)silane as a radical mediator. The reaction proceeds via a radical chain mechanism involving a silyl radical addition to the malononitrile to form an imidoyl radical followed by α-cleavage to give a silyl isocyanide and an α-cyano radical. The reaction of a 3-butenyl-substituted malononitrile afforded a decyano/cyanosilylation product in good yield through 1,4-cyano transfer.
- Kawamoto, Takuji,Shimaya, Yudai,Curran, Dennis P.,Kamimura, Akio
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supporting information
p. 573 - 575
(2018/04/12)
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- Deboronative cyanation of potassium alkyltrifluoroborates: Via photoredox catalysis
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A photoredox catalytic method was developed for the direct cyanation of alkyltrifluoroborates. This reaction provides a new and useful transformation of the easily available alkyltrifluoroborates. The photocatalytic reaction can tolerate a variety of functional groups with mild reaction conditions. Mechanistic investigations are consistent with the present reaction following a radical pathway.
- Dai, Jian-Jun,Zhang, Wen-Man,Shu, Yong-Jin,Sun, Yu-Yang,Xu, Jun,Feng, Yi-Si,Xu, Hua-Jian
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p. 6793 - 6796
(2016/06/01)
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- Efficient nickel-catalyzed hydrocyanation of alkenes using acetone cyanohydrin as a safer cyano source
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An active nickel catalyst prepared in situ from a Ni(II) compound, phosphine ligand, and zinc powder was found to be an efficient catalyst system for the hydrocyanation of various alkenes using acetone cyanohydrin as a safer cyano source. The combination of NiCl2·6H2O and 1,3-bis(diphenylphosphino)propane was the most efficient catalyst precursor in DMF. Under the optimized conditions, various styrenes, heterocyclic alkenes, and aliphatic alkenes were converted to their corresponding nitriles in excellent yields.
- Nemoto, Koji,Nagafuchi, Tsuyoshi,Tominaga, Ken-ichi,Sato, Kazuhiko
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p. 3199 - 3203
(2016/07/06)
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- Radical Reactions of N -Heterocyclic Carbene Boranes with Organic Nitriles: Cyanation of NHC-Boranes and Reductive Decyanation of Malononitriles
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The observation that NHC-boryl radicals abstract cyano groups from various organic nitriles has been parlayed into two complementary transformations. In the main group chemistry aspect, reactions of various NHC-boranes with simple organic dinitriles selectively provide stable NHC-boryl mono- or dinitriles, depending on the nitrile source. In the organic synthesis aspect, reaction of malononitriles and related derivatives with readily available 1,3-dimethylimidazol-2-ylidene borane provides reductively decyanated products in good yields.
- Kawamoto, Takuji,Geib, Steven J.,Curran, Dennis P.
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supporting information
p. 8617 - 8622
(2015/07/15)
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- Indium(III)-catalyzed one-pot synthesis of alkyl cyanides from carboxylic Acids
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The one-pot preparation of alkyl cyanides from carboxylic acids via alkyl iodides or alkyl bromides, which were in situ generated either by indium(III)-catalyzed reductive iodination or bromination of carboxylic acids, is described. Georg Thieme Verlag Stuttgart New York.
- Moriya, Toshimitsu,Shoji, Kohei,Yoneda, Shinichiro,Ikeda, Reiko,Konakahara, Takeo,Sakai, Norio
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p. 3233 - 3238
(2013/12/04)
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- Degradation of MAC13243 and studies of the interaction of resulting thiourea compounds with the lipoprotein targeting chaperone LolA
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The discovery of novel small molecules that function as antibacterial agents or cellular probes of biology is hindered by our limited understanding of bacterial physiology and our ability to assign mechanism of action. We previously employed a chemical genomic strategy to identify a novel small molecule, MAC13243, as a likely inhibitor of the bacterial lipoprotein targeting chaperone, LolA. Here, we report on the degradation of MAC13243 into the active species, S-(4-chlorobenzyl)isothiourea. Analogs of this compound (e.g., A22) have previously been characterized as inhibitors of the bacterial actin-like protein, MreB. Herein, we demonstrate that the antibacterial activity of MAC13243 and the thiourea compounds are similar; these activities are suppressed or sensitized in response to increases or decreases of LolA copy number, respectively. We provide STD NMR data which confirms a physical interaction between LolA and the thiourea degradation product of MAC13243, with a K d of ~150 μM. Taken together, we conclude that the thiourea series of compounds share a similar cellular mechanism that includes interaction with LolA in addition to the well-characterized target MreB.
- Barker, Courtney A.,Allison, Sarah E.,Zlitni, Soumaya,Nguyen, Nick Duc,Das, Rahul,Melacini, Giuseppe,Capretta, Alfredo A.,Brown, Eric D.
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supporting information
p. 2426 - 2431
(2013/05/21)
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- Monoalkylation of acetonitrile by primary alcohols catalyzed by iridium complexes
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The monoalkylation of acetonitrile by primary alcohols was achieved in a one-pot sequence in the presence of iridium catalysts. A diversity of nitriles has been obtained from aryl- and alkyl-methanols in excellent yield.
- Anxionnat, Bruno,Gomez Pardo, Domingo,Ricci, Gino,Cossy, Janine
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supporting information; experimental part
p. 4084 - 4087
(2011/09/21)
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- Design, synthesis, and biological evaluation of indole derivatives as novel nociceptin/orphanin FQ (N/OFQ) receptor antagonists
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A novel series of 2-(1,2,4-oxadiazol-5-yl)-1H-indole derivatives as nociceptin/orphanin FQ (N/OFQ) receptor antagonists was discovered. Systematic modification of our original lead by changing the pendant functional groups, linker, heterocyclic core, and
- Sugimoto, Yuichi,Shimizu, Atsushi,Kato, Tetsuya,Satoh, Atsushi,Ozaki, Satoshi,Ohta, Hisashi,Okamoto, Osamu
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p. 3569 - 3573
(2007/10/03)
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- Borrowing hydrogen: Indirect "Wittig" olefination for the formation of C-C bonds from alcohols
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The successful development of an indirect three-step domino sequence for the formation of C-C bonds from alcohol substrates is described. An iridium-catalysed dehydrogenation of alcohol 1 affords the intermediate aldehyde 2. The desired C-C bond can then be formed by a facile Wittig olefination, yielding the intermediate alkene 3. In the final step the alkene is hydrogenated to afford the indirect Wittig product, the alkane 4. The key to this process is the concept of borrowing hydrogen; hydrogen removed in the initial dehydrogenation step is simply borrowed by the iridium catalyst. Functioning as a hydrogen reservoir, the catalyst facilitates C-C bond formation before subsequently returning the borrowed hydrogen in the final step. Herein we present full details of our examination into both the substrate and reaction scope and the limitations of the catalytic cycle. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Black, Phillip J.,Edwards, Michael G.,Williams, Jonathan M. J.
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p. 4367 - 4378
(2007/10/03)
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- Catalytic electronic activation: Indirect "Wittig" reaction of alcohols
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Hydrogen atoms are borrowed during the in situ oxidation of the starting alcohol to the corresponding aldehyde and are subsequently returned in the hydrogenation of the alkene intermediate, which is formed by Wittig olefination of the aldehyde. This proce
- Edwards, Michael G.,Williams, Jonathan M.J.
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p. 4740 - 4743
(2007/10/03)
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- One-step conversion of alcohols into nitriles with simultaneous two-carbon chain elongation. (Cyanomethyl)trimethylphosphonium iodide as a reagent with a dual mode of action
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Treatment of alcohols with an excess of (cyanomethyl)trimethylphosphonium iodide leads, after aqueous hydrolysis, to the clean formation of nitriles with two more carbon atoms than present in the original alcohol. Benzylic, allylic, and aliphatic alcohols without β-branching (RCH2- CH2OH) have been converted to nitriles with success. The required phosphonium iodide is simple to prepare and can be stored for a long time at room temperature.
- Zaragoza, Florencio
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p. 4963 - 4964
(2007/10/03)
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- The novel preparation of hydrocinnamonitriles via the reduction of α- phenylsulfonyl cinnamonitriles with SmI2/CH3OH/THF system
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Hydrocinnamonitriles were readily obtained via the reduction of α- phenylsulfonyl cinnamonitriles by SmI2/CH3OH/THF system.
- Guo, Hongyun,Zhang, Yongmin
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p. 1879 - 1885
(2007/10/03)
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- Structure-based design of inhibitors of purine nucleoside phosphorylase. 1. 9-(Arylmethyl) derivatives of 9-deazaguanine
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Purine nucleoside phosphorylase (PNP, EC 2.4.2.1) is a salvage enzyme important to the T-cell-mediated part of the immune system and as such is an important therapeutic target. This paper describes the design, synthesis, and enzymatic evaluation of potent, competitive inhibitors of PNP. Potential inhibitors were designed using the three-dimensional structure of the enzyme in an iterative process that involved interactive computer graphics to model the native enzyme and complexes of it with the inhibitors, Monte Carlo-based conformational searching, and energy minimization. Studies of the enzyme/inhibitor complexes were used to determine priorities of the synthetic efforts. The resulting compounds were then evaluated by determination of their IC50 values and by X-ray diffraction analysis using difference Fourier maps. In this manner, we have developed a series of 9-(arylmethyl)- 9-deazapurines (2-amino-7-(arylmethyl)-4H-pyrrolo[3,2-d]-pyrimidin-4-ones) that are potent, membrane-permeable inhibitors of the enzyme. The IC50 values of these compounds range from 17 to 270 nM (in 1 mM phosphate), with 9-(3,4-dichlorobenzyl)-9-deazaguanine being the most potent inhibitor. X-ray analysis explained the role of the aryl groups and revealed the rearrangement of hydrogen bonds in the binding of the 9-deazaguanines in the active site of PNP relative to the binding of the 8-aminoguanines that results in more potent inhibition of the enzyme.
- Montgomery,Niwas,Rose,Secrist III,Babu,Bugg,Erion,Guida,Ealick
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