- High-Fidelity Sequence-Selective Duplex Formation by Recognition-Encoded Melamine Oligomers
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Melamine oligomers composed of repeating triazine-piperidine units and equipped with phenol and phosphine oxide side-chains form H-bonded duplexes. The melamine backbone provides sufficient rigidity to prevent intramolecular folding of oligomers up to thr
- Ballester, Pablo,Bolgar, Peter,Hunter, Christopher A.,Troselj, Pavle
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Read Online
- Discovery of tert-amine-based RORγt agonists
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The nuclear receptor retinoic acid receptor-related orphan receptor gamma-t (RORγt) is a transcription factor regulating Th17 cell differentiation and proliferation from naive CD4+ T cells. Since Th17 cells have demonstrated the antitumor efficacy by eliciting remarkable activation of CD8+ T cells, RORγt agonists could be applied as potential small molecule therapeutics for cancer immunotherapy. Based on the previously reported RORγt agonist 1 and its resolved co-crystal structure, a series of new tertiary amines were designed, synthesized and biologically evaluated, yielding optimal moieties with improved chemical properties and biological responses. The combination of these optimal moieties resulted in identification of novel RORγt agonists such as 8b with further elevated RORγt agonism responses at a target-based level as well as in cell-based assays, which provided some structural knowledge for further optimization of RORγt agonists as small molecule therapeutics for cancer immunotherapy.
- Qiu, Ruomeng,Yu, Mingcheng,Gong, Juwen,Tian, Jinlong,Huang, Yafei,Wang, Yonghui,Xie, Qiong
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- Continuous flow heterogeneous catalytic reductive aminations under aqueous micellar conditions enabled by an oscillatory plug flow reactor
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Despite the fact that continuous flow processing exhibits well-established technical advances, aqueous micellar chemistry, a field that has proven extremely useful in shifting organic synthesis to sustainable water-based media, has mostly been explored under conventional batch-based conditions. This is particularly because of the fact that the reliable handling of slurries and suspensions in flow has been considered as a significant technical challenge. Herein, we demonstrate that the strategic application of an oscillatory plug flow reactor enables heterogeneous catalytic reductive aminations in aqueous micellar media enhancing mass transport and facilitating process simplicity, stability and scalability. The micellar flow process enabled a broad range of substrates, including amino acid derivatives, to be successfully transformed under reasonably mild conditions utilizing only very low amounts of Pd/C as a readily available heterogeneous catalyst. The preparative capabilities of the process along with the recyclability of the heterogenous catalyst and the aqueous reaction media were also demonstrated. This journal is
- ?tv?s, Sándor B.,Buchholcz, Balázs,Darvas, Ferenc,Kappe, C. Oliver,Novák, Zoltán,Sipos, Gellért,Wernik, Michaela
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supporting information
p. 5625 - 5632
(2021/08/16)
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- Cine-Silylative Ring-Opening of α-Methyl Azacycles Enabled by the Silylium-Induced C-N Bond Cleavage
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Described herein is the development of a borane-catalyzed cine-silylative ring-opening of α-methyl azacycles. This transformation involves four-step cascade processes: (i) exo-dehydrogenation of alicyclic amine, (ii) hydrosilylation of the resultant enamine, (iii) silylium-induced cis-β-amino elimination to open the ring skeleton, and (iv) hydrosilylation of the terminal olefin. The present borane catalysis also works efficiently for the C-N bond cleavage of acyclic tertiary amines. On the basis of experimental and computational studies, the silicon atom was elucidated to play a pivotal role in the β-amino elimination step.
- Zhang, Jianbo,Chang, Sukbok
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supporting information
p. 12585 - 12590
(2020/08/21)
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- INHIBITORS OF INDOLEAMINE 2,3-DIOXYGENASE AND METHODS OF THEIR USE
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The present invention provides compounds of formula (I): wherein all of the variables are as defined herein. These compounds are inhibitors of indoleamine 2,3-dioxygenase (IDO), which may be used as medicaments for the treatment of proliferative disorders, such as cancer, viral infections and/or autoimmune diseases.
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Page/Page column 86-87
(2020/02/16)
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- Cross-linked cyclodextrins bimetallic nanocatalysts: Applications in microwave-assisted reductive aminations
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The optimization of sustainable protocols for reductive amination has been a lingering challenge in green synthesis. In this context, a comparative study of different metal-loaded cross-linked cyclodextrins (CDs) were examined for the microwave (MW)-assisted reductive amination of aldehydes and ketones using either H2 or formic acid as a hydrogen source. The Pd/Cu heterogeneous nanocatalyst based on Pd (II) and Cu (I) salts embedded in a β-CD network was the most efficient in terms of yield and selectivity attained. In addition, the polymeric cross-linking avoided metal leaching, thus enhancing the process sustainability; good yields were realized using benzylamine under H2. These interesting findings were then applied to the MW-assisted one-pot synthesis of secondary amines via a tandem reductive amination of benzaldehyde with nitroaromatics under H2 pressure. The formation of a CuxPdy alloy under reaction conditions was discerned, and a synergic effect due to the cooperation between Cu and Pd has been hypothesized. During the reaction, the system worked as a bifunctional nanocatalyst wherein the Pd sites facilitate the reduction of nitro compounds, while the Cu species promote the subsequent imine hydrogenation affording structurally diverse secondary amines with high yields.
- Acciardo, Elisa,Cravotto, Giancarlo,Gaudino, Emanuela Calcio,Manzoli, Maela,Tabasso, Silvia,Varma, Rajender S.
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- Tertiary amine derivative or salt thereof, preparation method and application thereof
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Belonging to the technical field of chemical medicine, the invention relates to a tertiary amine RORgamma t regulator, in particular to a new tertiary amine compound or salt thereof with RORgamma t inhibition or agonist activity shown as general formula I, a preparation method and a pharmaceutical composition thereof. The tertiary amine compound or a salt thereof provided by the invention can be used for preparation of drugs treating or preventing RORgamma t receptor related diseases.
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Paragraph 0260; 0263; 0264; 0265
(2019/01/24)
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- Metal- and Base-Free Room-Temperature Amination of Organoboronic Acids with N-Alkyl Hydroxylamines
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We have found that readily available N-alkyl hydroxylamines are effective reagents for the amination of organoboronic acids in the presence of trichloroacetonitrile. This amination reaction proceeds rapidly at room temperature and in the absence of added metal or base, it tolerates a remarkable range of functional groups, and it can be used in the late-stage assembly of two complex units.
- Sun, Hong-Bao,Gong, Liang,Tian, Yu-Biao,Wu, Jin-Gui,Zhang, Xia,Liu, Jie,Fu, Zhengyan,Niu, Dawen
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supporting information
p. 9456 - 9460
(2018/07/29)
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- Direct Reductive Amination of Carbonyl Compounds with H2 Using Heterogeneous Catalysts in Continuous Flow as an Alternative to N-Alkylation with Alkyl Halides
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A general continuous-flow procedure for direct reductive amination of secondary and primary amines with aromatic and aliphatic aldehydes as well as ketones is reported. The use of hydrogen gas and commercially available Pt/C as a heterogeneous catalyst is a key. In addition to exhibiting an excellent functional group tolerance, this method allows the fast formation of C?N bonds without production of any hazardous chemical waste. Applications to the synthesis of key intermediates toward active pharmaceutical ingredients (Donepezil and Arformoterol/Tamsulosin) are also described. (Figure presented.).
- Laroche, Benjamin,Ishitani, Haruro,Kobayashi, Shū
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supporting information
p. 4699 - 4704
(2018/12/04)
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- Efficient and Selective Hydrosilylation of Secondary and Tertiary Amides Catalyzed by an Iridium(III) Metallacycle: Development and Mechanistic Investigation
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Readily accessible cationic IrIII metallacycles catalyze efficiently the chemoselective hydrosilylation of tertiary and secondary amides to amines. The catalyst described herein operates at low loadings using inexpensive 1,1,3,3-tetramethyldisiloxane and allows fast reactions with high yields, selectivities, and turnover numbers. A transient iminium intermediate has been observed for the first time by using mass spectrometry, and the activation of the catalyst and the silane reagent have been studied by using DFT calculations. These fundamental insights support the present and future improvements of IrIII metallacycles through proper ligand modifications and enable further broad applications of catalysts based on metallacycles.
- Corre, Yann,Trivelli, Xavier,Capet, Frédéric,Djukic, Jean-Pierre,Agbossou-Niedercorn, Francine,Michon, Christophe
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p. 2009 - 2017
(2017/06/13)
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- Mild Metal-Free Hydrosilylation of Secondary Amides to Amines
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The combination of amide activation by Tf2O with B(C6F5)3-catalyzed hydrosilylation with TMDS constitutes a method for the one-pot reduction of secondary amides to amines under mild conditions. The method displays a broad applicability for the reduction of many types of substrates, and shows good compatibility and excellent chemoselectivity for many sensitive functional groups. Reductions of a multifunctionalized α,β-unsaturated amide obtained from another synthetic methodology, and a C-H functionalization product produced the corresponding amines in good to excellent yield. Chemoselective reduction of enantiomeric pure (ee >99%) tetrahydro-5-oxo-2-furaneamides yielded 5-(aminomethyl)dihydrofuran-2(3H)-ones in a racemization-free manner. The latter were converted in one pot to N-protected 5-hydroxypiperidin-2-ones, which are building blocks for the synthesis of many natural products. Further elaboration of an intermediate led to a concise four-step synthesis of -epi-pseudoconhydrine.
- Huang, Pei-Qiang,Lang, Qi-Wei,Wang, Yan-Rong
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p. 4235 - 4243
(2016/06/09)
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- Ultrasound-assisted solventless synthesis of amines by in situ oxidation/reductive amination of benzyl halides
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Ultrasound-assisted solventless oxidation/reductive amination of benzyl halides was developed as a facile, efficient, and environmental friendly method toward N-alkylated amines. Aldehydes were formed in situ by oxidation of organic halides with N-methylmorpholine N-oxide (NMO), followed by direct reductive amination with amines using sodium borohydride and montmorillonite K-10 catalyst as the reducing system. This green and simple procedure enables N-alkylated amines to be prepared in good to excellent yields with high selectivity of the monoalkylation. This journal is the Partner Organisations 2014.
- Khumraksa, Bannarak,Phakhodee, Wong,Pattarawarapan, Mookda
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p. 20454 - 20458
(2014/06/09)
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- Pt/C catalysed direct reductive amination of nitriles with primary amines in a continuous flow multichannel microreactor
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Aliphatic and aromatic secondary amines were synthesised selectively by one pot reductive amination of nitriles with primary amines using Pt/C (3% by weight) catalyst in a continuous flow multichannel microreactor. Molecular hydrogen was used as a clean reducing agent at moderate reaction conditions. The Royal Society of Chemistry 2013.
- Sharma, Sumeet K.,Lynch, James,Sobolewska, Anna M.,Plucinski, Pawel,Watson, Robert J.,Williams, Jonathan M. J.
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- Synthesis of α-amino acids through samarium(II) iodide promoted reductive coupling of nitrones with CO2
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Several N-benzylnitrones reacted with carbon dioxide in the presence of samarium(II) iodide leading to α-amino acids as the products of reductive C-C coupling. The best selectivities were observed at a carbon dioxide pressure of 50 bar at ambient temperature. The influences of different functional groups in the nitrone backbone and of the coordinating additives to samarium(II) iodide on the product distribution were investigated. The racemic α-amino acids were obtained in up to 70% yield based on HPLC data. A novel approach to the synthesis ofα-amino acids is disclosed, involvingC-carboxylation of nitrones by gaseous CO2 under reductive coupling reaction conditions (SmI2, 0.1 M in THF) at ambient temperature and 50 bar of CO 2 pressure. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
- Prikhod'Ko, Alexander,Walter, Olaf,Zevaco, Thomas A.,Garcia-Rodriguez, Jaime,Mouhtady, Omar,Py, Sandrine
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supporting information; experimental part
p. 3742 - 3746
(2012/09/25)
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- PROCESS FOR THE PREPARATION OF (3R,3AS,6AR)-HEXAHYDROFURO [2,3-B] FURAN-3-YL (1S,2R)-3-[[(4-AMINOPHENYL) SULFONYL] (ISOBUTYL) AMINO]-1-BENZYL-2-HYDROXYPROPYLCARBAMATE
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The present invention relates to a process for the preparation of (3R,3a S,6aR)-hexa-hydrofuro [2,3-b] furan-3-yl (1S,2R)-3-[[(4-aminophenyl) sulfonyl] (isobutyl) amino]-1-benzyl-2-hydroxypropylcarbamate as well as novel intermediates for use in said process. (3R,3a S,6aR)-hexahydrofuro [2,3-b] furan-3-yl (1S,2R)-3-[[(4-aminophenyl) sulfonyl] (isobutyl) amino]-1-benzyl-2-hydroxypropylcarbamate is particularly useful as an HIV protease inhibitor.
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Page/Page column 27
(2010/04/06)
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- Hydroamination of carbonyl compounds with oximes
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N-alkyl(cycloalkyl)benzylamines, p-fluorobenzylamines, (1-phenylethyl) amines, [1-(p-fluorophenyl)ethyl]amines were synthesized by hydroamination of aldehydes and ketones with oximes.
- Tarasevich,Kozlov
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p. 379 - 383
(2007/10/03)
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- A one-pot oxidation-imine formation-reduction route from alcohols to amines using manganese dioxide-sodium borohydride: The synthesis of naftifine
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A new procedure for the one-pot conversion of alcohols into amines is described which utilises manganese dioxide in the presence of sodium borohydride; the scope of this process is outlined, as is its application to the preparation of the topical antifungal agent, naftifine.
- Kanno, Hisashi,Taylor, Richard J.K.
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p. 7337 - 7340
(2007/10/03)
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- In Situ Oxidation-Imine Formation-Reduction Routes from Alcohols to Amines
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(matrix presented) Manganese dioxide is employed as an in situ oxidant for the one-pot conversion of alcohols into imines. In combination with polymer-supported cyanoborohydride (PSCBH), a one-pot oxidation-imine formation-reduction sequence is reported. This procedure enables alcohols to be converted directly into both secondary and tertiary amines.
- Blackburn, Leonie,Taylor, Richard J. K.
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p. 1637 - 1639
(2007/10/03)
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- Reduction of imines via titanium-catalyzed hydromagnesation
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We have recently discovered that imines can be reduced to amines via a titanium catalyzed hydromagnesation reaction. These reactions employ n-BuMgCl (1.2 eq) as the stoichiometric reducing agent and Cp2TiCl2 (3-5 mol%) as a catalyst. Reactions are run under nitrogen at ambient temperature and pressure. For most aldimine and cyclic ketimine substrates amine products are obtained in yields ranging from 69-94%. The reaction is not tolerant of bulky nitrogen substituents or primary enolizable protons on the imine substrate.
- Amin, Sk. Rasidul,Crowe, William E.
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p. 7487 - 7490
(2007/10/03)
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- N-Benzyltriflamide: a Generally Useful Mitsunobu Reagent for Amine Synthesis
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N-Benzyl triflamide has been found to be generally useful as a Mitsunobu nucleophile for the preparation of a range of primary and secondary benzylamines from the corresponding alcohols, using the standard reagents DEAD and triphenylphosphine.
- Kathryn, E. Bell,Knight, David W.,Gravestock, Michael B.
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p. 8681 - 8684
(2007/10/02)
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- THE CHEMISTRY OF BENZOTRIAZOLE. PART 8. A NOVEL TWO-STEP PROCEDURE FOR THE N-ALKYLATION OF AMIDES
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Benzotriazole, aldehydes RCHO, and amides R1CONH2 react together with elimination of water to form 1:1:1 adducts which are reduced smoothly by NaBH4 to give the N-substituted amides R1CONHCH2R.Both steps occur in high yields and can be carried out on a large scale, thus comprising a convenient general method for the N-alkylation of amides.
- Katritzky, Alan R.,Drewniak, Malgorzata
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p. 2339 - 2344
(2007/10/02)
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- DIAMINO KETONES AND ALCOHOLS AS ANALGESIC AGENTS
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Analgesic activity is exhibited by compounds having the formula STR1 and pharmaceutically acceptable salts thereof wherein R. sub.1, R. sub.2 and R 4 are each independently hydrogen, alkyl, carboxyalkyl, halosubstituted alkyl, hydroxyalkyl, aminoalkyl, me
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- The Reduction of β-Iminoketones
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The reduction of N-substituted 3-imino-2,2-dimethyl-1-phenylpropan-1-ones and N-substituted 3-imino-2,2-dimethyl-1-phenylbutan-1-ones is reported.Catalytic hydrogenation with palladium led mainly to the related aminoketones in the case of the propanone derivatives.No reduction was observed for butanone derivatives.Both propanone and butanone derivatives were reduced to the related aminoalcohols by lithium aluminium hydride, the reaction being highly stereoselective in the latter case.When using sodium borohydride as the reducing agent, fragmentation was observed with the formation of mixtures of products from which, in favourable cases, benzyl alcohol and N-substituted alkyl amines were isolated.All of these results are discussed and interpreted.
- Armesto, Diego,Perez-Ossorio, Rafael,Plumet, Joaquin,Ramos, Ana
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p. 901 - 914
(2007/10/02)
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- Preparation of amines by the reduction of imines with phosphorous acid
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This invention relates to the preparation of amines by the reduction of imines with phosphorous acid, preferably under basic conditions.
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- α-Amino phosphonic acids
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This invention relates to the preparation of α-amino phosphonic acids by the direct addition of phosphorous acid to imines.
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