- Transition metal-free, chemoselective arylation of thioamides yielding aryl thioimidates or N-aryl thioamides
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Reactions of secondary thioamides with diaryliodonium salts under basic, transition metal-free conditions resulted in chemoselective S-arylation to provide aryl thioimidates in good to excellent yields. Equimolar amounts of thioamide, base and diaryliodonium salt were sufficient to obtain a diverse selection of products within short reaction times. Reactions with thiolactams delivered N-arylated thioamides in good yield at room temperature.
- Villo, Piret,Kervefors, Gabriella,Olofsson, Berit
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supporting information
p. 8810 - 8813
(2018/08/17)
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- Unique physicochemical and catalytic properties dictated by the B3NO2 ring system
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The expansion of molecular diversity beyond what nature can produce is a fundamental objective in chemical sciences. Despite the rich chemistry of boron-containing heterocycles, the 1,3-dioxa-5-aza-2,4,6-triborinane (DATB) ring system, which is characterized by a six-membered B3NO2 core, remains elusive. Here, we report the synthesis of m-terphenyl-templated DATB derivatives, displaying high stability and peculiar Lewis acidity arising from the three suitably arranged boron atoms. We identify a particular utility for DATB in the dehydrative amidation of carboxylic acids and amines, a reaction of high academic and industrial importance. The three boron sites are proposed to engage in substrate assembly, lowering the entropic cost of the transition state, in contrast with the operative mechanism of previously reported catalysts and amide coupling reagents. The distinct mechanistic pathway dictated by the DATB core will advance not only such amidations, but also other reactions driven by multisite activation.
- Noda, Hidetoshi,Furutachi, Makoto,Asada, Yasuko,Shibasaki, Masakatsu,Kumagai, Naoya
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p. 571 - 577
(2017/06/01)
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- Pathways in the Degradation of Geminal Diazides
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The degradation of geminal diazides is described. We show that diazido acetates are converted into tetrazoles through the treatment with bases. The reaction of dichloro ketones with azide anions provides acyl azides, through in situ formation of diazido ketones. We present experimental and theoretical evidence that both fragmentations may involve the generation of acyl cyanide intermediates. The controlled degradation of terminal alkynes into amides (by loss of one carbon) or ureas (by loss of two carbons) is also shown.
- Holzschneider, Kristina,H?ring, Andreas P.,Haack, Alexander,Corey, Daniel J.,Benter, Thorsten,Kirsch, Stefan F.
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p. 8242 - 8250
(2017/08/14)
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- Selective Palladium-Catalyzed Aminocarbonylation of Olefins to Branched Amides
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A general and efficient protocol for iso-selective aminocarbonylation of olefins with aliphatic amines has been developed for the first time. Key to the success for this process is the use of a specific 2-phosphino-substituted pyrrole ligand in the presence of PdX2(X=halide) as a pre-catalyst. Bulk industrial and functionalized olefins react with various aliphatic amines, including amino-acid derivatives, to give the corresponding branched amides generally in good yields (up to 99 %) and regioselectivities (b/l up to 99:1).
- Liu, Jie,Li, Haoquan,Spannenberg, Anke,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 13544 - 13548
(2016/10/21)
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- One-Pot Amide Bond Formation from Aldehydes and Amines via a Photoorganocatalytic Activation of Aldehydes
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A mild, one-pot, and environmentally friendly synthesis of amides from aldehydes and amines is described. Initially, a photoorganocatalytic reaction of aldehydes with di-isopropyl azodicarboxylate leads to an intermediate carbonyl imide, which can react with a variety of amines to afford the desired amides. The initial visible light-mediated activation of a variety of monosubstituted or disubstituted aldehydes is usually fast, occurring in a few hours. Following the photocatalytic reaction, addition of the primary amine at room temperature or the secondary amine at elevated temperatures leads to the corresponding amide from moderate to excellent yields without epimerization. This methodology was applied in the synthesis of Moclobemide, a drug against depression and social anxiety.
- Papadopoulos, Giorgos N.,Kokotos, Christoforos G.
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p. 7023 - 7028
(2016/08/30)
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- Catalytic chemical amide synthesis at room temperature: One more step toward peptide synthesis
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An efficient method has been developed for direct amide bond synthesis between carboxylic acids and amines via (2-(thiophen-2-ylmethyl)phenyl)boronic acid as a highly active bench-stable catalyst. This catalyst was found to be very effective at room temperature for a large range of substrates with slightly higher temperatures required for challenging ones. This methodology can be applied to aliphatic, α-hydroxyl, aromatic, and heteroaromatic acids as well as primary, secondary, heterocyclic, and even functionalized amines. Notably, N-Boc-protected amino acids were successfully coupled in good yields with very little racemization. An example of catalytic dipeptide synthesis is reported.
- Mohy El Dine, Tharwat,Erb, William,Berhault, Yohann,Rouden, Jacques,Blanchet, Jér?me
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p. 4532 - 4544
(2015/05/13)
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- Catalyst and method for producing the same
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PROBLEM TO BE SOLVED: To provide a method for producing an amide compound from a primary alcohol and at least one selected from a primary amine, a secondary amine and derivatives of those under relatively mild conditions with high selectivity and a high conversion ratio.SOLUTION: A method for producing an amide compound comprises a step of obtaining the amide compound from a primary alcohol and at least one selected from a primary amine, a secondary amine and derivatives of those, in the presence of a catalyst comprising a carrier formed by crosslinking a crosslinkable functional group of a styrene-based polymer having a side chain containing the crosslinkable functional group, and a nanosize cluster and carbon black supported on the carrier, wherein the nanosize cluster is at least one selected from a nanosize gold cluster and a nanosize cluster of gold and at least one group 8 metal selected from iron, cobalt and nickel.
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-
Paragraph 0074; 0082; 0083
(2016/11/07)
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- AIBN-initiated metal free amidation of aldehydes using N-chloroamines
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An efficient and environmentally benign amidation of aldehydes with N-chloroamines has been developed using AIBN as an initiator. This methodology offers a metal free and base free approach and is endowed with mild reaction conditions, high yields, and good functional group tolerance.
- Vanjari, Rajeshwer,Guntreddi, Tirumaleswararao,Singh, Krishna Nand
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p. 351 - 356
(2014/01/06)
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- Catalytic acylation of amines with aldehydes or aldoximes
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The simple nickel salt NiCl2?6H2O catalyzes the coupling of aldoximes with amines to give secondary or tertiary amide products. The aldoxime can be prepared in situ from the corresponding aldehyde. The use of 18O-labeled oximes has allowed insight into the mechanism of this reaction.
- Allen, C. Liana,Davulcu, Simge,Williams, Jonathan M. J.
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supporting information; experimental part
p. 5096 - 5099
(2011/02/21)
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- Direct and waste-free amidations and cycloadditions by organocatalytic activation of carboxylic acids at room temperature
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(Chemical Equation Presented) Taming carboxylic acids: ortho-Iodo- and ortho-bromophenylboronic acids are exceptional organocatalysts in atom-economical amidations between free carboxylic acids and amines, including functionalized ones, and can also provide LUMO-lowering activation in [4 + 2] cycloadditions of α,β-unsaturated carboxylic acids.
- Al-Zoubi, Raed M.,Marion, Olivier,Hall, Dennis G.
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supporting information; experimental part
p. 2876 - 2879
(2009/02/06)
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- Catalytic metathesis of simple secondary amides
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(Chemical Equation Presented) Trading places: The metathesis of secondary amides through a transacylation mechanism has been achieved by employing catalytic quantities of an organic imide and a Bronsted base (see scheme). Equilibrium-controlled exchange between various amide pairs is demonstrated for substrates bearing N-alkyl and N-aryl substituents.
- Bell, Christen M.,Kissounko, Denis A.,Gellman, Samuel H.,Stahl, Shannon S.
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p. 761 - 763
(2007/10/03)
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- Intramolecular and intermolecular Schmidt reactions of alkyl azides with aldehydes
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Despite recent advances in the use of alkyl azides in ring expansion reactions of ketones, there has been little work done on the corresponding chemistry of aldehydes. In the present study, the Lewis acid-promoted reactions of alkyl azides with aldehydes
- Lee, Huey-Lih,Aubé, Jeffrey
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p. 9007 - 9015
(2008/02/10)
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- TiIV-mediated reactions between primary amines and secondary carboxamides: Amidine formation versus transamidation
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Titanium(IV)-mediated reactions between primary amines and secondary carboxamides exhibit different outcomes, amidine formation versus transamidation, depending on the identity of the TiIV complex used and the reaction conditions employed. The present study probes the origin of this divergent behavior. We find that stoichiometric TiIV, either Cp*TiIV complexes or Ti(NMe2)4, promotes formation of amidine and oxotitanium products. Under catalytic conditions, however, the outcome depends on the identity of the TiIV complex. Competitive amidine formation and transamidation are observed with Cp*TiIV complexes, generally favoring amidine formation. In contrast, the use of catalytic Ti(NMe2)4 (≤20 mol %) results in highly selective transamidation. The ability of TiIV to avoid irreversible formation of oxotitanium products under the latter conditions has important implications for the use of TiIV in catalytic reactions.
- Kissounko, Denis A.,Hoerter, Justin M.,Guzei, Ilia A.,Cui, Qiang,Gellman, Samuel H.,Stahl, Shannon S.
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p. 1776 - 1783
(2007/10/03)
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- Catalytic transamidation and amide metathesis under moderate conditions
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Disclosed is a method of manipulating the carboxamide functionality in a catalytic manner. The method includes the steps of reacting amides with or without amines in the presence of various types of metal catalysts, at a temperature of about 250° C. or less.
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Page 2-3; Sheet 1; Sheet 2
(2008/06/13)
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- Platinum catalysed hydrolytic amidation of unactivated nitriles
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The platinum(II) complex, [(Me2PO··H··OPMe2)PtH(PMe2OH)], efficiently catalyses the direct conversion of unactivated nitriles to N- substituted amides with both primary and secondary amines. Possible mechanisms for this reaction are discussed and evidence for initial amidine formation is reported. Isolated yields vary from 51-89%. (C) 2000 Elsevier Science Ltd.
- Cobley, Christopher J.,Van Den Heuvel, Marco,Abbadi, Abdelilah,De Vries, Johannes G.
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p. 2467 - 2470
(2007/10/03)
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- Solid-supported chloro[1,3,5]triazine. A versatile new synthetic auxiliary for the synthesis of amide libraries
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(equation presented) 2,4,6-Trichloro[1,3,5]triazine was loaded on different types of NH2-functionalized resins to give a new supported reagent. The best results, in term of yields products, were obtained using the chlorotriazine linked to a polystyrene-poly(ethylene glycol) resin. This reagent was employed for the solution-phase synthesis of different amides and dipeptides.
- Masala, Simonetta,Taddei, Maurizio
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p. 1355 - 1357
(2008/02/09)
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- Charge-directed conjugate addition reactions of silylated α-β- unsaturated amidate anions
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A variety of N-substituted α-silylated-α,β-unsaturated amidate anions (2) have been found to be excellent Michael acceptors in charge-directed conjugate addition reactions with Grignard and organolithium reagents. The effects of olefin substitution, Si-substitution, N-substitution, and amidate counterion have been studied. Anionic acceptors may be prepared in situ by the addition of silylated vinyllithium reagents to isocyanates and then allowed to undergo conjugate addition reactions with subsequently added nucleophiles, but it was found to be more efficient to isolate neutral acceptors and regenerate the acceptor anion through the use of excess nucleophile. β-Substituted acceptors were found to react only with reactive organolithium reagents while a β,β-disubstituted acceptor failed to undergo conjugate addition reactions. A primary amide acceptor (14d) also undergoes addition reactions with larger quantitites of nucleophiles suggesting that dianionic amidate acceptors (31) are involved. Diene acceptor 24 was found to undergo a 1,6-addition reaction with n-BuLi. Sodium and potassium amidate salts were found to be inferior to lithium and magnesium salts in addition reactions in keeping with the expectation that an increase in carbonyl-group charge burden retards conjugate reactions. Triphenylsilyl-containing acceptor 16 was found to be more reactive in reactions with n-BuMgCl but less reactive with bulkier tert-BuMgCl. Adduct dianions can be monoalkylated with alkyl iodides and used in Peterson olefination reactions.
- Cooke Jr.,Pollock
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p. 7474 - 7481
(2007/10/02)
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- Dodecacarbonyltriruthenium catalyzed one-to-one addition of N-substituted formamides to olefins
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Dodecacarbonyltriruthenium (Ru3(CO)12) showed high catalyitic activity for the first one-to-one addition of N-substituted formamides to both terminal and internal olefins at 180-200 deg C under a carbon monoxide pressure of 20 kg cm-2.The addit
- Tsuji, Yasushi,Yoshii, Seiji,Ohsumi, Tatsuya,Kondo, Teruyuki,Watanabe, Yoshihisa
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p. 379 - 386
(2007/10/02)
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