- Development of a triazinedione-based dehydrative condensing reagent containing 4-(dimethylamino)pyridine as an acyl transfer catalyst
-
A new triazinedione-based reagent, (N,N′-dialkyl)triazinedione-4-(dimethylamino)pyridine (ATD-DMAP) was developed for the operationally simple dehydrative condensation of carboxylic acids. This reagent comprises an ATD core and DMAP as the leaving group, which is liberated into the reaction system to accelerate acyl transfer reactions. Upon adding ATD-DMAP to a mixture of carboxylic acids and alcohols in the presence of an amine base, the corresponding esters were formed rapidly at room temperature. Moreover, dehydrative condensation between carboxylic acids and amines using ATD-DMAP proceeded in high yield.
- Liu, Jie,Fujita, Hikaru,Kitamura, Masanori,Shimada, Daichi,Kunishima, Munetaka
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supporting information
p. 4712 - 4719
(2021/06/11)
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- Water-soluble alkyne amide condensing agent as well as preparation method and application thereof
-
The invention discloses a water-soluble alkyne amide condensing agent and an application method of the water-soluble alkyne amide condensing agent in synthesis of amide, polypeptide, ester and thioester compounds. The alkyne amide condensing agent has good performance and can efficiently and conveniently promote formation of amide bonds and ester bonds, alpha-chiral centers of carboxylic acid is free of racemization in the reaction process, carboxylic acid activation and a subsequent amidation reaction can be performed spontaneously, and extra additives and catalysts are not needed. After amidation and esterification reactions are finished, reaction by-products and the excessive alkyne amide condensing agent can be converted into substances capable of being dissolved in water through treatment by a weakly-acidic aqueous solution, and then high-purity products can be obtained through extraction and/or recrystallization. The whole process is simple to operate, has the characteristics ofconvenience in purification, wide application range, economic performance and environmental protection, conforms to the direction of green chemistry in modernization, and has good application prospects.
- -
-
Paragraph 0261-0266
(2021/02/10)
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- Water-removable ynamide coupling reagent for racemization-free syntheses of peptides, amides, and esters
-
A novel ynamide coupling reagent, the by-product of which can be removed by water, was reported. It promotes the direct coupling between carboxylic acids and amines, alcohols or thiols to provide amides, peptides, esters and thioesters, respectively. No detectable racemization was observed for all the coupling reactions of carboxylic acids containing an α-chiral center. Importantly, a simple acidic aqueous work-up removed the by-product readily to afford pure coupling products in good to excellent yields without the use of column chromatography, thus making this method more environmentally benign, user friendly and cost-effective. The robustness of the water-removable ynamide coupling reagent was further exemplified by the racemization/epimerization-free synthesis of carfilzomib, in which no column chromatography purification was involved for the entire 12-step synthesis.
- Liu, Tao,Zhang, Xue,Peng, Zejun,Zhao, Junfeng
-
supporting information
p. 9916 - 9921
(2021/12/24)
-
- Method for click construction of amido bond by using pyrimidine condensing agent and application of amido bond in synthesis of amide and polypeptide
-
The invention discloses a method for click construction of an amido bond by using a pyrimidine condensing agent and an application of the amido bond in synthesis of amide and polypeptide. The amido bond construction method comprises the following steps: adding an organic solvent dissolved with organic alkali into a carboxylic acid component and an amine component, stirring for reaction, adding an organic solvent dissolved with a pyrimidine condensing agent, continuously stirring for reaction, concentrating, separating and purifying to obtain an amide or polypeptide product. According to the amido bond construction method, the use amount of the condensing agent is small, and the condensing agent is safe, odorless and easy to store and has good atom economy. The amido bond construction reaction time is only several seconds to ten minutes, and the amide or polypeptide synthesis time is greatly shortened. Besides, the amido bond construction reaction can also be quickly carried out in an organic phase-water phase biphasic system and in the organic phase-water phase biphasic system under the condition that alkali is not added, so that a mild and feasible path is provided for the amido bond construction reaction in an alkali-sensitive biological system.
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-
Paragraph 0187-0190
(2021/05/29)
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- Alpha-carbonyl alkenyl ester compound as well as preparation method and application thereof
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The invention provides an alpha-carbonyl alkenyl ester compound and a preparation method thereof. The alpha-carbonyl alkenyl ester compound is also used for reacting with primary or secondary amine to prepare an amide compound. Two steps of reactions are combined to develop an amido bond and peptide bond forming method which takes carboxylic acid and amine as starting raw materials and allene ketone as a condensing agent. Meanwhile, the alpha-carbonyl alkenyl ester compound of the alpha-amino acid is used as a polypeptide synthesis building block for solid-phase synthesis of polypeptide. The method is mild in reaction condition, simple to operate and high in yield. Compared with an existing amido bond condensation reagent, allene ketone has the advantages of being easy and convenient to prepare, good in stability, small in molecular weight and free of racemization when alpha-chiral carboxylic acid is activated and the like. The compound is a novel amido bond and peptide bond condensation reagent.
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-
Paragraph 0456-0461
(2021/08/25)
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- Allenone-Mediated Racemization/Epimerization-Free Peptide Bond Formation and Its Application in Peptide Synthesis
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Allenone has been identified as a highly effective peptide coupling reagent for the first time. The peptide bond was formed with an α-carbonyl vinyl ester as the key intermediate, the formation and subsequent aminolysis of which proceed spontaneously in a racemization-/epimerization-free manner. The allenone coupling reagent not only is effective for the synthesis of simple amides and dipeptides but is also amenable to peptide fragment condensation and solid-phase peptide synthesis (SPPS). The robustness of the allenone-mediated peptide bond formation was showcased incisively by the synthesis of carfilzomib, which involved a rare racemization-/epimerization-free N to C peptide elongation strategy. Furthermore, the successful synthesis of the model difficult peptide ACP (65-74) on a solid support suggested that this method was compatible with SPPS. This method combines the advantages of conventional active esters and coupling reagents, while overcoming the disadvantages of both strategies. Thus, this allenone-mediated peptide bond formation strategy represents a disruptive innovation in peptide synthesis.
- Wang, Penghui,Wang, Xuewei,Wang, Zhengning,Zhao, Junfeng
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supporting information
p. 10374 - 10381
(2021/07/26)
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- Rapid access to cinnamamides and piper amides: Via three component coupling of arylaldehydes, amines, and Meldrum's acid
-
A practical method for the synthesis of cinnamamides and piper amides via a conceptually novel three component reaction of aldehydes, amines and Meldrum's acid has been reported. The reaction proceeds under operationally simple conditions without the aid of coupling reagents, oxidants, or catalysts, which are essential for the preparation of cinnamamides/piper amides via known methods. The formation of undesired chemical wastes that generally originate from the use of coupling reagents, oxidants, or catalysts has been avoided to make this reaction more atom economical.
- Ghosh, Santanu,Jana, Chandan K.
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supporting information
p. 5803 - 5807
(2019/11/11)
-
- Synthesis of zanthoxylamide protoalkaloids and their in silico ADME-Tox screening and in vivo toxicity assessment in zebrafish embryos
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Inspired by the simple and attractive structure of zanthoxylamide protoalkaloids: armatamide, rubecenamide, lemairamin, rubemamine and zanthosine; isolated from plants of the genus Zanthoxylum. We report the synthesis of a series of 29 substituted N-pheny
- Puerto Galvis, Carlos E.,Kouznetsov, Vladimir V.
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p. 291 - 299
(2018/11/24)
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- An Efficient Solvent-Free Microwave-Assisted Synthesis of Cinnamamides by Amidation Reaction Using Phenylboronic Acid/Lewis Base Co-catalytic System
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A microwave-assisted dehydrative amide condensation reaction is reported as an efficient access to cinnamamide derivatives under solvent-free conditions. This protocol between conjugated carboxylic acids and amines is based on the use of a co-catalytic system, including the presence of the commercially available phenylboronic acid and 4-(N, N-dimethylamino)pyridine N-oxide (DMAPO), with a complete chemoselectivity in favor of the corresponding α,β-unsaturated amides. The implementation of the reaction needs no special precaution, and less reactive amines, such as substituted anilines, are also efficient under these conditions. A series of novel conjugated amides have been evaluated for their cytotoxic activities against several human cancer cell lines.
- Carboni, Bertrand,Khaldoun, Khadidja,Safer, Abdelmounaim,Saidi-Besbes, Salima,Carreaux, Fran?ois,Le Guével, Rémy
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p. 3891 - 3900
(2019/10/11)
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- Direct Amidation of Carboxylic Acids through an Active α-Acyl Enol Ester Intermediate
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The development of a highly efficient and simple protocol for the direct amidation of carboxylic acids is described employing ynoates as novel coupling reagents. The transformation proceeds in good to excellent yields via in situ α-acyl enol ester intermediates formation under mild reaction conditions. This useful method has been demonstrated for a range of substrates to provide a succinct access to structurally diverse amides, including key intermediates of glibenclamide, tiapride hydrochloride, and nateglinide, and can be conducted on a mole scale.
- Xu, Xianjun,Feng, Huangdi,Huang, Liliang,Liu, Xiaohui
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p. 7962 - 7969
(2018/06/18)
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- Design, synthesis of N-phenethyl cinnamide derivatives and their biological activities for the treatment of Alzheimer's disease: Antioxidant, beta-amyloid disaggregating and rescue effects on memory loss
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Gx-50 is a bioactive compound for the treatment of Alzheimer's disease (AD) found in Sichuan pepper (Zanthoxylum bungeanum). In order to find a stronger anti-AD lead compound, 20 gx-50 (1-20) analogs have been designed and synthesized, and their molecular structures were determined based on nuclear magnetic resonance (NMR) and mass spectrometry (MS) analysis, as well as comparison with literature data. Compounds 1-20 were evaluated for their anti-AD potential by using DPPH radical scavenging assay for considering their anti-oxidant activity, thioflavin T (ThT) fluorescence assay for considering the inhibitory or disaggregate potency of Ab, and transgenic Drosophila model assay for evaluating their rescue effect on memory loss. Finally, compound 13 was determined as a promising anti-AD candidate.
- Chai, Tian,Zhao, Xiao-Bo,Wang, Wei-Feng,Qiang, Yin,Zhang, Xiao-Yun,Yang, Jun-Li
-
-
- Mining Plants for Bacterial Quorum Sensing Modulators
-
The bacterial plant pathogen Agrobacterium tumefaciens uses quorum sensing (QS) in order to regulate the transfer of DNA into the host plant genome, and this results in the induction of crown gall tumors. The deleterious results of these infections are wi
- David, Shimrit,Mandabi, Aviad,Uzi, Shaked,Aharoni, Asaph,Meijler, Michael M.
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p. 247 - 252
(2018/02/06)
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- Boronic acid-DMAPO cooperative catalysis for dehydrative condensation between carboxylic acids and amines
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Arylboronic acid and 4-(N,N-dimethylamino)pyridine N-oxide (DMAPO) cooperatively catalyse the dehydrative condensation reaction between carboxylic acids and amines to give the corresponding amides under azeotropic reflux conditions. This cooperative use is much more effective than their individual use as catalysts, and chemoselectively promotes the amide condensation of (poly)conjugated carboxylic acids. The present method is practical and scalable, and has been applied to the synthesis of sitagliptin and a drug candidate.
- Ishihara, Kazuaki,Lu, Yanhui
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p. 1276 - 1280
(2016/02/05)
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- METHOD FOR PRODUCING CARBOXYLIC ACID AMIDE
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PROBLEM TO BE SOLVED: To use arylboronic acid with a chemical structure more simpler than that of the conventional one in a method for producing carboxylic acid amide. SOLUTION: Provided is a method for producing carboxylic acid amide capable of obtaining carboxylic acid amide by dehydration condensation reaction between carboxylic acid and amine. As the carboxylic acid, carboxylic acid having two or more hydrogen atoms at the α position, carboxylic acid having hydrogen atoms and a methyl group at the α position, α, β-unsaturated carboxylic acid or aromatic carboxylic acid is used. Further, B(OH)3, PhB(OH)2 or the like are used as a catalyst, and 4-dimethylaminopyridine, its N-oxide or the like are used as an additive. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
- -
-
Paragraph 0034; 0048; 0049; 0051
(2017/01/31)
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- Synthesis of Amides with Remote Stereocenters by Catalytic Asymmetric γ-Alkynylation of α,β-Unsaturated Amides
-
An iridium-catalyzed enantioselective hydroalkynylation of α,β-unsaturated amides was described. The selectivity of this reaction is distinct from that observed in many catalytic hydroalkynylations of α,β-unsaturated carbonyl compounds. It occurs selectively at the γ instead of the β position. Preliminary mechanistic studies suggest that the reaction proceeds through alkene isomerization followed by hydroalkynylation. This method provides a straightforward route for the synthesis of amides with a remote stereocenter at the γ position.
- Wang, Zi-Xuan,Bai, Xiao-Yan,Yao, Han-Chao,Li, Bi-Jie
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supporting information
p. 14872 - 14875
(2016/11/28)
-
- Ynamides as Racemization-Free Coupling Reagents for Amide and Peptide Synthesis
-
A highly efficient, two-step, one-pot synthetic strategy for amides and peptides was developed by employing ynamides as novel coupling reagents under extremely mild reaction conditions. The ynamides not only are effective for simple amide and dipeptide synthesis but can also be used for peptide segment condensation. Importantly, no racemization was detected during the activation of chiral carboxylic acids. Excellent amidation selectivity toward amino groups in the presence of -OH, -SH, -CONH2, ArNH2, and the NH of indole was observed, making the protection of these functional groups unnecessary in amide and peptide synthesis.
- Hu, Long,Xu, Silin,Zhao, Zhenguang,Yang, Yang,Peng, Zhiyuan,Yang, Ming,Wang, Changliu,Zhao, Junfeng
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supporting information
p. 13135 - 13138
(2016/10/22)
-
- Design, synthesis, and evaluation of caffeic acid amides as synergists to sensitize fluconazole-resistant Candida albicans to fluconazole
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A series of caffeic acid amides were designed, synthesized, and their synergistic activity with fluconazole against fluconazole-resistant Candida albicans was evaluated in vitro. The title caffeic acid amides 3-30 except 26 exhibited potent activity, and the subsequent SAR study was conducted. Compound 3, 5, 21, and 34c, at a concentration of 1.0 μg/ml, decreased the MIC80 of fluconazole from 128.0 μg/ml to 1.0-0.5 μg/ml against the fluconazole-resistant C. albicans. This result suggests that the caffeic acid amides, as synergists, can sensitize drug-resistant fungi to fluconazole. The SAR study indicated that the dihydroxyl groups and the amido groups linking to phenyl or heterocyclic rings are the important pharmacophores of the caffeic acid amides.
- Dai, Li,Zang, Chengxu,Tian, Shujuan,Liu, Wei,Tan, Shanlun,Cai, Zhan,Ni, Tingjunhong,An, Maomao,Li, Ran,Gao, Yue,Zhang, Dazhi,Jiang, Yuanying
-
-
- Synthesis and structure-activity relationship analysis of caffeic acid amides as selective matrix metalloproteinase inhibitors
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Four series of acid amides were synthesized, and through measurement using a fluorogenic substrate assay with human recombinant MMP-1, MMP-2 and MMP-9, compound 3f showed considerable inhibitory activities against MMP-2, MMP-9 and the best selectivity over MMP-1. Preliminary structure-activity relationship analysis indicated that caffeic acid amides with electron-donating groups at para-position of amino phenyl group showed better inhibitory activities and selectivity than those with electron-withdrawing groups, and the presence of adjacent dihydroxy in the caffeoyl group was very important for the MMP-2 and MMP-9 inhibitory activities.
- Shi, Zhi-Hao,Li, Nian-Guang,Shi, Qian-Ping,Tang, Hao,Tang, Yu-Ping,Li, Wei,Yin, Lian,Yang, Jian-Ping,Duan, Jin-Ao
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p. 1206 - 1211
(2013/03/14)
-
- The triflic acid-mediated cyclisation of N-benzyl-cinnamamides
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N-Benzyl-cinnamamides cyclise with triflic acid to form 5-aryl-benzazepinones and/or cinnamamides.
- King, Frank D.,Caddick, Stephen
-
supporting information
p. 487 - 491
(2013/07/27)
-
- Metal-free oxidative amide formation with N-hydroxysuccinimide and hypervalent iodine reagents
-
An oxidative amide formation using N-hydroxysuccinimide and hypervalent iodine reagents was developed. The method enables a wide range of aldehydes and amines to be coupled under mild reaction conditions providing amide in good to excellent yield. The radical species in the reaction mixture was observed for the first time using ESR measurement, and along with other mechanistic investigations, a plausible mechanism of the reaction was proposed.
- Yao, Haoyi,Tang, Yun,Yamamoto, Kana
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supporting information; experimental part
p. 5094 - 5098
(2012/10/08)
-
- Amidation of aldehydes and alcohols through α-iminonitriles and a sequential oxidative three-component strecker reaction/thio-michael addition/alumina-promoted hydrolysis process to access β-mercaptoamides from aldehydes, amines, and thiols
-
Mild and general alumina-promoted hydrolysis conditions for converting α-iminonitriles into carboxamides have been developed. In combination with the oxidative three-component Strecker reaction, the one-pot direct amidation of aldehydes and alcohols is reported. Subsequently, an Yb(OTf) 3-catalyzed Michael addition of thiols to α,β-unsaturated α-iminonitriles is reported for the synthesis of β-mercapto-α- iminonitriles. The successful integration of an oxidative Strecker reaction, thio-Michael addition, and neutral-alumina-promoted hydrolysis of β-mercapto-α-iminonitriles into a three-component one-pot process allowed us to develop the direct conversion of amines, aldehydes, and thiols into β-mercaptoamides. All of these procedures were applicable to aromatic and aliphatic amines and aldehydes. First direct: The direct amidation reactions of aldehydes and alcohols were performed in combination with the oxidative three-component synthesis of α-iminonitriles. In addition, β-mercaptoamides were readily accessed from α,β-unsaturated aldehydes, amines, and thiols by a sequential process that involved a three-component Strecker reaction, Yb(OTf)3-catalyzed thio-Michael addition, and hydrolysis of the resulting β-mercapto-α-iminonitriles (see scheme). Copyright
- Gualtierotti, Jean-Baptiste,Schumacher, Xavier,Fontaine, Patrice,Masson, Géraldine,Wang, Qian,Zhu, Jieping
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supporting information
p. 14812 - 14819
(2013/01/15)
-
- Diacetoxyiodobenzene mediated one-pot synthesis of diverse carboxamides from aldehydes
-
A novel, one-pot, and highly facile protocol has been devised for an easy access of a series of novel glycosyl carboxamides from aldehydes using diacetoxyiodobenzene in the presence of ionic liquid at ambient temperature.
- Prasad, Virendra,Kale, Raju R.,Mishra, Bhuwan B.,Kumar, Dhananjay,Tiwari, Vinod K.
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supporting information; experimental part
p. 2936 - 2939
(2012/08/07)
-
- Synthesis and antioxidant capacities of hydroxyl derivatives of cinnamoylphenethylamine in protecting DNA and scavenging radicals
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Cinnamoylphenethylamine (CNPA) derivatives including feruloylphenethylamine (FRPA), caffeoylphenethylamine (CFPA), cinnamoyltyramine (CNTA), feruloyltyramine (FRTA) and caffeoyltyramine (CFTA) were synthesized in order to investigate the influence of the number and position of hydroxyl group on Cu2+/glutathione (GSH) and 2,2′-azobis(2-amidinopropane hydrochloride) (AAPH)-induced oxidation of DNA. The radical-scavenging properties of these CNPA derivatives were also evaluated by trapping 2,2′-azinobis(3-ethylbenzothiazoline-6-sulphonate) cationic radical (ABTS), 2,2′-diphenyl-1-picrylhydrazyl radical (DPPH) and galvinoxyl radical. In addition, these CNPA derivatives were tested by linoleic acid (LH)-β-carotene-bleaching experiment. The chemical kinetic was employed to treat the results from AAPH-induced oxidation of DNA and gave the order of antioxidant ability as CFTA > CFPA > FRTA > FRPA. CFTA and CFPA also possessed high abilities to inhibit Cu2+/GSH-mediated degradation of DNA, whereas FRPA and FRTA can protect LH against the auto-oxidation efficiently. Finally, CFPA and FRPA exhibited high activity in trapping ABTS, DPPH and galvinoxyl radicals. Therefore, the cinnamoyl group bearing ortho-dihydroxyl or hydroxyl with ortho-methoxyl benefited for CNPA derivatives to protect DNA, while hydroxyl in tyramine cannot enhance the radical-scavenging abilities of CNPA derivatives.
- Yang, Yang,Song, Zhi-Guang,Liu, Zai-Qun
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experimental part
p. 445 - 453
(2012/05/20)
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- A general and selective iron-catalyzed aminocarbonylation of alkynes: Synthesis of acryl- and cinnamides
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Entering the iron age: The first general method for iron-catalyzed monocarbonylation of alkynes has been developed. A range of structurally diverse cinnamides and acrylamides have been obtained smoothly starting from commercially available amines and alkynes in the presence of [Fe 3(CO)12] and ligand L (see scheme). The method is highly chemo- and regioselective and requires no expensive catalyst.
- Driller, Katrin Marie,Prateeptongkum, Saisuree,Jackstell, Ralf,Beller, Matthias
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supporting information; experimental part
p. 537 - 541
(2011/03/16)
-
- Induction of adiponectin by natural and synthetic phenolamides in mouse and human preadipocytes and its enhancement by docosahexaenoic acid
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Adiponectin, the adipose-derived cytokine, plays an important role in preventing metabolic syndromes. To develop new adiponectin inducers, eight species of ferulic esters and amides, and five related compounds were synthesized and tested on the stimulation of adiponectin production in mouse 3T3-L1 and normal human preadipocytes. The ferulamides with an aromatic ring in the N-substituent are very active in inducing adiponectin as compared with the known active compounds, curcumin, [6]-gingerol, and capsaicin, and furthermore the activities of these ferulamides are remarkably stronger than those of the corresponding esters or the straight chain octylamide. The most active compound, N-(2-phenylethyl)ferulamide (7), was found to activate the PPAR (peroxisome proliferator-activated receptor) γ-RXR (retinoid X receptor) α heterodimeric complex in the PPRE (PPAR-responsive element)-driven luciferase reporter assay. The adiponectin production by 7 is synergistically enhanced by coaddition of a PPARγ-specific agonist, pioglitazone (PGZ), or another PPARγ agonist, docosahexaenoic acid (DHA), in cultured preadipocytes. The compound 7 alone did not show a statistically significant effect on the plasma adiponectin level in KK-Ay/Ta mice, while 1% 7 in the diets significantly lowered the blood glucose and triglyceride levels and 0.3% 7 mixed with DHA oil in the diets significantly increased the adiponectin level as compared with the control. These results suggest that the present ferulamides would be useful lead compounds in developing more potent agents for treatment of metabolic syndromes through promoting the endogenous adiponectin production, and that such an activity is possibly enhanced by the coadministration with DHA.
- Yamazaki, Yoshimitsu,Kawano, Yasuhiro,Uebayasi, Masami
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p. 290 - 300
(2008/09/16)
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- Development of chlorotriazine polymer dehydrocondensing reagents (Poly-Trzs)
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Polymer-type dehydrocondensing reagents comprising of a triazine dehydrocondensing reagent, itself in a polymerized form (Poly-Trz-MMs'), have been developed by exploiting the chemical properties of cyanuric chloride that readily binds to alcohol or amines. A chlorotriazine polymer bearing two alkoxy substituents at the 4- and 6- positions (Poly-O-Trz-Cl) was prepared by alternating copolymerization between cyanuric chloride and tetra(ethylene glycol). Similarly, polymers bearing both alkoxy and amino substituents (Poly-N-Trz-Cl) were synthesized from tetra(ethylene glycol) bis(4,6-dichlorotriazin-2-yl) ether 6 and tris(2-aminoethyl)amine 7 and/or ethylenediamine 8. All the polymers were shown to be good reagents for dehydrocondensation of carboxylic acids and amines in the presence of NMM, compared to the corresponding monomeric dehydrocondensing reagent (DMT-MM). The advantages of the polymeric reagents are as follows: (1) both the reaction and isolation procedure of dehydrocondensation can be greatly simplified, (2) the dehydrocondensation can be conducted in protic solvents as well as in common organic solvents, (3) the reagents can be efficiently prepared at a low cost, and (4) these reagents are considered eco-friendly, generating a lower amount of waste compared to conventionally related reagents because of high loading of the dehydrocondensing activity (ca. 3 mequiv/g).
- Kunishima, Munetaka,Yamamoto, Kazuyoshi,Hioki, Kazuhito,Kondo, Tomohito,Hasegawa, Masumi,Tani, Shohei
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p. 2604 - 2612
(2007/10/03)
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- Immobilized triazine-type dehydrocondensing reagents for carboxamide formation: ROMP-Trz-Cl and ROMP(OH)-Trz-Cl
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New triazine-type dehydrocondensing reagents, such as ROMP-Trz-Cl and ROMP(OH)-Trz-Cl, were synthesized by a ring opening metathesis polymerization (ROMP) method, and these showed higher loading than conventional polymer-supported condensing reagents. The
- Hioki, Kazuhito,Kameyama, Satomi,Tani, Shohei,Kunishima, Munetaka
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p. 825 - 828
(2008/02/08)
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- Phenylsilane as an active amidation reagent for the preparation of carboxamides and peptides
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The use of phenylsilane as a mild coupling reagent for amidation reactions is reported. Applicability to both solution- and solid-phase chemistry has been demonstrated for a variety of amines and carboxylic acids.
- Ruan, Zheming,Lawrence, R. Michael,Cooper, Christopher B.
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p. 7649 - 7651
(2007/10/03)
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- Development of novel polymer-type dehydrocondensing reagents comprised of chlorotriazines
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A novel immobilized dehydrocondensing reagent comprised of a triazine-type dehydrocondensing reagent itself in a polymerized form was synthesized by copolymerization between tetra(ethylene glycol) bis(dichlorotriazinyl) ether and tris(2-aminoethyl)amine.
- Kunishima, Munetaka,Yamamoto, Kazuyoshi,Watanabe, Yasunobu,Hioki, Kazuhito,Tani, Shohei
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p. 2698 - 2700
(2007/10/03)
-
- 3-HYDROXY-4-OXO-1,2,3-TRIAZINES AND DERIVATIVES THEREOF FOR AMIDE AND ESTER BOND FORMATION
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The present invention relates to the use of a compound of formula I as a coupling reagent in forming amide or ester bonds from a reaction between a carboxylic acid and an amine or an alcohol, respectively. The compounds of formula I are especially useful as coupling reagents in the preparation of peptide bonds during peptide synthesis. In particular, the compounds of formula I are useful in promoting the formation of reactive reaction intermediates, inhibiting side reactions and in suppression of racemization. In addition, the present invention provides novel compounds of Formula I, and salts of N-oxides thereof.
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-
- Development of a simple system for dehydrocondensation using solid-phase adsorption of a water-soluble dehydrocondensing reagent (DMT-MM)
-
It has been indicated that hydrophilic solid powder to which aqueous solution of a novel dehydrocondensing reagent DMT-MM is adsorbed becomes a simple solid-phase dehydrocondensing reagent of low cost. Reaction in a liquid-liquid biphasic system on the surface of a solid phase with a large area was accelerated by suspending this powder in a dichloromethane solution of a carboxylic acid and an amine to be condensed. The reaction was rapid with a high yield despite the heterogeneity of the system. Like general solid-phase reagents, a hydrophobic carboxamide alone could be isolated at a relatively high purity only by filtration of the resulting suspension of reaction mixture.
- Watanabe, Yasunobu,Fuji, Takako,Hioki, Kazuhito,Tani, Shohei,Kunishima, Munetaka
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p. 1223 - 1226
(2007/10/03)
-
- METHOD FOR STORING QUATERNARY AMMONIUM SALT
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A method of improving the stability of a quaternary ammonium salt and a method of efficiently preparing the quaternary ammonium salt having improved stability.
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- New observations on peptide bond formation using CDMT
-
The optimized formation of the peptide bond by means of 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) has been found to occur rapidly and essentially quantitatively in a one-pot, one-step procedure. This new method is effective for the coupling of a variety of reactive partners, including chiral amino acids (e.g. N-acetyl-L-leucine) without significant loss of configuration. Significant racemization was observed when the typical literature conditions were used, due to the formation of an azlactone intermediate which is configurationally unstable under the reaction conditions. A simpler, precipitative workup procedure is also disclosed in this report.
- Garrett, Christine E.,Jiang, Xinglong,Prasad, Kapa,Repi?, Oljan
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p. 4161 - 4165
(2007/10/03)
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- Approach to green chemistry of DMT-MM: Recovery and recycle of coproduct to chloromethane-free DMT-MM
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A simple procedure for the isolation of 2-hydroxy-4,6-dimethoxy-1,3,5-triazine (HO-DMT), a coproduct arising from dehydrating condensation using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) has been established. HO-DMT can be recycled by treatment with POCl3 to give 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT), which is further converted to DMT-MM. Alternatively, reaction with triflic anhydride followed by addition of N-methylmorpholine gives DMT-MM triflate.
- Kunishima, Munetaka,Hioki, Kazuhito,Wada, Ayako,Kobayashi, Hiroko,Tani, Shohei
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p. 3323 - 3326
(2007/10/03)
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- Formation of carboxamides by direct condensation of carboxylic acids and amines in alcohols using a new alcohol- and water-soluble condensing agent: DMT-MM
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Selective formation of carboxamides in an alcohol or water by an exceptionally convenient one-step procedure in which a condensing agent is simply added to a mixture of acids and amines has been achieved successfully by using a new condensing agent, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM). Activation of carboxylic acids by DMT-MM in the presence of amines and subsequent aminolysis of the resulting acyloxytriazine in alcoholic solvents occurred selectively and led to the formation of carboxamides in excellent yields. The rate of aminolysis of the acyloxytriazine intermediate can be estimated to be about 2×104 times greater than that of methanolysis. The amide/ester selectivity observed using DMT-MM was much larger than that obtained with DCC or EDC. Condensation of polar substrates, such as amino acid esters and their hydrochlorides, glucosamine hydrochloride, sodium acetate and dicarboxylic acids, proceeded successfully in MeOH, water or aqueous MeOH in good yields. The present reaction is technically quite simple and easy to achieve. It proceeds by simple mixing of acids, amines and DMT-MM without any additives, and the MeOH is readily removable by a rotary evaporator after completion of the reaction.
- Kunishima, Munetaka,Kawachi, Chiho,Hioki, Kazuhito,Terao, Keiji,Tani, Shohei
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p. 1551 - 1558
(2007/10/03)
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- Efficient procedure for the preparation of amides using polymer-bound reagents
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An effective method for the conversion of acids into amides is presented. The two-step procedure includes the preparation of acid chloride intermediates using Pol-Ph3P and subsequent treatment of these intermediates with amines and polymer-bound base. The amides were accessible in high yields and purities without further purification.
- Buchstaller,Ebert,Anlauf
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p. 1001 - 1005
(2007/10/03)
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- Unsaturated enamides via organometallic addition to isocyanates: The synthesis of Lansamide-I, Lansiumamides A-C and SB-204900
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Styryl Grignard addition to vinyl isocyanates is employed to prepare the naturally occurring enamides Lansamide-I, Lansiumamides A and B, and SB- 204900; the synthesis of Lansiumamide C is also reported. (C) 2000 Elsevier Science Ltd.
- Stefanuti, Ian,Smith, Stephen A.,Taylor, Richard J. K.
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p. 3735 - 3738
(2007/10/03)
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- Synthesis and characterization of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)- 4-methylmorpholinium chloride
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4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) was quantitatively synthesized by the coupling of 2-chloro-4,6- dimethoxy-1,3,5-triazine and N-methylmorpholine in THF, and fully characterized. Condensation of carboxylic acids and amines by DMTMM proceeded effectively in THF to give the corresponding amides in good yield.
- Kunishima, Munetaka,Kawachi, Chiho,Iwasaki, Fumiaki,Terao, Keiji,Tani, Shohei
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p. 5327 - 5330
(2007/10/03)
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- 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride: An efficient condensing agent leading to the formation of amides and esters
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4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) was quantitatively synthesized by the coupling of 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) and N- methylmorpholine (NMM) in THF, and characterized. Condensation of carboxylic acids and amines by DMTMM proceeded effectively in THF to give the corresponding amides in good yields. The corresponding esters can be obtained by esterification of carboxylic acids with DMTMM in methanol, ethanol, isopropyl alcohol, or t-butyl alcohol in the presence of NMM. The amount of alcohols can be reduced to a stoichiometric amount by conducting the reaction in THF. Since the reactions proceed under atmospheric conditions without drying of the solvent, and the co- product (4,6-dimethoxy-1,3,5-triazin-2(1H)-one) arising from DMTMM after condensation can be readily removed by extraction, this method is a very practical one.
- Kunishima, Munetaka,Kawachi, Chiho,Morita, Jun,Terao, Keiji,Iwasaki, Fumiaki,Tani, Shohei
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p. 13159 - 13170
(2007/10/03)
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- Isolation and Activity of N-p-Coumaroyltyramine, an α-Glucosidase Inhibitor in Welsh Onion (Allium fistulosum)
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A phenolic amide, N-p-coumaroyltyramine (1), was isolated as an α-glucosidase inhibitor from methanol extracts of Welsh onion (Allium fistulosum). The inhibitory activity of 1 against a yeast enzyme was as high as Ki 8.4 × 10-7 M. From a structure-activity relationship study of 1 and its related compounds, the occurrence of α-glucosidase inhibitory activity required a p-coumaramide structure, with an amide hydrogen and alkyl or aralkyl substituent on the amide part.
- Nishioka, Tetsuo,Watanabe, Jun,Kawabata, Jun,Niki, Ryoya
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p. 1138 - 1141
(2007/10/03)
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- Inhibition of in vitro prostaglandin and leukotriene biosyntheses by cinnamoyl-β-phenethylamine and N-acyldopamine derivatives
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N-trans- and N-cis-Feruloyltyramines were isolated as the inhibitors of in vitro prostaglandin (PG) synthesis from an Indonesian medicinal plant, Ipomoea aquatica (Convolvulaceae). In order to clarify structure activity relationships, cinnamoyl-β-phenethylamines with possible combinations of naturally occurring cinnamic acids and β-phenethylamines were synthesized and tested for their inhibitory activities against PG synthetase and arachidonate 5-lipoxygenase. The compounds containing catechol groups such as N-caffeoyl-β-phenethylamine (CaP) showed higher inhibitory effects on PG synthetase. The catechol group was found to M essential for the inhibition of arachidonate 5-lipoxygenase. The investigation of concentration dependent effects on PG biosynthesis revealed that CaP enhanced PG biosynthesis at a lower concentration range, whereas it inhibited the reaction at a higher concentration. The effects of CaP on each reaction step were investigated with purified PG endoperoxide synthase and microsomal PG synthetase. CaP inhibited the cyclooxygenase reaction, while it enhanced the hydroperoxidase reaction. N-Acyldopamines which contain catechol and lipophylic group were synthesized from dopamine and fatty acids to test their inhibitory effects on arachidonate 5-lipoxygenase. N-Linoleoyldopamine was the most active compound and its IC50 value was 2.3 nM in our assay system, in which an IC50 value of AA 861, a specific inhibitor of 5-lipoxygenase, was 8 nM.
- Tseng,Iwakami,Mikajiri,Shibuya,Hanaoka,Ebizuka,Padmawinata,Sankawa
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p. 396 - 400
(2007/10/02)
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