- Supported-Pd catalyzed tandem approach for N-arylbenzamides synthesis
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Aryl iodides as dual arylating agent for C-terminal from oxalic acid [(CO2H)2] and N-terminal from sodium azide (NaN3) for N-aryl benzamides (Ar-CO-NH-Ar) synthesis is a rare invention which has been attempted successfully under this study. A single step tandem approach for the synthesis of N-aryl benzamides has been developed through bifunctional transformation of aryl iodides with in-situ CO from (CO2H)2 and NaN3 following two different pathways of carbonylation and azidation. The polystyrene supported palladium (Pd@PS) catalyst was found to be well compatible to perform the domino-reaction in a double layer vial (DLV) system under base, ligand and additive-free conditions. Moreover, the same approach was further extended with aryl azides for unsymmetric N-aryl benzamides (Ar-CO-NH-Ar') synthesis. Furthermore, the DFT studies were also performed to support the proposed mechanism.
- Bhattacherjee, Dhananjay,Das, Pralay,Giri, Kousik,Shaifali,Sharma, Ajay Kumar,Sharma, Navneet,Sheetal
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- Palladium Catalyzed Cascade Azidation/Carbonylation of Aryl Halides with Sodium Azide for the Synthesis of Amides
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Amide synthesis is one of the most important transformations in organic chemistry due to their ubiquitous presence in our daily life. In this communication, a palladium catalyzed cascade azidation/carbonylation of aryl halides for the synthesis of amides was developed. Both iodo- and bromobenzene derivatives were transformed to the corresponding amides using PdCl2/xantphos as the catalyst system and sodium azide as the nitrogen-source. The reaction proceeds via a cascade azidation/carbonylation process. A range of alkyl and halogen substituted amides were prepared in moderate to good yields.
- Qi, Zhuang,Li, Shan-Shan,Li, Lin,Qin, Qi,Yang, Li-Miao,Liang, Ying-Kang,Kang, Yun,Zhang, Xiang-Zhi,Ma, Ai-Jun,Peng, Jin-Bao
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p. 503 - 506
(2021/02/06)
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- Ligand-free copper-catalyzed direct amidation of diaryliodonium salts using nitriles as amidation reagents
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An efficient and practical methodology for the synthesis of N-arylamides has been developed via copper-catalyzed amidation of diaryliodonium salts with nitriles. Various substituted aryl nitriles and aliphatic nitriles could be applied in the reaction, providing a series of N-arylated amides in moderate to good yields. This procedure provides an alternative route for the synthesis of various N-arylamides. A proposed mechanism based on control experiments is also presented.
- Cheng, Hui-cheng,Guo, Penghu,Ji, Hong-bing,Ma, Jiao-li,Zhang, Yang,Zhou, Lichao,Zhou, Xuming
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supporting information
(2021/04/19)
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- New half-sandwich (η6-p-cymene)ruthenium(II) complexes with benzothiazole hydrazone Schiff base ligand: Synthesis, structural characterization and catalysis in transamidation of carboxamide with primary amines
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Few half-sandwich (η6-p-cymene) ruthenium(II) complexes supported by benzothiazole hydrazone Schiff bases were synthesized. The new complexes possess the general formulae [Ru(η6-p-cymene)(L)Cl] (1-3) (L = salicyl((2-(benzothiazol-2-yl)hydrazono)methylphenol) (SAL-HBT), 2-((2-(benzothiazol-2-yl)hydrazono)methyl)-6 methoxyphenol) (VAN-HBT) or naphtyl-2-((2-(benzothiazol-2-yl)hydrazono)methyl phenol) (NAP-HBT). All compounds were fully studied by analytical, spectroscopic techniques (IR, NMR) and also by mass spectrometry. The solid state structure of the complex 3 reveals the coordination of p-cymene moieties with ruthenium(II) in a three-legged piano-stool geometry along with benzothiazole hydrazone Schiff base ligand in a monobasic bidentate fashion. The catalytic properties of the complexes were screened in transamidation of primary amide with amines after optimization with respect to solvent, substituents, time and catalyst loading. The results show that the complex 3 is the most efficient catalyst for the transamidation of carboxamides with amines.
- Vijayapritha, Subbarayan,Viswanathamurthi, Periasamy
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supporting information
(2020/10/18)
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- Preparation method of N-aryl amide compound
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The invention discloses a preparation method of an N-aryl amide compound, which comprises the following steps: (1) putting diaryliodonium salt and Cu(OAc)2 into a Schlenk tube provided with a magneticstirring rod; (2) sequentially adding DCE, H2O and nitrile by using an injector, sealing the Schlenk tube, and stirring for reaction at 80 DEG C; (3) cooling the obtained solution to room temperature, and performing extraction with EtOAc; and combining organic layers, performing washing with saline water, and performing drying with anhydrous Na2SO4; and (4) removing volatile matters in vacuum, and purifying residues through column chromatography to obtain the N-aryl amide compound. Through a large number of experiments, a substrate with a simple structure is screened, the reaction conditionsare mild, the yield is high, the pollution is small, and the application prospect is wide.
- -
-
Paragraph 0057-0061
(2020/07/13)
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- Green synthetic method of N-arylamides using recyclable cheap metal catalyst
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Magnetically separable and reusable Fe/Cu oxide (Fe3O4-Cu2O) nanoparticles were employed as an efficient catalyst for the arylation of benzamide, which was carried out with a range of both arylboronic acid and benzamide to afford N-arylamide in good to excellent yield.
- Wang, Xingyang,Liu, Jianhui,An, Guanghui
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supporting information
(2020/10/05)
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- Switching from biaryl formation to amidation with convoluted polymeric nickel catalysis
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A stable, reusable, and insoluble poly(4-vinyl-pyridine) nickel catalyst (P4VP-NiCl2) was prepared through the molecular convolution of poly(4-vinylpyridine) (P4VP) and nickel chloride. We proposed a coordination structure of the Ni center in the precatalyst based on elemental analysis and Ni K-edge XANES, and we confirmed that it is consistent with Ni K-edge EXAFS. The Suzuki?Miyaura-type coupling of aryl halides and arylboronic esters proceeded using P4VP-NiCl2 (0.1 mol % Ni) to give the corresponding biaryl compounds in up to 94% yield. Surprisingly, when the same reaction of aryl halides and arylboronic acid/ester was carried out in the presence of amides, the amidation proceeded predominantly to give the corresponding arylamides in up to 99% yield. In contrast, the reaction of aryl halides and amides in the absence of arylboronic acid/ester did not proceed. P4VP-NiCl2 successfully catalyzed the lactamization for preparing phenanthridinone. P4VP-NiCl2 was reused five times without significant loss of catalytic activity. Pharmaceuticals, natural products, and biologically active compounds were synthesized efficiently using P4VPNiCl2 catalysis. Nickel contamination in the prepared pharmaceutical compounds was not detected by ICP-MS analysis. The reaction was scaled to multigrams without any loss of chemical yield. Mechanistic studies for both Suzuki?Miyaura and amidation were performed.
- Sen, Abhijit,Dhital, Raghu N.,Sato, Takuma,Ohno, Aya,Yamada, Yoichi M.A.
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p. 14410 - 14418
(2020/12/21)
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- o-Phthalic Anhydride/Zn(OTf)2 co-catalyzed Beckmann rearrangement under mild conditions
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o-Phthalic anhydride/Zn(OTf)2 co-catalyzed Beckmann rearrangement was developed, producing the corresponding amide in up to 99% yield with acid-sensitive functionalities tolerated well, and the scale of the reaction could be enlarged to 77 mmol and the excellent yield was maintained. A successive procedure was developed. Moreover, the reaction was carried out at rt under nearly neutral conditions, and the workup was concise. These features illustrated the potential of the protocol in amide synthesis.
- Xu, Ze-Feng,Zhang, Teng,Hong, Wenjun
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supporting information
p. 3113 - 3117
(2019/05/08)
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- Vilsmeier-Haack reagent mediated synthetic transformations with an immobilized iridium complex photoredox catalyst
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An immobilized iridium complex photocatalyst Ir(ppy)2(PDVB-py) was synthesized by immobilization of the iridium complex onto the nanoporous vinylpyridine-divinylbenzene copolymer (PDVB-py). Its application for the synthesis of amides, nitriles, and anhydrides was reported via reactions under the action of the visible-light-driven in situ generated Vilsmeier-Haack reagent from CBr4 in DMF. The results showed that this heterogeneous photocatalyst has extremely high activity and excellent stability to be recycled five times.
- Zhi, Peng,Xi, Zi-Wei,Wang, Dan-Yan,Wang, Wei,Liang, Xue-Zheng,Tao, Fei-Fei,Shen, Run-Pu,Shen, Yong-Miao
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p. 709 - 717
(2019/01/10)
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- Microdroplets as Microreactors for Fast Synthesis of Ketoximes and Amides
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The formation of amide bonds is one of the most valuable transformations in organic synthesis. Beckmann rearrangement is a well-known method for producing secondary amides from ketoximes. This study demonstrates the rapid synthesis of ketoximes and amides in microdroplets. Many factors are found to affect the yield, such as microdroplet generation devices, temperature, catalysts, and concentrations of reactants. In particular, the temperature has a great influence on the synthesis of amide, which is demonstrated by a sharp ascendance to the yield when the temperature was increased to 45 °C. The best amide yield (93.3%) can be obtained by using coaxial flowing devices, a sulfonyl chloride compound as a catalyst, and heating to 55 °C in microdroplets. The yields can reach 78.7-91.3% for benzoylaniline and 87.2-93.4% for benzophenone oximes in several seconds in microdroplets compared to 10.1-66.1% and 82.5-93.3% in several hours in the bulk phase. Apart from the dramatically decreased reaction time and enhanced reaction yields, the microdroplet synthesis is also free of severe reaction environments (anhydrous and anaerobic conditions). In addition, the synthesis in microdroplets also saves reactants and solvents and reduces the waste amounts. All of these merits indicate that the microdroplet synthesis is a high-efficiency green methodology.
- Zhang, Wenwen,Yang, Shiwei,Lin, Qiuyu,Cheng, Heyong,Liu, Jinhua
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p. 851 - 859
(2019/01/24)
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- Direct amide synthesis: via Ni-mediated aminocarbonylation of arylboronic acids with CO and nitroarenes
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Herein we describe an alternative and unconventional approach of an aminocarbonylation reaction to access aryl amides from readily available and low-cost arylboronic acids and nitroarenes. Nickel metal can serve as both reductant and catalyst in this direct aminocarbonylation. This protocol exhibits a good functional group compatibility and allows a variety of aryl amides to be synthesized, including several drug-like molecules.
- Shen, Ni,Cheung, Chi Wai,Ma, Jun-An
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supporting information
p. 13709 - 13712
(2019/11/19)
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- Highly Chemoselective, Transition-Metal-Free Transamidation of Unactivated Amides and Direct Amidation of Alkyl Esters by N-C/O-C Cleavage
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The amide bond is one of the most fundamental functional groups in chemistry and biology and plays a central role in numerous processes harnessed to streamline the synthesis of key pharmaceutical and industrial molecules. Although the synthesis of amides is one of the most frequently performed reactions by academic and industrial scientists, the direct transamidation of tertiary amides is challenging due to unfavorable kinetic and thermodynamic contributions of the process. Herein, we report the first general, mild, and highly chemoselective method for transamidation of unactivated tertiary amides by a direct acyl N-C bond cleavage with non-nucleophilic amines. This operationally simple method is performed in the absence of transition metals and operates under unusually mild reaction conditions. In this context, we further describe the direct amidation of abundant alkyl esters to afford amide bonds with exquisite selectivity by acyl C-O bond cleavage. The utility of this process is showcased by a broad scope of the method, including various sensitive functional groups, late-stage modification, and the synthesis of drug molecules (>80 examples). Remarkable selectivity toward different functional groups and within different amide and ester electrophiles that is not feasible using existing methods was observed. Extensive experimental and computational studies were conducted to provide insight into the mechanism and the origins of high selectivity. We further present a series of guidelines to predict the reactivity of amides and esters in the synthesis of valuable amide bonds by this user-friendly process. In light of the importance of the amide bond in organic synthesis and major practical advantages of this method, the study opens up new opportunities in the synthesis of pivotal amide bonds in a broad range of chemical contexts.
- Li, Guangchen,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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supporting information
p. 11161 - 11172
(2019/08/07)
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- Palladium-Catalyzed Amide Synthesis via Aminocarbonylation of Arylboronic Acids with Nitroarenes
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A palladium-catalyzed aminocarbonylation of aryl boronic acids with nitroarenes for the synthesis of amides has been developed. A wide range of substrates were well-tolerated and gave the corresponding amides in moderate to good yields. No external oxidant or reductant was needed in this procedure. This procedure provides a redox-economical process for the synthesis of amides.
- Peng, Jin-Bao,Li, Da,Geng, Hui-Qing,Wu, Xiao-Feng
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supporting information
p. 4878 - 4881
(2019/06/17)
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- Carbon-Carbon Bond Formation of Trifluoroacetyl Amides with Grignard Reagents via C(O)-CF3 Bond Cleavage
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The reaction of trifluoroacetyl amides with Grignard reagent for the substitution of CF3 group with various alkyl or aryl groups is described. A variety of aryl, quinolin-8-yl, and (hetero)alkyl functional groups as well as F, Cl, and Br atoms are well tolerated. These moisture-stable and easily available trifluoroacetyl amides can be conveniently obtained and used as new versatile precursors for isocyanates. The control experiments show that the reaction proceeds via an isocyanate intermediate and/or alkoxide/amide dual anionic intermediate.
- Zhu, Longzhi,Le, Liyuan,Yan, Mingpan,Au, Chak-Tong,Qiu, Renhua,Kambe, Nobuaki
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- Carbon-Carbon Bond Formation of Trifluoroacetyl Amides with Grignard Reagents via C(O)-CF3 Bond Cleavage
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The reaction of trifluoroacetyl amides with Grignard reagent for the substitution of CF3 group with various alkyl or aryl groups is described. A variety of aryl, quinolin-8-yl, and (hetero)alkyl functional groups as well as F, Cl, and Br atoms are well tolerated. These moisture-stable and easily available trifluoroacetyl amides can be conveniently obtained and used as new versatile precursors for isocyanates. The control experiments show that the reaction proceeds via an isocyanate intermediate and/or alkoxide/amide dual anionic intermediate.
- Zhu, Longzhi,Le, Liyuan,Yan, Mingpan,Au, Chak-Tong,Qiu, Renhua,Kambe, Nobuaki
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p. 5635 - 5644
(2019/05/10)
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- Au(i)/Au(iii)-Catalyzed C-N coupling
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Cycling between Au(i) and Au(iii) is challenging, so gold-catalyzed cross-couplings are rare. The (MeDalphos)AuCl complex, which we showed was prone to undergo oxidative addition, is reported here to efficiently catalyze the C-N coupling of aryl iodides and amines. The transformation does not require an external oxidant or a directing group. It is robust and works with a wide scope of aryl iodides and N-nucleophiles under mild conditions. Mechanistic studies, including the NMR and MS characterization of a key aryl amido Au(iii) complex, strongly support a 2e redox cycle in which oxidative addition precedes transmetalation and reductive elimination is the rate-determining step.
- Rodriguez, Jessica,Adet, Nicolas,Saffon-Merceron, Nathalie,Bourissou, Didier
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supporting information
p. 94 - 97
(2019/12/25)
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- Palladium-Catalyzed, ortho-Selective C-H Halogenation of Benzyl Nitriles, Aryl Weinreb Amides, and Anilides
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A palladium-catalyzed, ortho-selective C-H halogenation methodology is reported herein. The highlight of the work is the highly selective C(sp2)-H functionalization of benzyl nitriles in the presence of activated C(sp3)-H bond, which results in good yields of the halogenated products with excellent regioselectivity. Along with benzyl nitriles, aryl Weinreb amides and anilides have been evaluated for the transformation using aprotic conditions. Mechanistic studies yield interesting aspects with respect to the pathway of the reaction and the directing group abilities.
- Das, Riki,Kapur, Manmohan
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p. 1114 - 1126
(2018/06/18)
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- Hypervalent Iodine-Mediated Oxidative Rearrangement of N-H Ketimines: An Umpolung Approach to Amides
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An umpolung approach to amides via hypervalent iodine-mediated oxidative rearrangement of N-H ketimines under mild reaction conditions is described. This strategy provides target amides with excellent selectivity in good yields. In addition, preliminary m
- Zhao, Zhenguang,Peng, Zhiyuan,Zhao, Yongli,Liu, Hao,Li, Chongnan,Zhao, Junfeng
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p. 11848 - 11853
(2017/11/28)
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- Metal-Free Oxidative C=C Bond Cleavage of Electron-Deficient Enamines Promoted by tert -Butyl Hydroperoxide
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A novel tert -butyl hydroperoxide (TBHP)-promoted oxidative C=C double-bond cleavage of enamines is described. Heating a solution of an electron-deficient enamine in chlorobenzene at 80 °C in the presence of TBHP for two hours led to cleavage of the C=C bond. This study offers a new strategy to carry out C=O double-bond formation by the use of TBHP.
- Adib, Mehdi,Pashazadeh, Rahim,Gohari, Seyed Jamal Adin,Shahsavari, Fatemeh
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supporting information
p. 1481 - 1485
(2017/08/15)
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- Base-promoted synthesis of N-arylbenzamides by N-benzoylation of dimethylphenylthioureas
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An efficient synthesis of 10 N-arylbenzamides was achieved by N-benzoylation of N,N-dimethyl-(N'-phenyl)thioureas with 4-substituted benzoyl chlorides in dimethylacetamide in the presence of K2CO3. The features of this method include
- Liu, Xing,Xu, Wan,Zeng, Meng-Tian,Liu, Min,Chang, Cai-Zhu,Zhu, Hui,Dong, Zhi-Bing
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p. 484 - 486
(2017/08/18)
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- Palladium-Catalyzed Carbonylative Synthesis of Amides from Aryltriazenes under Additive-Free Conditions
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An interesting palladium-catalyzed carbonylative synthesis of amides from aryltriazenes was developed. By using Pd(MeCN2)Cl2 as the catalyst precursor under CO pressure through a N2 extrusion/CO insertion sequence, a broad range of aryltriazenes were transformed into the corresponding amides in good yields with excellent functional group tolerance. Remarkably, no additives such as acids or phosphine ligands were required.
- Yin, Zhiping,Wang, Zechao,Wu, Xiao-Feng
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supporting information
p. 3992 - 3995
(2017/07/28)
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- Synthesis of Quinazolines from N,N′-Disubstituted Amidines via I2/KI-Mediated Oxidative C-C Bond Formation
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An I2/KI-promoted oxidative C-C bond formation reaction from C(sp3)-H and C(sp2)-H bonds has been used to construct quinazoline skeletons from N,N′-disubstituted amidines. The required substrates are readily prepared from the corresponding acyl chlorides, anilines, and alkyl/benzylamines by sequential amidation, chlorination, and amination reactions. Under the optimal oxidative cyclization conditions, all these amidines were conveniently transformed into the expected products in moderate to good yields. This practical and environmentally benign approach works well with crude amidine intermediates and can also be carried out on a gram scale.
- Lv, Zhigang,Wang, Bingnan,Hu, Zhiyuan,Zhou, Yiming,Yu, Wenquan,Chang, Junbiao
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supporting information
p. 9924 - 9930
(2016/11/02)
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- TBHP-mediated highly efficient dehydrogenative cross-oxidative coupling of methylarenes with acetanilides
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A TBHP-mediated dehydrogenative cross-oxidative-coupling approach has been developed for the synthesis of N-arylbenzamides from methylarenes and acetanilides. This cross-coupling method is free of transition metal catalysts and ligands, and no extra organic solvents are required, which make it an useful and attractive strategy for the straightforward construction of C-N bonds. Besides, this conversion is an important complement to the conventional C-N forming strategies.
- Chen, Cui,Liu, Weibing,Zhou, Peng
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supporting information
p. 2250 - 2255
(2016/11/17)
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- Copper(I) iodide–catalyzed amidation of phenylboronic acids/aryl bromides using 4-dimethylaminopyridine as ligand
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An efficient one-pot synthesis of N-arylbenzamide is described via reaction of phenylboronic acid/aryl bromide with benzamide in the presence of CuI (5?mol%) as catalyst, 4-dimethylaminopyridine (20?mol%) as the ligand, and Cs2CO3(2?mmol) as the base. This protocol was applied to synthesize a small library of N-arylbenzamide in high yields.
- Alapati, Mohan Lakshmi Punna Rao,Abburu, Sridhar Rao,Mutyala, Krishnaji Rao,Mukkamala, Saratchandra Babu
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supporting information
p. 1242 - 1248
(2016/08/06)
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- Catalyst-Free Singlet Oxygen-Promoted Decarboxylative Amidation of α-Keto Acids with Free Amines
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A novel catalyst-free decarboxylative amidation of α-keto acids with amines under mild conditions has been developed. Advantages of the new protocol include avoidance of metal catalysts and high levels of functional group tolerance. In addition, the reaction can be scaled up and shows high chemoselectivity. Preliminary mechanistic studies suggest that singlet oxygen, generated from oxygen under irradiation, is the key promoter for this catalyst-free transformation.
- Xu, Wen-Tao,Huang, Bei,Dai, Jian-Jun,Xu, Jun,Xu, Hua-Jian
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p. 3114 - 3117
(2016/07/14)
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- Silver-promoted decarboxylative amidation of α-keto acids with amines
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A general and effective method for the synthesis of amides through decarboxylative amidation of α-keto acids with amines has been developed. The reaction proceeded smoothly to afford the corresponding amide products in good yield under air and shows excellent functional group tolerance. In addition, the protocol can be further applied in the synthesis of heterocyclic compounds like benzimidazoles.
- Xu, Xiao-Lan,Xu, Wen-Tao,Wu, Ji-Wei,He, Jian-Bo,Xu, Hua-Jian
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p. 9970 - 9973
(2016/11/06)
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- Stable and Reusable Binaphthyl-Supported Palladium Catalyst for Aminocarbonylation of Aryl Iodides
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A binaphthyl-supported Pd nanoparticles (Pd-BNP)-catalyzed aminocarbonylation of aryl iodides in the presence of carbon monoxide and amines for the synthesis of amides has been developed. This methodology provides an efficient route for the synthesis of a COX-2 enzyme inhibitor having anti-inflammatory activity.
- Sharma, Nidhi,Sekar, Govindasamy
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supporting information
p. 314 - 320
(2016/02/14)
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- A One-Pot, fast, and efficient amidation of carboxylic acids, α-amino acids and sulfonic acids using pph3/n-chlorobenzotriazole system
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Triphenylphosphine (PPh3)/N-chlorobenzotriazole (NCBT), and amine (primary and secondary aliphatic amines and also substituted anilines) in CH2Cl2 efficiently converted carboxylic acids, α-amino acids, and sulfonic acids to the corresponding amides and sulfonamides at room temperature. Good to excellent yields, inexpensive, and fast reaction conditions are the important features of this procedure.
- Rouhi-Saadabad, Hamed,Akhlaghinia, Batool
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p. 1703 - 1714
(2015/09/15)
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- Fluorescent benzene-centered mono-, bis- and tris-triazapentadiene-boron complexes
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A series of novel benzene centered mono-, bis- and tris-1,3,5-triazapentadiene ligands 6a-e was synthesized and investigated with respect to their reactivity towards triphenylborane. The resulting blue-fluorescent boron complexes 14a-e with a six-membered
- Glotzbach, Christoph,G?deke, Nadine,Fr?hlich, Roland,Daniliuc, Constantin-Gabriel,Saito, Shohei,Yamaguchi, Shigehiro,Würthwein, Ernst-Ulrich
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p. 9659 - 9671
(2015/06/16)
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- Natural organic acids promoted Beckmann rearrangement: Green and expeditious synthesis of amides under solvent-free conditions
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Naturally occurring organic acids are reported to be highly efficient promoters of the Beckmann rearrangement. Citric, oxalic, tartaric, malic, succinic, malonic, and fumaric acids efficiently promote the Beckmann rearrangement under solvent-free conditions and thermal and microwave irradiation. Tartaric acid was found to be the best promoter of the Beckmann rearrangement under conventional conditions as well as under microwave irradiation. Compared with conventional heating, microwave irradiation provides higher reaction rate and slightly higher yields.
- Rohokale, Sandeep Vasantrao,Kote, Santosh Rajaram,Deshmukh, Santosh Rangnath,Thopate, Shankar Ramchandra
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p. 575 - 578
(2014/01/17)
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- Pd-catalyzed chemoselective carbonylation of aminophenols with iodoarenes: Alkoxycarbonylation vs aminocarbonylation
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Palladium-catalyzed chemoselective carbonylation of aminophenols with iodoarenes was realized by changing ligand and base. 3- or 4-Aminophenols afforded esters in high yields and selectivities using 1,3-bis(diphenylphosphino)propane as the ligand and K2CO3 as the base, and gave amides in high yields and selectivities using 1,3-bis(diisobutylphosphino)propane as the ligand and DBU as the base. 2-Aminophenol only gave amides in high yields under both conditions.
- Xu, Tongyu,Alper, Howard
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supporting information
p. 16970 - 16973
(2015/02/02)
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- Synthesis of amides through an oxidative amidation of tetrazoles with aldehydes under transition-metal-free conditions
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A simple, inexpensive and efficient one-pot synthesis of amides was achieved in good yields via the direct oxidative amidation of tetrazoles with aldehydes under transition-metal-free conditions.
- Du, Juan,Luo, Kai,Zhang, Xiuli
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p. 54539 - 54546
(2015/01/09)
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- Visible-light-mediated decarboxylation/oxidative amidation of α-keto acids with amines under mild reaction conditions using O2
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Photochemistry has ushered in a new era in the development of chemistry, and photoredox catalysis has become a hot topic, especially over the last five years, with the combination of visible-light photoredox catalysis and radical reactions. A novel, simple, and efficient radical oxidative decarboxylative coupling with the assistant of the photocatalyst [Ru(phen)3]Cl 2 is described. Various functional groups are well-tolerated in this reaction and thus provides a new approach to developing advanced methods for aerobic oxidative decarboxylation. The preliminary mechanistic studies revealed that: 1)an SET process between [Ru(phen)3]2+* and aniline play an important role; 2)O2 activation might be the rate-determining step; and 3)the decarboxylation step is an irreversible and fast process. Bring to light: A new approach to oxidative decarboxylation under visible light using O2 as the oxidant has been developed. A variety of functional groups were well-tolerated in this reaction and insights into the mechanism were investigated with the assistance of EPR spectroscopy, cyclic voltammetry, and theoretical studies.
- Liu, Jie,Liu, Qiang,Yi, Hong,Qin, Chu,Bai, Ruopeng,Qi, Xiaotian,Lan, Yu,Lei, Aiwen
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p. 502 - 506
(2014/01/23)
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- DDQ-promoted direct transformation of benzyl hydrocarbons to amides via tandem reaction of the CDC reaction and Beckmann rearrangement
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An atom-efficient and transition metal-free approach to amides from the corresponding benzyl hydrocarbons through C-H and C-C bond cleavage has been developed. Mechanistic studies have shown that a DDQ-promoted cross-dehydrogenative coupling (CDC) reaction with subsequent oxidation and rearrangement are involved in this transformation. The Royal Society of Chemistry.
- Qiu, Jun,Zhang, Ronghua
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supporting information
p. 6008 - 6012
(2013/09/12)
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- Atmospheric pressure aminocarbonylation of aryl iodides using palladium nanoparticles supported on MOF-5
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An efficient amide synthesis by atmospheric pressure aminocarbonylation using palladium nanoparticles supported on MOF-5 is reported. Interestingly, only 0.5 wt% palladium loading was required to achieve high yields. The catalyst is recyclable and offers negligible palladium leaching.
- Dang, Tuan T.,Zhu, Yinghuai,Ghosh, Subhash C.,Chen, Anqi,Chai, Christina L. L.,Seayad, Abdul M.
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supporting information; experimental part
p. 1805 - 1807
(2012/03/08)
-
- NOVEL BIARYLAMIDE DERIVATIVE AND COMPOSITIONS CONTAINING THE DERIVATIVE AS AN ACTIVE INGREDIENT
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The present invention relates to a novel biarylamide derivative and a pharmaceutical composition or a cosmetic composition comprising the same as an active ingredient. More particularly, the present invention relates to a novel biarylamide derivative, a pharmaceutical composition or a cosmetic composition for preventing or treating a pigmentation disorder caused by an abnormal excess of melanin or a disease caused by melanocyte hyperplasia comprising the same as an active ingredient. The biarylamide derivative of the present invention inhibits melanin production and thus inhibits melanocyte hyperplasia. Therefore, a cosmetic composition comprising the biarylamide is excellent in a whitening effect, and a pharmaceutical composition comprising the biarylamide is effective in the prevention or treatment of pigmentation disorders of skin such as lentigo, melasma, freckle, etc. and malignant melanoma.
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Page/Page column 10
(2012/12/13)
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- Citric acid catalysed Beckmann rearrangement, under solvent free conditions
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Citric acid is reported to be a highly efficient and eco-friendly catalyst for the Beckmann rearrangement under solvent free conditions.
- Thopate, Shankar Ramchandra,Kote, Santosh Rajaram,Rohokale, Sandeep Vasantrao,Thorat, Nitin Madhukar
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experimental part
p. 124 - 125
(2011/07/07)
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- Influence of polarity on the scalability and reproducibility of solvent-free microwave-assisted reactions
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Organic reactions performed in the absence of solvent in domestic ovens without appropriate temperature control are generally considered as not reproducible, particularly when different instruments are used. For this reason, reproducibility has historically been one of the major issues associated with Microwave-Assisted Organic Synthesis (MAOS) especially when domestic ovens are involved. The lack of reproducibility limits the general applicability and the scale up of these reactions. In this work several solvent-free reactions previously carried out in domestic ovens have been translated into a single-mode microwave reactor and then scaled up in a multimode oven. The results show that most of these reactions, although not considered as reproducible, can be easily updated and applied in microwave reactors using temperature-controlled conditions. Furthermore, computational calculations can assist to explain and/or predict whether a reaction will be reproducible or not.
- Diaz-Ortiz, Ange,De La Hoz, Antonio,Alcazar, Jesus,Carrillo, Jose R.,Herrero, Maria A.,Fontana, Alberto,Munoz, Juan De M.,Prieto, Pilar,De Cozar, Abel
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experimental part
p. 109 - 116
(2012/04/18)
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- Manganese-catalyzed cleavage of a carbon-carbon single bond between carbonyl carbon and α-carbon atoms of ketones
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Singled out: Treatment of ketones with carbodiimides in the presence of a catalytic amount of either [{HMn(CO)4}3] or [Mn 2(CO)10] gave amides in good to excellent yields. In this reaction, the carbon-carbon single bond of a ketone is cleaved efficiently. The reaction also proceeded by using isocyanates instead of carbodiimides. Copyright
- Kuninobu, Yoichiro,Uesugi, Tadamasa,Kawata, Atsushi,Takai, Kazuhiko
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p. 10406 - 10408
(2011/12/04)
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- Convenient palladium-catalyzed aminocarbonylation of anilines to N-arylbenzamides
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The first one-pot diazotization/aminocarbonylation reaction of anilines to benzamides has been developed. In the presence of commercially available palladium acetate/P(o-Tolyl)3 as the catalyst system without base at low temperature (50°C) a variety of amides were synthesized in moderate to good yields.
- Wu, Xiao-Feng,Schranck, Johannes,Neumann, Helfried,Beller, Matthias
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experimental part
p. 3702 - 3704
(2011/08/06)
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- A simple and highly efficient one-pot procedure for the synthesis of amides via beckmann rearrangements using 1-tosylimidazole (TsIm)
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A facile and highly efficient method for one-pot Beckmann rearrangement of ketoximes into N-substituted amides using N-(p-toluenesulfonyl)imidazole (TsIm) is described. In this method, ketoximes are refluxed with TsIm and Cs2CO3 in the presence of SiO2 as a recyclable catalyst in DMF affording the corresponding amides in high yields. This methodology is highly efficient and regioselective for various structurally diverse ketoximes including symmetrical and unsymmetrical as well as cyclic oximes. The results of quantum mechanical studies used to rationalize the experimental outcomes are discussed. Copyright Taylor & Francis Group, LLC.
- Rad, Mohammad Navid Soltani,Khalafi-Nezhad, Ali,Behrouz, Somayeh,Amini, Zohreh,Behrouz, Marzieh
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experimental part
p. 1658 - 1671
(2010/09/09)
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- Amidation of aryl halides catalyzed by the efficient and recyclable Cu 2O nanoparticles
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Cu2O nanoparticles/DMEDA (N,N′-dimethylethylenediamine) was proved to be an efficient catalyst system for amidation of aryl halides under mild condition. This method displayed excellent selectivity and the catalyst was recyclable without loss of activity. The low cost, simple operation and excellent yields make this approach attractive for industrial applications. Cu2O nanoparticles/DMEDA (N,N′-dimethylethylenediamine) was proved to be an efficient catalyst system for amidation of aryl halides under mild condition. This method displayed excellent selectivity and the catalyst was recyclable without loss of activity. The low cost, simple operation and excellent yields make this approach attractive for industrial applications. Copyright
- Yao, Zijian,Wei, Xianwen
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experimental part
p. 2260 - 2268
(2011/10/12)
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- ANTI-CANCER AGENTS AND ANDROGEN INHIBITION ACTIVITY COMPOUND
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A qualitative 3D pharmacophore model (a common feature based model or Catalyst HipHop algorithm) developed from well-known natural product androgen receptor down-regulating agents (ARDAs). The 3D pharmacophore model is used as a template in virtual screening compounds for new ARDAs. ARDA compounds and compounds that strongly inhibit the growth of human prostate LNCaP cells. The compounds may be used in compositions and methods of inhibiting cell proliferation of a cancer and methods of preventing or treating cancer, including prostate cancer.
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Page/Page column 31
(2008/12/06)
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- Potent anti-prostate cancer agents derived from a novel androgen receptor down-regulating agent
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The search for novel androgen receptor (AR) down-regulating agents by catalyst HipHop pharmacophore modeling led to the discovery of some lead molecules. Unexpectedly, the effect of these leads on human prostate cancer LNCaP cell viability did not correlate with the ability of the compounds to cause down-regulation of AR protein expression. Through rational synthetic optimization of the lead compound (BTB01434), we have discovered a series of novel substituted diaryl molecules as potent anti-prostate cancer agents. Some compounds (1-6) were shown to be extremely potent inhibitors of LNCaP cell viability with GI50 values in the nanomolar range (1.45-83 nM). The most potent compound (4-methylphenyl)[(4-methylphenyl)sulfonyl]amine (5) with a GI50 value of 1.45 nM is 27,000 times more potent than our lead compound BTB01434 (GI50 = 39.8 μM). In addition, some of the compounds exhibited modest anti-androgenic activities and one was also a potent inhibitor (GI50 = 850 nM) of PC-3 (AR-null) cell growth. A clear structure-activity relationship (SAR) has been established for activity against LNCaP cells, where potent molecules possess two substituted/unsubstituted aromatic rings connected through a sulfonamide linker. These novel compounds are strong candidates for development for the treatment of hormone-sensitive and importantly hormone-refractory prostate cancers in humans.
- Purushottamachar, Puranik,Khandelwal, Aakanksha,Vasaitis, Tadas S.,Bruno, Robert D.,Gediya, Lalji K.,Njar, Vincent C.O.
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p. 3519 - 3529
(2008/12/20)
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- Palladium-catalyzed cyclocarbonylation of o-lodoanilines with Imidoyl Chlorides to produce quinazolin-4(3H)-ones
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A wide variety of substituted quinazolin-4(3H)-ones were prepared in 63-91% yields by the palladium-catalyzed cyclocarbonylation of o-iodoanilines with imidoyl chlorides and carbon monoxide. The reaction is believed to proceed via in situ formation of an amidine, followed by oxidative addition, CO insertion, and intramolecular cyclization to give the substituted quinazolin-4(3H)-ones.
- Zheng, Zhaoyan,Alper, Howard
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supporting information; experimental part
p. 829 - 832
(2009/04/07)
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- Mercury-catalyzed rearrangement of ketoximes into amides and lactams in acetonitrile
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(Chemical Equation Presented) An acetonitrile solution of mercury(II) chloride has been found to catalyze efficiently the conversion of a diverse range of ketoximes into their corresponding amides/lactams.
- Ramalingan, Chennan,Park, Yong-Tae
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p. 4536 - 4538
(2008/02/04)
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- Efficient microwave access to polysubstituted amidines from imidoylbenzotriazoles
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Microwave reactions of primary and secondary amines with imidoylbenzotriazoles 6a-w gave diversely substituted amidines 7a-Aa in 76-94% yields. Convenient preparations of a variety of amides 5a-Ab (87-96%) and imidoylbenzotriazoles 6a-w (56-95%) have also been developed using microwave irradiation under mild conditions and short reaction times. These results demonstrate further the advantages of microwave synthesis and introduce a new application of imidoylbenzotriazoles in the preparation of polysubstituted amidines.
- Katritzky, Alan R.,Cai, Chunming,Singh, Sandeep K.
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p. 3375 - 3380
(2007/10/03)
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- A new direct synthesis of aromatic amides in the presence of triethyl phosphite and 4-dimethylaminopyridine
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Aromatic amides have been prepared in high to moderate yields by a new direct synthesis from aromatic carboxylic acids and aromatic amines in the presence of a novel reagent, namely triethyl phosphite-4-dimethylaminopyridine (TEP-4-DMAP), using pyridine as a solvent, at 120-130°C for 6-8 hours.
- Chiriac, Constantin I.,Tanasǎ, Fulga,Onciu, Marioara
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p. 269 - 272
(2007/10/03)
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- Fluorous Coupling Reagents: Application of 2-Chloro-4,6- bis[(heptadecafluorononyl)oxy]-1,3,5-triazine in Peptide Synthesis
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Benzyloxycarbonyl N-protected and C-terminus methyl ester protected amino acids react in THF in the presence of 4-methylmorpholine and fluorous condensation reagent, 2-chloro-4,6-bis[(heptadecafluorononyl)oxy[-1,3,5- triazine, to form di- and tripeptides
- Markowicz, Marcin W.,Dembinski, Roman
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- Synthesis and Biological Evaluation of 2,3,5-Substituted [1,2,4]Thiadiazoles as Allosteric Modulators of Adenosine Receptors
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A number of 2,3,5-substituted [1,2,4]thiadiazole analogues of SCH-202676 (N-(2,3-diphenyl-[1,2,4]thiadiazole-5(2H)-ylidene)methanamine, 7a) were synthesized and tested as potential allosteric modulators of adenosine receptors. All compounds were capable of displacing the binding of the radiolabeled agonist [3H]CCPA to human A1 adenosine receptors, whereas modest and varying effects were observed on the binding of [3H]DPCPX, a radiolabeled antagonist for this receptor subtype. Four compounds, 7a (SCH-202676), 7k (LUF5792), 71 (LUF5794), and 8e (LUF5789), were selected for more detailed characterization. They all proved allosteric inhibitors of agonist binding, with 7k being most potent, whereas their effects on antagonist binding were more ambiguous. Subsequently, experiments were done on human adenosine A2A and A3 receptors. Compounds 7a and 7l displayed peculiar displacement characteristics of both radiolabeled agonist and antagonist binding to A2A receptors, whereas 7a showed some activity on A3 receptors.
- Van Den Nieuwendijk, Adrianus M. C. H.,Pietra, Daniele,Heitman, Laura,G?bly?s, Anikó,IJzerman, Adriaan P.
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p. 663 - 672
(2007/10/03)
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