- Chemoselective Alkylation of Aminoacetophenones with Alcohols by Using a Palladacycle-Phosphine Catalyst
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The development of efficient and environmentally benign palladacycle-phosphine catalyzed process to enable the formation of chemoselective C-alkylated or N-alkylated aminoacetophenones with alcohols is described. This methodology proved to be tunable by variation of the base and the temperature, which allows for the isolation of structurally diverse C-alkylated and N-alkylated aminoacetophenones. Moreover, this methodology has been applied to the synthesis of biologically and industrially important donepezil.
- Mamidala, Ramesh,Subramani, M. Siva,Samser, Shaikh,Biswal, Priyabrata,Venkatasubbaiah, Krishnan
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- AgPd Nanoparticles Deposited on WO2.72 Nanorods as an Efficient Catalyst for One-Pot Conversion of Nitrophenol/Nitroacetophenone into Benzoxazole/Quinazoline
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We report a seed-mediated growth of 2.3 nm AgPd nanoparticles (NPs) in the presence of 40 × 5 nm WO2.72 nanorods (NRs) for the synthesis of AgPd/WO2.72 composites. The strong interactions between AgPd NPs and WO2.72 NRs make the composites, especially the Ag48Pd52/WO2.72, catalytically active for dehydrogenation of formic acid (TOF = 1718 h-1 and Ea = 31 kJ/mol) and one-pot reactions of formic acid, 2-nitrophenol, and aldehydes into benzoxazoles in near quantitative yields under mild conditions. The catalysis can also be extended to the one-pot reactions of ammonium formate, 2-nitroacetophenone, and aldehyde for high yield syntheses of quinazolines. Our studies demonstrate a new catalyst design to achieve a green chemistry approach to one-pot reactions for the syntheses of benzoxazoles and quinazolines.
- Yu, Chao,Guo, Xuefeng,Xi, Zheng,Muzzio, Michelle,Yin, Zhouyang,Shen, Bo,Li, Junrui,Seto, Christopher T.,Sun, Shouheng
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- Efficient photocatalytic one-pot hydrogenation and N-alkylation of nitrobenzenes/benzonitriles with alcohols over Pd/MOFs: Effect of the crystal morphology & “quasi-MOF” structure
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One-pot multi-step reactions over visible-light induced catalysis feature the sustainable green process. Here, ligand structure change and 2-MI coordinated modulation were adapted to adjust the crystal size, morphology and crystalline structure of Fe-MOFs; double solvent impregnation was employed for the Pd loading; “quasi-MOF” materials with retained morphology were formed with calcination under N2. Above modified materials were employed as multifunctional photocatalysts for highly efficient one-pot hydrogenation and N-alkylation of nitrobenzenes or benzonitriles with alcohols after in situ Pd photoreduction. Photocatalytic performance was evidently affected by the Fe-MOFs crystal size, morphology, crystalline structure alteration and “quasi-MOF” construction. One-pot hydrogenation and N-alkylation of benzonitriles with alcohols was achieved with excellent catalytic performance firstly in heteroegeneous catalysis. Reaction mechanism was proposed with the assistance of in situ DRIFTS.
- Bian, Fengxia,Cheng, Hongmei,Jiang, Heyan,Liu, Xingyan,Long, Xingyu,Yang, Chaofen
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p. 121 - 131
(2020/06/23)
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- Divergent strategy for the chemoselective synthesis of N-Arylbenzimidazoles and N-Arylindazoles from arylamino oximes
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An efficient and divergent synthesis of N-arylbenzimidazoles and N-arylindazoles from arylamino oximes based on reaction conditions selection was developed. The synthesis was approached by treating oximes with BTC and the chemoselectivity was regulated by the amount of Et3N. This switchable N–N and N–C bond formation process features mild reaction conditions, simple execution, high chemoselectivity and broad substrate scope.
- Li, Zhen-Hua,Sun, Xiao-Meng,Qin, Jin-Jing,Tan, Zhi-Yong,Wang, Wen-Biao,Ma, Yao
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- Para-Selective C-H Olefination of Aniline Derivatives via Pd/S,O-Ligand Catalysis
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Herein we report a highly para-selective C-H olefination of aniline derivatives by a Pd/S,O-ligand-based catalyst. The reaction proceeds under mild reaction conditions with high efficiency and broad substrate scope, including mono-, di-, and trisubstituted tertiary, secondary, and primary anilines. The S,O-ligand is responsible for the dramatic improvements in substrate scope and the high para-selectivity observed. This methodology is operationally simple, scalable, and can be performed under aerobic conditions.
- Naksomboon, Kananat,Poater, Jordi,Bickelhaupt, F. Matthias,Fernández-Ibá?ez, M. ángeles
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supporting information
p. 6719 - 6725
(2019/05/06)
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- Design, synthesis and biological activity of selective hCAs inhibitors based on 2-(benzylsulfinyl)benzoic acid scaffold
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A large library of derivatives based on the scaffold of 2-(benzylsulfinyl)benzoic acid were synthesised and tested as atypical inhibitors against four different isoforms of human carbonic anhydrase (hCA I, II, IX and XII, EC 4.2.1.1). The exploration of the chemical space around the main functional groups led to the discovery of selective hCA IX inhibitors in the micromolar/nanomolar range, thus establishing robust structure-activity relationships within this versatile scaffold. HPLC separation of some selected chiral compounds and biological evaluation of the corresponding enantiomers was performed along with molecular modelling studies on the most active derivatives.
- Rotondi, Giulia,Guglielmi, Paolo,Carradori, Simone,Secci, Daniela,De Monte, Celeste,De Filippis, Barbara,Maccallini, Cristina,Amoroso, Rosa,Cirilli, Roberto,Akdemir, Atilla,Angeli, Andrea,Supuran, Claudiu T.
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p. 1400 - 1413
(2019/08/26)
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- Organometallic titanocene complex as highly efficient bifunctional catalyst for intramolecular Mannich reaction
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Bifunctional catalysts bearing two catalytic sites, Lewis acidic organometallic titanocene and Br?nsted acidic COOH, have been assembled in situ from Cp2TiCl2 with carboxylic acid ligands, showing high catalytic activity over an intramolecular Mannich reaction towards synthesis of 2-aryl-2,3-dihydroquinolin-4(1H)-ones. The determination of the bifunctional catalyst Cp2Ti(C8H4NO6)2 was elucidated by single X-ray HR-MS and investigation of catalytic behavior. In particular, masking the Br?nsted acidic COOH catalytic site with dormant COOMe lowered the reaction yield greatly, indicating that two catalytic sites work together to maintain high catalytic efficiency.
- Wang, Yunyun,Jian, Yajun,Wu, Ya,Sun, Huaming,Zhang, Guofang,Zhang, Weiqiang,Gao, Ziwei
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- C–C bond-forming reactions of ground-state aryl halides under reductive activation
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Under basic conditions aryl halides can undergo SRN1 reactions, BHAS reactions and benzyne formations. Appropriate complex substrates afford an opportunity to study inherent selectivities. SRN1 reactions are usually favoured under ph
- Emery, Katie J.,Tuttle, Tell,Kennedy, Alan R.,Murphy, John A.
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p. 7875 - 7887
(2016/11/17)
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- Direct synthesis of 2-aryl-4-quinolones via transition-metal-free intramolecular oxidative C(sp3)-H/C(sp3)-H coupling
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A novel, metal-free oxidative intramolecular Mannich reaction was developed between secondary amines and unmodified ketones, affording a simple and direct access to a broad range of 2-arylquinolin-4(1H)-ones through C(sp3)-H activation/C(sp3)-C(sp3) bond formation from readily available N-arylmethyl-2-aminophenylketones, using TEMPO as the oxidant and KOtBu as the base.
- Hu, Wei,Lin, Jian-Ping,Song, Li-Rui,Long, Ya-Qiu
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supporting information
p. 1268 - 1271
(2015/05/20)
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- Copper-catalyzed intramolecular oxidative C(sp3)-H amidation of 2-aminoacetophenones: Efficient synthesis of indoline-2,3-diones
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An efficient synthesis of diverse indoline-2,3-diones from 2-aminoacetophenones through copper-catalyzed intramolecular C(sp3)-H amidation is developed. The reaction proceeds in DMSO by using O2 as the sole oxidant to provide the desired products in moderate to good yields.
- Huang, Jinbo,Mao, Tingting,Zhu, Qiang
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supporting information
p. 2878 - 2882
(2014/05/20)
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- Intramolecular dehydrative coupling of tertiary amines and ketones promoted by KO-t-Bu/DMF: A new synthesis of indole derivatives
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A new synthesis of indole derivatives has been achieved through intramolecular dehydrative coupling of tertiary amines and ketones promoted by KO-t-Bu/DMF. The reaction probably proceeds via an α-amino alkyl radical pathway.
- Wei, Wen-Tao,Dong, Xue-Jiao,Nie, Shao-Zhen,Chen, Yan-Yan,Zhang, Xue-Jing,Yan, Ming
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supporting information
p. 6018 - 6021
(2014/01/06)
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- Iridium catalysed chemoselective alkylation of 2′-aminoacetophenone with primary benzyl type alcohols under microwave conditions
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2′-Aminoacetophenone was chemoselectively alkylated with a range of substituted benzyl, heteroaryl alcohols to afford either the corresponding C- or N- alkylated products in good yield.
- Bhat, Shailen,Sridharan, Visuvanathar
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supporting information; experimental part
p. 4701 - 4703
(2012/05/31)
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- A novel intramolecular photocyclization of N-(2-bromoalkanoyl) derivatives of 2-acylanilines via 1,8-hydrogen abstraction
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The photochemical reactions of different N-(2-acylphenyl)-2-bromo-2- methylpropanamides have been investigated. Irradiation of the N-unsubstituted anilides 1a-1c gave the corresponding dehydrobromination, cyclization, and bromo-migration products 2, 3, and 4, respectively (Table 1). Irradiation of the N-alkyl anilides 1e-1g afforded the corresponding deacylation and cyclization products 5 and 6, respectively, whereas irradiation of the N-alkyl anilides 1i-1k, carrying 2-benzoyl groups on the aromatic rings, afforded the unexpected tricyclic lactams 7 (besides 2, 5, and 6). The formation of the cyclization products 6 could be rationalized in terms of an electrocyclic ring closure of the 6π-electron-conjugated enamides 2 produced by dehydrobromination of 1, followed by thermal 1,5-acyl migration (Path B in the Scheme). The formation of the bridged lactams 7 probably follows a mechanism involving the 1,7-diradical 8 generated by ζ-H-abstraction (1.8-H transfer) by an excited acyl O-atom (Path A).
- Nishio, Takehiko,Koyama, Hiroyuki,Sasaki, Daigo,Sakamoto, Masami
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p. 996 - 1003
(2007/10/03)
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- On the synthesis and reactivity of 1-benzyl-2-arylquinoline-4-thiones
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A panel of 1-benzyl-2-aryl-4-quinolones was synthesized in three steps and converted to the corresponding 4-thione derivatives using Lawesson's reagent. The representative vinylogous thioamide (5a) was alkylated to afford a novel series of quinolinium sal
- Niedzinski, Edmund J.,Lashley, Matthew R.,Nantz, Michael H.
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p. 623 - 627
(2007/10/03)
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