- Visible-Light Induced C(sp2)?H Amidation with an Aryl–Alkyl σ-Bond Relocation via Redox-Neutral Radical–Polar Crossover
-
We report an approach for the intramolecular C(sp2)?H amidation of N-acyloxyamides under photoredox conditions to produce δ-benzolactams with an aryl-alkyl σ-bond relocation. Computational studies on the designed reductive single electron transfer strategy led us to identify N-[3,5-bis(trifluoromethyl)benzoyl] group as the most effective amidyl radical precursor. Upon the formation of an azaspirocyclic radical intermediate by the selective ipso-addition with outcompeting an ortho-attack, radical–polar crossover was then rationalized to lead to the rearomative ring-expansion with preferential C?C bond migration.
- Chang, Sukbok,Jeong, Jiwoo,Jung, Hoimin,Keum, Hyeyun,Kim, Dongwook
-
supporting information
p. 25235 - 25240
(2021/10/25)
-
- Room Temperature Benzofused Lactam Synthesis Enabled by Cobalt(III)-Catalyzed C(sp2)?H Amidation
-
Benzofused lactams, especially indolin-2-one and dihydroquinolin-2-one are popular structural motives in durgs and natural products. Herein, we developed a room temperature and robust synthesis of benzofused lactams through cobalt(III)-catalyzed C(sp
- Tian, Xun,Li, Xin,Duan, Shengzu,Du, Ya,Liu, Tongqi,Fang, Yongsheng,Chen, Wen,Zhang, Hongbin,Li, Minyan,Yang, Xiaodong
-
p. 1050 - 1058
(2020/12/18)
-
- Schmidt reaction on substituted 1-indanones / N-alkylation: Synthesis of benzofused six-membered ring lactams and their evaluation as antimicrobial agents
-
Background: The presence of bicyclic lactams is reflected in various pharmaceuticals, natural products, agrochemicals and active components of various dyes. Nowadays, to see the increasing rate of antimicrobial resistance and high incidence of microbial infections, there is a strong need to develop novel antimicrobial agents. In this study, we synthesized some benzofused six membered ring lactams and their alkyl derivatives as a trial to obtain valuable precursors for the discovery of future an-timicrobial drugs. Methods: The substituted lactams 3,4-dihydro-2(1H)-quinolinones 3a-c and 3,4-dihydro-1(2H)-isoquinolinones 4a-c were synthesized by Schmidt reaction on indanones 2a-c which were obtained by Friedel-Crafts reaction on β-substituted α,β-unsaturated carboxylic acids 1a-c. Lactams 6 and 7 were obtained by N-alkylation on benzofused lactams 3a-c and 4a-c in good to excellent yields. Structures of all products were well characterized by the rigorous analysis of their IR,1H NMR,13C NMR, MS and elemental analysis. The in vitro antimicrobial activities of all the synthesized compounds 6 and 7 were determined against Gram-positive, Gram-negative bacteria and the fungal species Candida albi-cans using broth macrodilution method. Results: The Schmidt reaction of 3-methylindanone, 3-phenylindanone and 3,3-dimethylindanone using methane sulphonic acid was found to behave differently with respect to isolated yield as well as isomeric ratio of both lactams. Bacterial growth inhibition was observed with bicyclic lactam derivatives although their MIC values were higher than ampicillin. The significant inhibitory effects were shown by majority of compounds with MIC values 125-250 μg/ml. Antifungal activity of bicyclic lactam derivatives was observed against C. albicans. However, MICs values of all tested compounds were higher compared to standard antifungal agent miconazole. Conclusion: The four Schmidt experimental conditions were tried with the aim of achieving both 6-membered ring lactams in equal ratio and NaN3/MeSO3H was identified to fulfill our purpose. As evident by structure-activity relationship, the tested compounds have not resulted in superior antibacterial or anti-fungal compounds compared to standard antimicrobials. Hence, there is still a need to carry out further modifications in bicyclic lactams structure in order to more efficacious antimicrobial lead molecules.
- Arora, Rashi,Bala, Renu,Kumari, Poonam,Sood, Sumit,Yadav, Ajar Nath,Singh, Nasib,Singh, Karan
-
p. 606 - 613
(2019/05/01)
-
- Novel nano-titania embedded on graphite (nano-TiO2@Cg) as an efficient, eco-friendly, and recyclable catalyst for one-pot, solvent-free synthesis of 4-aryl-3,4-dihydroquinolin-2(1H)-ones, 3-methyl-4-aryl/alkyl-2,4,5,7-tetrahydropyrazolo[3,4-b]pyridin-6-ones, and coumarin-3-carboxylic esters
-
Abstract: A novel acid catalyst has been synthesized by commercial anatase phase nano-TiO2 and graphite (nano-TiO2@Cg) via a simple procedure and characterized by Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, field emission scanning electron microscopy, and potentiometric titration techniques. It has been utilized as a convenient nano-catalyst to accelerate the one-pot, solvent-free, three-component reaction of Meldrum’s acid, aromatic amines (5-methylpyrazol-3-amine), and various aromatic aldehydes to form 4-aryl-3,4-dihydroquinolin-2-(1H)-ones and 3-methyl-4-aryl/alkyl-2,4,5,7-tetrahydropyrazolo[3,4-b]pyridin-6-ones, respectively. The catalytic activity has also examined for the preparation of coumarin-3-carboxylic esters from Meldrum’s acid, salicylaldehydes, and alcohols successfully. Low catalyst loading, clean process without utilizing any hazardous solvent, easy workup procedure, reusability and recyclability of the nano-catalyst within four runs without activity loss, high yields of the products, in addition with utilizing a vast range of substrates are some highlighted points of the reported protocols. Graphical abstract: [Figure not available: see fulltext.]
- Nikoofar, Kobra,Molaei Yielzoleh, Fatemeh
-
p. 7353 - 7367
(2018/08/29)
-
- Palladium-Catalyzed Ullmann Cross-Coupling of β-Iodoenones and β-Iodoacrylates with o-Halonitroarenes or o-Iodobenzonitriles and Reductive Cyclization of the Resulting Products to Give Diverse Heterocyclic Systems
-
The palladium-catalyzed Ullmann cross-coupling of β-iodoenones and β-iodoacrylates such as 5 (X = I) with o-halonitroarenes and o-iodobenzonitriles including 2 affords products such as compound 7. These can be engaged in a range of reductive cyclization r
- Khan, Faiyaz,Dlugosch, Michael,Liu, Xin,Khan, Marium,Banwell, Martin G.,Ward, Jas S.,Carr, Paul D.
-
p. 2770 - 2773
(2018/05/22)
-
- AlCl 3 -Mediated Synthesis of 4-Aryl-2-quinolone-3-carboxylates
-
4-Aryl-2-quinolones are important skeletons from both chemical and medicinal viewpoints. We herein report the development of an efficient synthetic method for 3-substituted 4-aryl-2-quinolones. The key reaction in this process involves an AlCl 3/sub
- Yang, Seung-Hye,Jo, Seohyun,Shin, Dongyun
-
p. 1614 - 1619
(2017/08/11)
-
- Practical synthetic strategies towards lipophilic 6-iodotetrahydroquinolines and -dihydroquinolines
-
The synthesis of novel tetrahydroquinolines (THQ) and dihydroquinolines (DHQ) are reported using three practical, scalable synthetic approaches to access highly lipophilic analogues bearing a 6-iodo substituent, each with a different means of cyclisation. A versatile and stable quinolin-2-one intermediate was identified, which could be reduced to the corresponding THQ with borane reagents, or to the DHQ with diisobutylaluminium hydride via a novel elimination that is more favourable at higher temperatures. Coupling these strongly electron-donating scaffolds to electron-accepting moieties caused the resulting structures to exhibit strong fluorescence.
- Chisholm, David R.,Zhou, Garr-Layy,Pohl, Ehmke,Valentine, Roy,Whiting, Andrew
-
supporting information
p. 1851 - 1862
(2016/10/05)
-
- Efficient one-pot synthesis of dihydroquinolinones in water at room temperature
-
A mild and robust one-pot protocol for the Rh-catalyzed 1,4-addition of 2-aminoboronic acid to α,β-unsaturated esters for the efficient synthesis of dihydroquinolinones has been developed. Furthermore the addition of a variety of substituted boronic acids to diverse α,β-unsaturated esters has been investigated. The reactions proceed in water containing catalytic amounts of the commercially available designer surfactant TPGS-750-M (via the formation of nanomicelles). This mild and easy to perform process proceeds at room temperature and tolerates a wide range of functionalities.
- Linsenmeier, Anna M.,Braje, Wilfried M.
-
p. 6913 - 6919
(2015/08/24)
-
- Tandem superelectrophilic hydroarylation of CC bond and carbonyl reduction in cinnamides: Synthetic rout to 3,3-diarylpropylamines, valuable pharmaceuticals
-
Cinnamides ArCHCHCONRR′ in reactions with arenes Ar′H under the action of Bronsted (TfOH, FSO3H) or Lewis (AlBr3) superacids at rt for 1-2 h give CC bond hydroarylation products ArAr′CHCH2CONRR′ in yields of 63-98%. Reduction (LiAlH4/Et2O) of carbonyl group in the latter results in the formation of 3,3-diarylpropylamines ArAr′CHCH2CH2NRR′, valuable drugs. The reaction intermediates, superelectrophilic dications ArC+H-CH2C(OH+)NRR′, have been characterized by DFT calculations in terms of global electrophilicity index, natural charges, and atomic orbitals contributions.
- Zakusilo, Dmitry N.,Ryabukhin, Dmitry S.,Boyarskaya, Irina A.,Yuzikhin, Oleg S.,Vasilyev, Aleksander V.
-
p. 102 - 108
(2015/02/02)
-
- Sequential rhodium/palladium catalysis: Enantioselective formation of dihydroquinolinones in the presence of achiral and chiral ligands
-
Compatible combinations of achiral and chiral ligands can be used in rhodium/palladium catalysis to achieve highly enantioselective domino reactions. The difference in rates of catalysis and minimal effects of ligand interference confer control in the dom
- Zhang, Lei,Qureshi, Zafar,Sonaglia, Lorenzo,Lautens, Mark
-
p. 13850 - 13853
(2015/01/16)
-
- Regiodivergent access to five- and six-membered benzo-fused lactams: Ru-catalyzed olefin hydrocarbamoylation
-
We report herein a new strategy of the Ru-catalyzed intramolecular olefin hydrocarbamoylation for the regiodivergent synthesis of five- and six-membered benzo-fused lactams starting from N-(2-alkenylphenyl)formamides. Using a combined catalyst of Ru3
- Li, Bin,Park, Yoonsu,Chang, Sukbok
-
p. 1125 - 1131
(2014/02/14)
-
- ZrOCl2 · 8H2O: An efficient, ecofriendly, and recyclable catalyst for ultrasound-accelerated, one-pot, solvent-free synthesis of 8-aryl-7,8-dihydro-[1,3]dioxolo[4,5-g] quinolin-6-(5H)-one and 4-aryl-3,4-dihydroquinolin-2(1 H)-one derivatives
-
A convenient, one-pot, solvent-free reaction of amines, aromatic aldehydes, and Meldrum's acid to form 8-aryl-7,8-dihydro-[1,3]dioxolo[4,5-g]quinolin-6- (5H)-one and 4-aryl-3,4-dihydroquinolin-2-(1H)-one in the presence of 10 mol% ZrOCl2 · 8H2O under ultrasonic irradiation is described. This new protocol offers several advantages including low catalyst loading, clean reaction, easy workup, use of recyclable and ecofriendly catalyst, short reaction times, good yields, and solvent-free conditions. Copyright
- Azarifar, Davood,Sheikh, Davood
-
supporting information
p. 2517 - 2526
(2013/07/26)
-
- Synthesis and anticancer activity of aminodihydroquinoline analogs: Identification of novel proapoptotic agents
-
A series of 2-aminodihydroquinoline analogs were synthesized and their in vitro cytotoxicities against metastatic breast adenocarcinoma cell line MDA-MB-231 were tested. Five out of 16 compounds exhibited promising activity and structure-activity relationship revealed major role of dialkylaminoethyl substituents on dihydroquinoline ring for the activity. Two compounds, 5f and 5h, presented cytotoxicity with IC50 values of about 2 μM when the compounds were treated to the cells without serum. The cell proliferation was inhibited mildly when the cells cultured with serum. Flow cytometry analyses showed that those compounds arrested the cells at G2/M checkpoint when the cell cycle is active while they induce apoptosis when the cell growth is restricted due to the absence of growth factors. These results suggest the two novel compounds may have anticancer activity through cell cycle arrest and pro apoptosis mechanism.
- Lee, Eun,Han, Seulaa,Jin, Guo Hua,Lee, Hwa Jin,Kim, Woo-Young,Ryu, Jae-Ha,Jeon, Raok
-
supporting information
p. 3976 - 3978
(2013/07/25)
-
- Palladium-catalyzed decarboxylative coupling of potassium nitrophenyl acetates with aryl halides
-
A palladium-catalyzed decarboxylative cross-coupling of potassium 2- and 4-nitrophenyl acetates with aryl chlorides and bromides has been developed. Because the nitro group can be readily converted to many other functional groups, the new reaction provides a useful method for the preparation of diverse 1,1-diaryl methanes and their derivatives.
- Shang, Rui,Huang, Zheng,Chu, Ling,Fu, Yao,Liu, Lei
-
p. 4240 - 4243
(2011/10/09)
-
- Rhodium-catalyzed domino conjugate addition-cyclization reactions for the synthesis of a variety of N- and O-heterocycles: Arylboroxines as effective carbon nucleophiles
-
Facile and efficient Rh(I)-catalyzed domino conjugate addition-cyclization reactions of olefins bearing two electrophilic sites and a pendant nucleophile with organoboroxines have been developed to afford a variety of N- and O-heterocycles, such as 3,4-dihydroquinolin-2(1H)-ones, 3,4-dihydrocoumarins, and pyrrolidin-2-ones, which constitute important motifs in biologically active natural and synthetic organic compounds.
- Park, Ja Ock,Youn, So Won
-
supporting information; experimental part
p. 2258 - 2261
(2010/07/17)
-
- Convergent synthesis of dihydroquinolones from o-aminoarylboronates
-
An efficient and convergent one-step synthesis of substituted dihydroquinolin-2-ones from α,β-unsaturated esters and aminoaryl pinacolboronates under rhodium catalysis is reported. The reaction is easily applicable in parallel synthesis format and provide
- Horn, Joachim,Li, Ho Yin,Marsden, Stephen P.,Nelson, Adam,Shearer, Rachel J.,Campbell, Amanda J.,House, David,Weingarten, Gordon G.
-
experimental part
p. 9002 - 9007
(2009/12/22)
-
- Recyclable selective palladium-catalyzed synthesis of five-, six- or seven-membered ring lactones and lactams by cyclocarbonylation in ionic liquids
-
The ionic liquids, BMIM PF6 or BMIM NTf2, are used successfully for the palladium-catalyzed cyclocarbonylation of 2-allylphenols and anilines, 2-vinylphenols, and 2-aminostyrenes. The reaction proceeds cleanly and efficiently to afford high yields of lactones or lactams with good or excellent selectivity for one isomer. The ionic liquid containing the palladium catalyst, and ligand, is recyclable in all cases.
- Ye, Fangguo,Alper, Howard
-
p. 1855 - 1861
(2007/10/03)
-
- Superelectrophilic activation of polyfunctional organic compounds using zeolites and other solid acids
-
Zeolites and other available solid acids have been successfully applied to initiate reactions, which were earlier recognised to involve superelectrophilic intermediates and thus required excess of superacids to be carried out.
- Koltunov, Konstantin Yu.,Walspurger, Stéphane,Sommer, Jean
-
p. 1754 - 1755
(2007/10/03)
-
- Reactions of 2-, 3- and 4-quinolinols with cyclohexane and benzene in superacids
-
Isomeric 2-, 3- and 4-quinolinols (11-13) underwent selective ionic hydrogenation with cyclohexane in CF3SO3H-SbF5 system to give 5,6,7,8-tetrahydro-2(1H)-quinolinone, 5,6,7,8-tetrahydro-3-quinolinol and 5,6,7,8-tetrahydro-4(1H)-quinolinone (28-30), respectively. When reaction was carried out in the presence of excess of aluminum chloride, 11 gave 3,4-dihydro-2(1H)-quinolinone (31), whereas 13 gave the product (30). Compounds (11) and (13) condense with benzene in the presence of aluminum halides producing phenyl substituted derivatives of 28, 31 and 30 (products 32-34), respectively. The mechanism of these and related reactions involving superelectrophilic dicationic intermediates is discussed.
- Koltunov, Konstantin Yu.,Prakash, G. K. Surya,Rasul, Golam,Olah, George A.
-
p. 757 - 772
(2007/10/03)
-
- Heterocyclic compounds, pharmaceutical compositions comprising same, and methods for inhibiting β-amyloid peptide release and/or its synthesis by use of such compounds
-
Disclosed are compounds which inhibit β-amyloid peptide release and/or its synthesis, and, accordingly, have utility in treating Alzheimer's disease. Also disclosed are pharmaceutical compositions comprising a compound which inhibits β-amyloid peptide release and/or its synthesis as well as methods for treating Alzheimer's disease both prophylactically and therapeutically with such pharmaceutical compositions.
- -
-
-