- Ruthenium-catalyzed intramolecular arene C(sp2)-H amidation for synthesis of 3,4-dihydroquinolin-2(1 H)-ones
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We report the [Ru(p-cymene)(l-proline)Cl] ([Ru1])-catalyzed cyclization of 1,4,2-dioxazol-5-ones to form dihydroquinoline-2-ones in excellent yields with excellent regioselectivity via a formal intramolecular arene C(sp2)-H amidation. The reactions of the 2- and 4-substituted aryl dioxazolones proceeds initially through spirolactamization via electrophilic amidation at the arene site, which is para or ortho to the substituent. A Hammett correlation study showed that the spirolactamization is likely to occur by electrophilic nitrenoid attack at the arene, which is characterized by a negative ρ value of -0.73.
- Au, Chi-Ming,Ling, Cho-Hon,Sun, Wenlong,Yu, Wing-Yiu
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p. 3310 - 3314
(2021/05/29)
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- Room Temperature Benzofused Lactam Synthesis Enabled by Cobalt(III)-Catalyzed C(sp2)?H Amidation
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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
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p. 1050 - 1058
(2020/12/18)
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- Synthesis of Lactams via Ir-Catalyzed C-H Amidation Involving Ir-Nitrene Intermediates
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x-membered lactams were synthesized via either an amidation of sp3 C-H bonds or an electrophilic substitution of arenes via Ir-nitrene intermediates. With the employment of a readily available iridium catalyst in dichloromethane or hexafluoro-2-propanol, a wide range of lactams were synthesized in good to excellent yields with high selectivity.
- Li, Xiaoxun,Liu, Jitian,Tang, Weiping,Wang, Shuojin,Ye, Wenjing,Zheng, Junrong
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- METHOD FOR PRODUCING LACTAM COMPOUND, AND LACTAM COMPOUND PRODUCED THEREBY
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The present invention relates to a method for producing a lactam compound from dioxazolone in the presence of a catalyst having a particular ligand, and to a lactam compound produced thereby, and can produce a lactam compound with excellent selectivity and an excellent yield by using the combination of a starting material having a particular functional group and a particular catalyst having a particular ligand.
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Paragraph 0174-0175
(2020/11/30)
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- Revisiting Arene C(sp2)?H Amidation by Intramolecular Transfer of Iridium Nitrenoids: Evidence for a Spirocyclization Pathway
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Two mechanistic pathways, that is, electrocyclization and electrophilic aromatic substitution, are operative in most intramolecular C?H amination reactions proceeding by metal nitrenoid catalysis. Reported here is an alternative mechanistic scaffold leading to benzofused δ-lactams selectively. Integrated experimental and computational analysis revealed that the reaction proceeds by a key spirocyclization step followed by a skeletal rearrangement. Based on this mechanistic insight, a new synthetic route to spirolactams has been developed.
- Hwang, Yeongyu,Park, Yoonsu,Kim, Yeong Bum,Kim, Dongwook,Chang, Sukbok
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p. 13565 - 13569
(2018/09/25)
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- Multibond Forming Tandem Reactions of Anilines via Stable Aryl Diazonium Salts: One-Pot Synthesis of 3,4-Dihydroquinolin-2-ones
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A fast and effective one-pot tandem process that generates Heck coupled products from readily available anilines via stable aryl diazonium tosylate salts was developed. The mild and simple procedure involves rapid formation of aryl diazonium salts using a polymer-supported nitrite reagent and p-tosic acid, followed by a base-free Heck-Matsuda coupling with acrylates and styrenes. Using 2-nitroanilines as substrates, the one-pot tandem process was extended for the direct synthesis of 3,4-dihydroquinolin-2-ones. In this case, following diazotization and Heck-Matsuda coupling to give methyl cinnamates, addition of hydrogen and reutilization of the palladium catalyst for reduction of the nitro group and hydrogenation of the alkene resulted in efficient formation of 3,4-dihydroquinolin-2-ones. The synthetic utility of this one-pot, four-stage process was demonstrated with the five-pot synthesis of a quinolinone-based sodium ion channel modulator.
- Faggyas, Réka J.,Grace, Megan,Williams, Lewis,Sutherland, Andrew
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p. 12595 - 12608
(2018/10/15)
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- Enabling CO Insertion into o-Nitrostyrenes beyond Reduction for Selective Access to Indolin-2-one and Dihydroquinolin-2-one Derivatives
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The transition metal-catalyzed reductive cyclization of o-nitrostyrene in the presence of carbon monoxide (CO) has been developed to be a general synthetic route to an indole skeleton, wherein CO was used as a reductant to deoxidize nitroarene into nitrosoarene and/or nitrene with CO2 release, but the selective insertion of CO into the heterocyclic product with higher atom economy has not yet been realized. Herein, the Pd-catalyzed reduction of o-nitrostyrene by CO and its regioselective insertion were efficiently achieved to produce synthetically useful five- and six-membered benzo-fused lactams. Detailed investigations revealed that the chemoselectivity to indole or lactam was sensitive to the nature of the counteranions of Pd2+ precursors, whereas ligands significantly decided the carbonylative regioselectivity by different reaction pathways. Using PdCl2/PPh3/B(OH)3 (condition A), an olefin hydrocarboxylation was primarily initiated followed by partial reduction of the NO2 moiety and cyclization reaction to give N-hydroxyl indolin-2-one, which was further catalytically reduced by CO to afford the indolin-2-one as the final product with up to 95% yield. When the reaction was conducted under the Pd(TFA)2/BINAP/TsOH·H2O system (condition B), complete deoxygenation and carbonylation of the NO2 group occurred initially to yield the corresponding isocyanate followed by internal hydrocyclization to generate 3,4-dihydroquinolin-2-one with up to 98% yield. Importantly, the methodology could be efficiently applied in the synthesis of marketed drug Aripiprazole.
- Yang, Li,Shi, Lijun,Xing, Qi,Huang, Kuo-Wei,Xia, Chungu,Li, Fuwei
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p. 10340 - 10348
(2018/10/20)
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- Pyrimidine heterocyclic compounds, preparation method and application thereof
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The present invention relates to compounds of a formula (I) shown in the description, and pharmaceutically acceptable salts, prodrugs and solvates thereof, and the compounds are useful for treating cancer and inflammation in mammals. The invention also discloses a preparation method for the compounds of the formula (I) and a pharmaceutical composition containing the compound.
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Paragraph 0209-0212
(2018/03/25)
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- Biocatalytic α-Oxidation of Cyclic Amines and N-Methylanilines for the Synthesis of Lactams and Formamides
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An environmentally friendly method for the synthesis of lactams and formamides through the biocatalytic α-oxidation of amines was developed by employing Pseudomonas plecoglossicida ZMU-T04 as a biocatalyst. In this biocatalytic process, the α-oxidation of cyclic amines and N-methylanilines proceeded smoothly to give the corresponding amides in low to high yields. Furthermore, it was demonstrated that synthetic 3,4-dihydroquinolin-2(1H)-one could be used as a key precursor of antidepressant bioactive molecules. The mechanism of this biocatalytic α-oxidation process was investigated by isotope- labeling experiments.
- Zheng, Daijun,Zhou, Xiaojian,Cui, Baodong,Han, Wenyong,Wan, Nanwei,Chen, Yongzheng
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p. 937 - 940
(2017/03/27)
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- Regiodivergent access to five- and six-membered benzo-fused lactams: Ru-catalyzed olefin hydrocarbamoylation
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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
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p. 1125 - 1131
(2014/02/14)
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- IMIDAZOLE COMPOUNDS AS MODULATORS OF FSHR AND USES THEREOF
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The present invention relates to imidazole compounds, and pharmaceutically acceptable compositions thereof, useful as positive allosteric modulators of follicle stimulating hormone receptor (FSHR).
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Paragraph 00231
(2015/01/16)
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- Reductive cyclizations of nitroarenes to hydroxamic acids by visible light photoredox catalysis
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We have developed a photocatalytic reduction of nitroarenes as an efficient, chemoselective route to biologically important N-phenyl hydroxamic acid scaffolds. Optimal conditions call for 2.5 mol% of a ruthenium photocatalyst, visible light irradiation, and a dihydropyridine terminal reductant. Because of the mild nature of the visible light activation, functional groups that might be sensitive to other non-photochemical reduction methods are easily tolerated. Georg Thieme Verlag Stuttgart New York.
- Cismesia, Megan A.,Ischay, Michael A.,Yoon, Tehshik P.
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p. 2699 - 2705
(2013/10/21)
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- The tandem reaction combining radical and ionic processes: an efficient approach to substituted 3,4-dihydroquinolin-2-ones
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3,4-Dihydroquinolin-2-ones are of great importance in the areas of pharmaceuticals. However, the direct intramolecular radical cyclizations of the corresponding amide compounds favor 5-exo products 2. Reports on the radical cyclization reactions producing
- Zhou, Wang,Zhang, Liangren,Jiao, Ning
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experimental part
p. 1982 - 1987
(2009/08/07)
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- PYRIMIDINE COMPOUNDS AND USE THEREOF
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The invention relates to novel pyrimidine compounds of general formula (I), in which: A represents a group C=W or CRfRg; B represents a chemical bond or a group CRhRi; X represents O, S, a group N-Rk or a group CRmRn; D represents C=O or a chemical bond; E represents a linear or branched 2- to 10-membered alkylene chain that, as members of a chain, can have 1 or 2 non-adjacent heteroatom group(s) K, which is selected among O, S, S(O), S(O)2 and N-Rp and which can comprise a carbonyl group and/or a cycloalkanediyl group and/or a double or triple bond; W represents oxygen or sulfur; Z, together with the carbon atoms, to which it is bound, represents a condensed, optionally substituted 5-, 6- or 7-membered carbocyclic compound or heterocyclic compound that has 1, 2, 3 or 4 heteroatoms, which are selected among N, O and S; J represents CH2, CH2-CH2 or CH2-CH2-CH2; M represents CH or N; Y represents CH2, CH2-CH2 or CH2-CH2-CH2 or M-X, together, represent CH=C or CH2-CH=C; n is 0 or 1, and; Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rk, Rp, R1, R2, R3, R4, R5 and R6 have the meanings cited in the claims and in the description. The invention also relates to the physiologically compatible acid addition salts of the aforementioned compounds, and to the use of these compounds of general formula (I) and of the physiologically compatible acid addition salts of compounds (I) for producing a pharmaceutical agent for treating diseases, which respond to the influence of dopamine D3 receptor antagonists or agonists.
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Page/Page column 44
(2010/02/15)
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- Synthesis of five-, six-, and seven-membered ring lactams by Cp*Rh complex-catalyzed oxidative N-heterocyclization of amino alcohols
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A new effective catalytic system consisting of [Cp*RhCl 2]2/K2CO3 (Cp* = pentamethylcyclopentadienyl) for the lactamization of amino alcohols has been developed. As an example, the reaction of 3-(2-aminophenyl)-1-propanol in the presence of [Cp*RhCl2]2 (5.0% Rh) and K 2CO3 (10%) in acetone gives 3,4-dihydro-2(1H)-quinolinone in an isolated yield of 80%. A variety of five-, six-, and seven-membered benzo-fused lactams are synthesized by this catalytic system.
- Fujita, Ken-Ichi,Takahashi, Yoshinori,Owaki, Maki,Yamamoto, Kazunari,Yamaguchi, Ryohei
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p. 2785 - 2788
(2007/10/03)
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- SUBSTITUTED BENZOLACTAM COMPOUNDS
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This invention relates to compounds of general formula (I): or a pharmaceutically acceptable salt thereof, W, T, Y, X, Q, R, R, and R are defined herein. This invention also relates to compounds of formula (I), depicted above, wherein Y is -NH-; T is (2S,3S)-2-phenylpiperidin-3-yl, where the phenyl group of said (2S, 3S)-2-phenylpiperidine-3-yl may optionally be substituted with fluoro; Q is oxygen and is double bonded to the carbon atom to which it is attached, X is methoxy or ethoxy, R is hydrogen, methyl or halo-C1-C2 alkyl, W is methylene, ethylene or vinylene; R and R are independently hydrogen or methyl, or one of R or R may be hydroxy, when W is ethylene, R and R are both methyl, when W is methylene, and R and R are both hydrogen, when W is vinylene. The invention is further directed to methods of treating various CNS and other disorders using said compounds and pharmaceutical compositions thereof.
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- Substituted benzolactam compounds
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This invention relates to compounds of the general formula (1): or a pharmaceutically acceptable salt thereof, W, T, Y, X, Q, R1, R2, and R3 are defined herein. This invention also relates to compounds of the formula I, depicted above, wherein Y is —NH—; T is (2S,3S)-2-phenylpiperidin-3-yl, where the phenyl group of said (2S, 3S)-2-phenylpiperidine-3-yl may optionally be substituted with fluoro; Q is oxygen and is double bonded to the carbon atom to which it is attached, X is methoxy or ethoxy, R1 is hydrogen, methyl or halo-C1-C2 alkyl, W is methylene, ethylene or vinylene; R2 and R3 are independently hydrogen or methyl, or one of R2 or R3 may be hydroxy, when W is ethylene, R2 and R3 are both methyl, when W is methylene, and R2 and R3 are both hydrogen, when W is vinylene. The invention is further directed to methods of treating various CNS and other disorders using said compounds and pharmaceutical compositions thereof.
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- Studies on new platelet aggregation inhibitors 1. Synthesis of 7-nitro-3,4-dihydroquinoline-2(1H)-one derivatives
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A series of 6-cyclic aliphatic amino-7-nitro-3,4-dihydroquinoline-2(1H)-ones were prepared and tested for platelet aggregation inhibitory effect, cardiotonic activity and chronotropic activity. These compounds appeared to show selective inhibitory activity against platelet aggregation. Among them, 6-(4-ethoxycarbonylpiperidino)-7-nitro-3,4-dihydroquinoline-2(1H)-one (22f) showed the most potent inhibitory activity and high selectivity. A divergent synthetic route to 6-cyclic aliphatic amino-7-nitro-3,4-dihydroquinoline-2(1H)-one derivatives has also been investigated.
- Iyobe,Uchida,Kamata,Hotel,Kusama,Harada
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p. 822 - 829
(2007/10/03)
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- Titanium(III)-induced transformation of hydroxylamines to imines or secondary amines
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N,N-Disubstituted and cyclic hydroxylamines can be converted into the corresponding imines efficiently upon treatment with anhydrons titanium trichloride in THF at room temperature. Similar treatment of N-allylhydroxylamines with anhydrous titanium trichloride gives 1-azadienes, which are versatile synthetie intermediates for aza-Diels-Alder reactions. On the other hand, the same hydroxylamines can be converted into the corresponding secondary amines upon treatment with aqueous titanium trichloride in methanol. It is noteworthy that optically active hydroxylamines, which have chirality at the α-position to nitrogen, can be converted into optically active secondary amines without loss of chirality. Dihydro-2(1H)-quinolinones can be prepared upon treatment of 1-hydroxy-3,4-dihydro-2(1H)-quinolinones with aqueous titanium trichloride. The substrates of N,N-disubstituted and cyclic hydroxylamines can be prepared readily upon treatment of nitrones with nucleophiles. Since nitrones can be prepared by metal-catalyzed oxidations of secondary amines with hydrogen peroxide, the present titanium(III)-promoted reaction of hydroxylamines will provide a convenient method for the synthesis of either α-substituted imines or amines from secondary amines.
- Kodera,Watanabe,Imada,Murahashi
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p. 2542 - 1549
(2007/10/02)
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- A Simple Synthesis of 5-Methoxyindole and 5-Methoxy-2-oxindole
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1-Methoxy- and 1-hydroxy-2-oxindoles rearranged in acidic solution to 5-substituted 2-aminophenylacetic acid derivatives which were cyclized to the corresponding 2-oxindoles with heating.The synthesis of 5-methoxyindole from 5-methoxy-2-oxindole was also described.
- Sakamoto, Takeshi,Hosoda, Isao,Kikugawa, Yasuo
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p. 1279 - 1281
(2007/10/02)
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- Synthesis and Antileukemic Activity of Bismethyl>-Substituted Pyrroloisoquinolines, Pyrroloquinolines, Pyrroloisobenzazepines, and Pyrrolobenzazepines
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A series of bismethyl>-substituted pyrrole-fused tricyclic heterocycles were synthesized by using 1,3-dipolar cycloaddition reactions with a trifluoromethanesulfonate salt of an appropriate Resissert compound or with a mesoionic oxazolone intermediate.All of the bis(carbamates) were active in vivo against P388 lymphocytic leukemia with 5,6-dihydro-8-methoxy-1,2-bis(hydroxymethyl)pyrroloisoquinoline bis (3c) showing the highest level of activity.
- Anderson, Wayne K.,Heider, Arvela R.,Raju, Natarajan,Yucht, Jeffery A.
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p. 2097 - 2102
(2007/10/02)
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- Inhibitors of cyclic AMP phosphodiesterase. 1. Analogues of cilostamide and anagrelide
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Evaluation of a series of lactam heterocyclic analogues of cilostamide as inhibitors of cyclic AMP phosphodiesterase derived from both human platelets and rat heart in comparison with their corresponding methoxy-substituted heterocycles has revealed that the N-cyclohexyl-N-methyl-4-oxybutyramide side chain of 2 is an important lipophilic and/or steric pharmacophore. Attachment of this side chain to the parent heterocycle of the potent cyclic AMP phosphodiesterase inhibitor anagrelide afforded the hybrid structure RS-82856, shown to be more potent than either of its progenitors as an inhibitor of cyclic AMP phosphodiesterase or of ADP-induced platelet aggregation. The available in vitro data suggest that 1 possesses potentially useful antithrombotic and cardiotonic properties.
- Jones,Venuti,Alvarez,Bruno,Berks,Prince
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p. 295 - 303
(2007/10/02)
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- 3-[2-(4-Anisidino)phenyl]-1-phenyl-1-propiophenones and propanols
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The invention relates to novel 1-(4-R1 O-phenyl)-2-(4-R2 -phenyl)-6-R3 -1,2,3,4-tetrahydroquinolines having anti-fertility and hypocholesterolemic activities, to their preparation, and to novel intermediates therefor.
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- Certain 1,2-diphenyl-1,2,3,4-tetrahydroquinoline compounds
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The invention relates to novel 1-(4-R1 O-phenyl)-2-(4-R2 -phenyl)-6-R3 -1,2,3,4-tetrahydroquinolines having antifertility and hypocholesterolemic activities, to their preparation, and to novel intermediates therefor.
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