- Synthesis and cytotoxic activity of acronycine analogues in the benzo[c]pyrano[3,2-h]acridin-7-one and naphtho[1,2-b][1,7] and [1,10]-phenanthrolin-7(14H)-one series
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Condensation of 1-bromo-2-naphthalenecarboxylic acid (9) with 7-methoxy-2,2-dimethyl-2H-1-benzopyran-5-ylamine (13) followed by acid-mediated cyclization afforded 6-methoxy-3,3-dimethyl-3,14-dihydro-7H-benzo[c]pyrano[3,2- h]acridin-7-one (15), which was further methylated into 6-methoxy-3,3,14- trimethyl-3,14-dihydro-7H-benzo[c]pyrano[3,2-h]acridin-7-one (benzo[c]acronycine) (3) and 6,7-dimethoxy-3,3-dimethyl-3H-benzo[c]pyrano[3,2-h] acridine (4). Osmium tetroxide oxidation of 15 gave the (±)-cis-diol 16, which afforded the benzopyranoacridine and benzopyranoacridone esters 17-22 upon acylation. Condensation of 9 with suitable aminoquinolines 23-25 afforded the carboxylic naphthylquinolylamines 26-28. Cyclization gave the corresponding naphtho[1,2-b][1,10]-phenanthrolin-7(14H)-ones 29 and 30, and naphtho[1,2-b][1,7]-phenanthrolin-7(14H)-one 31, which were subsequently N-methylated to the desired 14-methylnaphtho[1,2-b][1,10] and [1,7]-phenanthrolinones 6, 7, and 8. Benzo[c]pyrano[3,2-h]acridin-7-one derivatives 3, 16, and 22 displayed cytotoxic activities within the same range of magnitude as acronycine itself, whereas 7-alkoxybenzo[c]pyrano[3,2-h]acridine and 7-acyloxybenzo[c]pyrano[3,2-h]acridine derivatives 4 and 17-21 were less active when tested against L1210 murine leukemia cells in vitro. Naphthophenanthrolinones 6-8 were devoid of significant antiproliferative activity, but compounds 29-31 bearing no substituent on the nitrogen atom at position 14 were more potent.
- Bongui, Jean-Bernard,Elomri, Abdelhakim,Cahard, Dominique,Tillequin, Francois,Pfeiffer, Bruno,Pierre, Alain,Seguin, Elisabeth
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- Photoinduced Carbon Tetrabromide Initiated Aerobic Oxidation of Substituted Toluenes to Carboxylic Acids
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A mild and metal-free procedure is reported for the aerobic oxidation of substituted toluenes to carboxylic acids by using CBr 4 as initiator under irradiation from a 400 nm blue light-emitting diode.
- Li, Xiaoqing,Xu, Xiangsheng,Yan, Xiaoyu,Yan, Xinhuan,Zhang, Guofu,Zheng, Kun
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p. 272 - 274
(2020/02/18)
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- Synthesis method of benzoic acid compounds
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The invention discloses a photocatalytic oxidation synthesis method of benzoic acid compounds, and the photocatalytic oxidation synthesis method comprises the following specific steps: mixing and dissolving toluene compounds and a catalyst in a solvent, reacting for 24-60h in the presence of an oxidant under the conditions of 350-460 nm LED illumination and a temperature of 20-80 DEG C, and performing post-treatment on the reaction liquid to obtain the benzoic acid compounds. The photocatalytic oxidation synthesis method has the advantages of no need of metal catalysts, simple operation and mild reaction conditions; oxygen is used as an oxidant, and the photocatalytic oxidation synthesis method has high atom economy, cheap reagent and environmental protection. The photocatalytic oxidationsynthesis method has good substrate applicability, and various substituents can realize the synthesis of corresponding benzoic acid compounds.
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Paragraph 0178; 0179; 0180; 0181
(2019/12/25)
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- Ruthenium-Catalyzed Atropoenantioselective Synthesis of Axial Biaryls via Reductive Amination and Dynamic Kinetic Resolution
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The unprecedented ruthenium-catalyzed atropoenantioselective reductive amination of aldehydes with alkylamines via a cascade transfer hydrogenation and dynamic kinetic resolution strategy is described. This protocol features broad substrate scope and good functional group tolerance and allows the rapid assembly of axially chiral biaryls in good to high yields with high to excellent enantioselectivities. In addition, such structural motifs may have potential applications in enantioselective catalysis as chiral ligands or catalysts.
- Guo, Donghui,Zhang, Jianwei,Zhang, Bei,Wang, Jian
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p. 6284 - 6288
(2018/10/05)
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- Atropoenantioselective redox-neutral amination of biaryl compounds through borrowing hydrogen and dynamic kinetic resolution
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We report herein a novel atropoenantioselective redox-neutral amination of biaryl compounds triggered by a cascade of borrowing hydrogen and dynamic kinetic resolution under the cooperative catalysis of a chiral iridium complex and an achiral Br?nsted acid. This protocol features broad substrate scope and good functional-group tolerance, and allows the rapid assembly of axially chiral biaryl compounds in good to high yields and with high to excellent enantioselectivity.
- Zhang, Jianwei,Wang, Jian
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p. 465 - 469
(2017/12/15)
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- Atropoenantioselective Redox-Neutral Amination of Biaryl Compounds through Borrowing Hydrogen and Dynamic Kinetic Resolution
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We report herein a novel atropoenantioselective redox-neutral amination of biaryl compounds triggered by a cascade of borrowing hydrogen and dynamic kinetic resolution under the cooperative catalysis of a chiral iridium complex and an achiral Br?nsted acid. This protocol features broad substrate scope and good functional-group tolerance, and allows the rapid assembly of axially chiral biaryl compounds in good to high yields and with high to excellent enantioselectivity.
- Zhang, Jianwei,Wang, Jian
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p. 465 - 469
(2018/02/21)
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- Synthesis method of axially chiral dinaphthalene ligand precursor (s)-2,2'-dinaphthyl-1,1'-dicarboxylic acid
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The invention relates to the technical field of bromination, hydrolysis, oxidation and coupling reaction in organic synthesis, particularly a synthesis method of an axially chiral dinaphthalene ligand precursor (s)-2,2'-dinaphthyl-1,1'-dicarboxylic acid. The method comprises the following steps: synthesizing a compound 1-bromo-2-methylnaphthalene from an initial raw material 2-bromomethylnaphthalene, carrying out bromination, hydrolysis and oxidation on the 1-bromo-2-methylnaphthalene to obtain 1-bromo-2-naphthoic acid, generating an ester under the actions of methanol and thionyl chloride, protecting the carboxyl group, carrying out Ullmann reaction under the action of copper powder to perform coupling, carrying out hydrolysis to obtain 2,2'-dinaphthyl-1,1'-dicarboxylic acid, and finally, resolving to obtain the (s)-2,2'-dinaphthyl-1,1'-dicarboxylic acid. The method is simple to operate, and has the advantages of higher yield and favorable economical efficiency.
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Paragraph 0017; 0026; 0035; 0044; 0071; 0080
(2016/10/10)
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- Selenium-catalyzed C(sp3)-H acyloxylation: Application in the expedient synthesis of isobenzofuranones
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Oxidative Se-catalyzed C(sp3)-H bond acyloxylation has been used to construct a diverse array of isobenzofuranones from simple ortho-allyl benzoic acid derivatives. The synthetic procedure employs mild reaction conditions and gives high chemoselectivity enabled by an inexpensive organodiselane catalyst. The presented approach offers a new synthetic pathway toward the core structures of phthalide natural products.
- Kr?tzschmar, Felix,Kassel, Martin,Delony, Daniel,Breder, Alexander
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supporting information
p. 7030 - 7034
(2015/05/05)
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- Design and synthesis of new stable fluorenyl-based radicals
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Organic neutral radicals have long fascinated chemists with a fundamental understanding of structure-reactivity relationships in organic reactions and with applications as new functional materials. However, the elusive nature of these radicals makes the synthesis, isolation, and characterization very challenging. In this work, the synthesis of three long-lived, fluorenyl-based radicals are reported. The geometry and electronic structures of these radicals were systematically investigated with a combination of various experimental methods, besides density functional theory (DFT) calculations, which include X-ray crystallographic analysis, electron spin resonance (ESR), electron nuclear double resonance (ENDOR), cyclic voltammetry, and UV-vis-NIR measurements. Their half-life periods (τ1/2) in air-saturated solution under ambient conditions were also determined. Surprisingly, all three radicals showed remarkable stabilities: τ1/2 = 7, 3.5, and 43 days.
- Tian, Yi,Uchida, Kazuyuki,Kurata, Hiroyuki,Hirao, Yasukazu,Nishiuchi, Tomohiko,Kubo, Takashi
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p. 12784 - 12793
(2015/02/19)
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- New fluorescent blue oled host and dopant materials based on the spirobenzofluorene
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New spiro[benzo[c]fluorene-7,9'-fluorene] (SBFF)-based blue host materials, 9-phenyl-SBFF (BH-4P) and 5,9-diphenyl-SBFF (BH-6DP), were successfully prepared by spiro-formation of 9-phenyl-7H-benzo[c]fluoren- 7-one with 2-bromobiphenyl via lithiation and reaction of 5,9-dibromo-SBFF with phenylboronic acid through the Suzuki reaction, respectively. Diphenyl-[4-(2-[1,1;4,1]terphenyl-4-yl-vinyl)-phenyl]-amine (BD-1) and N,N-diphenyl-N',N'-diphenyl-SBFF-5,9-diamine (BD-6DPA) were used as dopant materials. Blue OLEDs with the configuration ITO/N,N'-bis-[4-(di-m-tolylamino) phenyl]-N,N'-diphenylbiphenyl-4,4'-diamine (DNTPD)/ bis[N-(1-naphthyl)-N-phenyl] benzidine (NPB)/host:5% dopant/SFC-137/Al-LiF were prepared from the two host materials doped with BD-1 and BD-6DPA dopants and the devices composed of BH-4P and BH-6DP doped with BD-6DPA showed blue EL spectra at 458 and 463 nm at 7 V and luminance efficiencies of 4.58 and 4.88 cd/A, respectively.
- Lee, In-Ho,Gong, Myoung-Seon
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p. 1475 - 1482
(2011/12/14)
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- A practical synthesis of C2-symmetric chiral binaphthyl ketone catalyst
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A practical synthesis of 11-membered C2-symmetric binaphthyl ketone (R)-1, a catalyst for asymmetric epoxidation, was developed. (±)-1,1'-Binaphthyl-2,2'-dicarboxylic acid [(±)-6] was efficiently resolved by (R)-(-)-1-cyclohexylethylamine to give (R)-6 in >99% ee and in 38% yield. Condensation of the acid chloride derived from (R)-6 with 1,3-dihydroxyacetone dimer at 60-70 °C provided the desired chiral ketone (R)-1 in 61-63% yield without need for high dilution techniques.
- Seki,Yamada,Kuroda,Imashiro,Shimizu
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p. 1677 - 1680
(2007/10/03)
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- Enantioselective catalysis of the triplex diels-alder reaction: A study of scope and mechanism
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Irradiation of the chiral sensitizers 1,1-bis(2,4-dicyanonaphthalene) and 1,r-bis(2,10-dicyanoanthracene) catalyzes the triplex Diels-Alder reaction of trans-β-methylstyrene with 1,3-cyclohexadiene to form the [4 + 2] cycloadducts endo-trans-6-methyl-5-phenylbicyclo[2.2.2]oct-2-ene. When the sensitizer is optically active and the irradiation is performed at low temperature in ether or toluene solution, the [4 + 2] cycloadducts are formed enantioselectively. The mechanism of the enantioselective triplex Diels-Alder reaction was examined by chemical and spectroscopic means. Interaction of the chiral sensitizer with the prochiral styrene forms diastereomeric exciplexes. The equilibration of these exciplexes is fast at room temperature but not at low temperature. The exciplexes react with diene to form a triplex. This reaction leads to cycloadduct formation. Enantioselection is a consequence of different trapping efficiencies for the diastereomeric exciplexes by diene.
- Kim, Ji-In,Schuster, Gary B.
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p. 9309 - 9317
(2007/10/02)
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- SYNTHESIS AND POLYMERIZATION OF SOME ETHYNYL TRIFLUOROMETHYL NAPHTHALENES
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Some bromonaphthoic acids were fluorinated with SF4 to bromo(trifluoromethyl)naphthalenes.Although a reaction of Grignard reagent of one of the bromides with Cl2C=CF2 gave low yield of a (dichlorofluorovinyl)(trifluoromethyl)naphthalene, lithio derivatives gave the desired ethynyl(trifluoromethyl)naphthalenes in improved yields after subsequent eliminations of the vinylic halogens with n-butyllithium.Polymerization of the acetylenes was carried out with photo-activated W(CO)6 catalyst to yield high-molecular-weight polymers.
- Okano, T.,Ito, K.,Kodaira, K.,Hosokawa, K.,Nishida, M.,et al.
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p. 139 - 152
(2007/10/02)
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- Dibenzocyclooctene-, Dibenzochalcocine-, and Diarenochalconinediones
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2,2'-Oxybis-, -thiobis-, and -methylenebisbenzoic esters 2a-c react with methyllithium in ether to give low yields of 5H-dibenzochalcocine-5,7(6H)-diones 6a, 7a, and dibenzocyclooctene-5,7(6H,12H)-dione (8), respectively.Very good yields of such heterocycles with oxygen (6a-h, 37), sulfur (7a-h, 38) and selenium (36) as key atom are obtained when diaryl ethers (21, 22, 25), -sulfides (27, 29, 30), and -selenides (33) that contain 2'-acetyl- (or -propionyl-) and 2-methoxycarbonyl groups are treated with sodium hydride in boiling toluene.Analogously are prepared the dibenzoxonine-11,13(6H,12H)diones 62a-c and 7H-benzonaphthothionine-7,9-(8H)-dione (65) which are expanded by one ring member.In the analogous reaction of a corresponding benzophenone derivative 35, spiro-3(2H),3'-dione (41) is formed in a tandem reaction. - Under phase transfer conditions the dibenzochalcocinediones 6, 7, 36 and also the corresponding nitrogen cycles 5 react to give mixtures of C- (42-45) and O-alkyl derivatives (46-49).Methyllithium and diisobutylaluminium hydride provide the carbinols 50-54.With bromine and SO2Cl2, respectively, the methylene group is mono- or dihalogenated to the products 56, 57; defined nitration was only possible for the oxacycle 6a.
- Hellwinkel, Dieter,Bohnet, Siegbert
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p. 1151 - 1174
(2007/10/02)
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- A Novel Clathrate Design: Selective Inclusion of Uncharged Molecules via the Binaphthyl Hinge and Appended Coordinating Groups. X-ray Crystal Structures and Binding Modes of 1,1'-Binaphthyl-2,2'-dicarboxylic Acid Host/Hydroxylic Guest Inclusions
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1,1'-Binaphthyl-2,2'-dicarboxylic acid (1) is demonstrated as a novel type of clathrate host whose main mode of action is derived from a combination of the steric barrier and the coordinative interaction principle which constitutes the new "coordinatoclathrate" strategy.Inclusion properties of the crystal lattice of 1 are revealed for a variety of uncharged organic guest molecules (30 examples), ranging from OH-, to NH-, to CH-acidic compounds such as alcohols, carboxylic acids, amides, and nitriles to rather unpolar compounds like bromobenzene and toluene.Marked discrimination selectivities in the clathrate formation from solvent mixtures are found in regard to the group functionality, the substitution pattern, and the molecular size of the guest species, making accessible a simple process for chemical compound separation.The stoichiometries and the increased-temperature as well as the reduced-pressure stabilities of the various clathrates are discussed.The principles of stucture of five different alcohol clathrates of 1 are determined with the aid of X-ray structure analysis at 273 K: 1*2MeOH (10) 1/n, a = 15.642 Angstroem, b = 14.532 Angstroem, c = 9.292 Angstroem, β = 95.14 deg, Z = 4>; 1*2EtOH (11) ; 1*2(2-PrOH) (13) ; 1*2-BuOH (15) 1/n, a = 12.009 Angstroem, b = 12.747 Angstroem, c = 14.982 Angstroem, β = 105.52 deg, Z = 4>; 1*ethylene glycol (24) 1/n, a = 14.276 Angstroem, b = 9.533 Angstroem, c = 15.556 Angstroem, β = 109.19 deg, Z = 4>.In all these cases, however, hydroxyl groups of the host molecules were found to be intercalated via large pseudo-ring formation between the carboxyl functions of at least two host units of opposite chirality with a different mode of hydrogen bridging.Depending on the host:guest stoichiometry (1:1 or 1:2) and on the nature of the guest molecules, these entities consist of three, four, or eight moieties (COOH, OH).The direction of the strong and cooperative bonds is always homodromic.The shape and the size of the cleft formed in the matrix of cooperating host moieties are shown to vary, matching the specific needs of coordinating interactions (hydrogen bonding) and topological requirements (branching, e.g.) of the guest species.
- Weber, Edwin,Csoregh, Ingeborg,Stensland, Brigitta,Czugler, Matyas
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p. 3297 - 3306
(2007/10/02)
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- Benzoisobenzofuran. Formation and Reactions of the Parent and Alkoxy-Substituted Derivatives
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Benzoisobenzofuran (1) is formed by base-induced 1,4-elimination of either acetal 9 or 11 and may be isolated in high yield as a cristalline solid.Cycloaddition reactions of preformed 1 have been carried out with various dienophiles.These reactions may also be accomplished by heating the acetals in the presence of dienophiles and acid catalyst, where 1 is generated as an intermediate.The cycloaddition reaction of 1 and maleic anhydride is found to be reversible at higher temperature (slow at 60 deg C).Unsymmetrical dienophiles react with 1 to give equal amounts of regioisomers, and evidence points to lack of regioselectivity under both kinetically controlled and equilibrating conditions.The acetals 9 and 11 are shown to interconvert with acid catalyst at 140 deg C, where 1 is an intermediate of greater stability than the acetals; the equilibrium K for 9 -> ( - ) 11 is approximately unity.Various acid-catalyzed cycloaddition reactions of ortho esters 8 and 10, yielding polysubstituted phenanthrene derivatives, are described.
- Cornejo, Jaime J.,Ghodsi, Shahram,Johnson, R. Douglas,Woodling, Rick,Rickburn, Bruce
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p. 3869 - 3876
(2007/10/02)
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