1015-89-0Relevant articles and documents
MeOTf- and TBD-Mediated Carbonylation of ortho-Arylanilines with CO2 Leading to Phenanthridinones
Wang, Sheng,Shao, Peng,Du, Gaixia,Xi, Chanjuan
, p. 6672 - 6676 (2016)
Carbonylation of o-arylanilines utilizing CO2 as a carbonyl source for the synthesis of important phenanthridinones with a free (NH)-lactam motif has been described under metal-free condition. A range of o-arylanilines were transformed to the corresponding phenanthridinones in high yields.
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Akermark et al.
, p. 1365 (1975)
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Radical Borylative Cyclization of Isocyanoarenes with N-Heterocyclic Carbene Borane: Synthesis of Borylated Aza-arenes
Liu, Yao,Li, Ji-Lin,Liu, Xu-Ge,Wu, Jia-Qiang,Huang, Zhi-Shu,Li, Qingjiang,Wang, Honggen
, p. 1891 - 1897 (2021)
Borylated aza-arenes are of great importance in the area of organic synthesis. A radical borylative cyclization of isocyanoarenes with N-heterocyclic carbene borane (NHC-BH3) under metal-free conditions was developed. The reaction allows the efficient assembly of several types of borylated aza-arenes (phenanthridines, benzothiazoles, etc.), which are difficult to access using alternative methods. Mild reaction conditions, a good functional-group tolerance, and generally good efficiencies were observed. The utility of these products is demonstrated, and the mechanism is discussed.
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Forrester et al.
, p. 3601 (1977)
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RADICALOID INTERMEDIATES IN THE PHOTOCHEMISTRY OF 6-CYANOPHENATHRIDINE N-OXIDE
Albini, Angelo,Pasani, Elisa,Buchardt, Ole
, p. 4849 - 4852 (1982)
Irradiation of 6-cyanophenanthridine N-oxide in presence of 2,3-dimethyl-2-butene resulted in a novel type of photoaddition with rearrangement to give 2-cyano-8,8,9,9-tetramethyl--dibenzo-1,3-oxazonin and 6-(2-cyano-1,1,2-trimethylpropyloxy)phenanthridine as a minor product, which is regarded as strong evidence for an initial photochemical generation of a biradical, and not an oxaziridine as previously suggested.
Reactivity of cyclopalladated compounds derived from biphenyl-2-ylamine towards carbon monoxide, tbutyl isocyanide and alkynes
Albert, Joan,D'Andrea, Luci?a,Granell, Jaume,Zafrilla, Javier,Font-Bardia, Mercè,Solans, Xavier
, p. 4895 - 4902 (2007)
The reactivity of the dimeric cyclopalladated compounds derived from biphenyl-2-ylamine (μ-X)2[κ2-N2′,C1-1-Pd-2-{(2′-NH2C6H4)C6H4}]2 [X = OAc (1), X = Cl (2)] towards unsaturated organic molecules is reported. Compound 1 reacted with carbon monoxide and tbutyl isocyanide producing phenanthridin-6(5H)-one and N-tert-butylphenanthridin-6-amine in 63% and 88% yield, respectively. Compound 2 reacted separately with diphenylacetylene and 3-hexyne, affording the mononuclear organopalladium compounds [κ2-N2″,C1-η2-C2,C3- 1-Pd{(R-C{double bond, long}C-R)2-2′-(2″-NH2C6H4)C6H4}Cl] [R = Ph (5), R = Et (6)] in 50-60% yield, which derived from the insertion of two alkyne molecules into the C-Pd σ bonds of 2. The crystal structure of compounds 5 and 6 has been determined. Compound 5 crystallized in the monoclinic space group P21/n with a = 13.3290(10) A?, b = 10.6610(10) A? and c = 22.3930(10) A? and β = 100.2690(10)°. Compound 6 crystallized in the triclinic space group P over(1, ?) with a = 7.271(7) A?, b = 10.038(3) A? and c = 16.012(5) A?, and α = 106.79(3)°, β = 96.25(4)° and γ = 99.62(4)°. The crystal structures of 5 and 6 have short intermolecular Pd-Cl?H-N-Pd non-conventional hydrogen bonds, which associated the molecules in chains in the first case and in dimers in the second.
Electrochemical Formation of N-Acyloxy Amidyl Radicals and Their Application: Regioselective Intramolecular Amination of sp2 and sp3 C-H Bonds
Zhang, Sheng,Li, Lijun,Xue, Mengyu,Zhang, Ruike,Xu, Kun,Zeng, Chengchu
, p. 3443 - 3446 (2018)
Electrochemical generation of N-acyloxy amidyl radicals via an inner-sphere electron-transfer process is described for the first time. With NaBr as the catalyst and electrolyte, the in situ generated amidyl radicals undergo intramolecular C(sp2/sp3)-H aminations to give lactams with unprecedented regio- and chemoselectivities. Moreover, the synthetic utility of current method is demonstrated by the synthesis of PJ34 and Phenaglaydon.
Annulation of Benzamides with Arynes Using Palladium with Photoredox Dual Catalysis
Zhao, Jie,Li, Hongji,Li, Pinhua,Wang, Lei
, p. 9007 - 9016 (2019)
Efficient annulation of benzamides with arynes using palladium and photoredox dual catalysis under an oxygen atmosphere is disclosed, which circumvents the use of external toxic metal oxidant and proceeds readily via aryne insertion at room temperature to construct the phenanthridinone backbone.
Dual Mechanisms for the Fragmentation of 1-Benzoylbenzotriazole upon Electron Impact
Yamada, Shuzo,Kamiyama, Yojiro,Ohashi, Mamoru
, p. 1 - 3 (1980)
The electron impact induced fragmentation of 1-benzoylbenzotriazole has been studied by 13C labelling experiments.It has been found that the loss of CO from the 2>+. ions proceeds by two routes; about 78percent of the ions decompose via the molecular ions of the corresponding thermal fragmentation product, 2-phenylbenzoxazole, and 22percent via those of the corresponding photochemical fragmentation product, 6-phenanthridone.
Palladium/Silver Synergistic Catalysis in Direct Aerobic Carbonylation of C(sp2)H Bonds Using DMF as a Carbon Source: Synthesis of Pyrido-Fused Quinazolinones and Phenanthridinones
Nageswar Rao,Rasheed, Sk.,Das, Parthasarathi
, p. 3142 - 3145 (2016)
An unprecedented Pd/Ag synergistic catalysis in the direct carbonylation of C(sp2)-H bonds utilizing DMF as the carbon source under oxygen is described and demonstrated in the synthesis of pyrido-fused quinazolinone and phenanthridinone scaffolds. Control experiments indicated that the C of the carbonyl group is derived from the methyl group of DMF and O originates from oxygen as in the case of Ge's recent work. This transformation offers an alternative avenue for CO-free carbonylations.
Intermolecular amidation of unactivated sp2 and sp3 C-H bonds via palladium-catalyzed cascade C-H activation/nitrene insertion
Thu, Hung-Yat,Yu, Wing-Yiu,Che, Chi-Ming
, p. 9048 - 9049 (2006)
This communication describes the Pd(OAc)2-catalyzed intermolecular amidation reactions of unactivated sp2 and sp3 C-H bonds using primary amides and potassium persulfate. The substrates containing a pendent oxime or pyridine group were amidated with excellent chemo- and regioselectivities. It is noteworthy that reactive C-X bonds were well-tolerated and a variety of primary amides can be effective nucleophiles for the Pd-catalyzed C-H amidation reactions. For the reaction of unactivated sp3 C-H bonds, β-amidation of 1° sp3 C-H bonds versus 2° C-H bonds is preferred. The catalytic reaction is initiated by chelation-assisted cyclopalladation involving C-H bond activation. Preliminary mechanistic study suggested that the persulfate oxidation of primary amides should generate reactive nitrene species, which then reacted with the cyclopalladated complex. Copyright
A Pd-catalyzed, boron ester-mediated, reductive cross-coupling of two aryl halides to synthesize tricyclic biaryls
Chen, Zhilong,Wang, Xiaodong
, p. 5790 - 5796 (2017)
Tricyclic biaryls are important scaffold structures in many natural products and lead compounds in drug discovery. The formation of a biaryl unit is often the key step for the synthesis of tricyclic biaryls. Despite significant progress toward the synthesis of biaryl compounds in recent years, the direct cross-coupling of two different aryl halides is still challenging and robust methods are lacking. Herein we report a direct cross-coupling of two different aryl halides in the presence of a palladium catalyst and boron ester, which provides a new and useful complementary method to synthesize tricyclic biaryls.
Continuous flow photochemistry as an enabling synthetic technology: Synthesis of substituted-6(5: H)-phenanthridinones for use as poly(ADP-ribose) polymerase inhibitors
Fang,Tranmer
, p. 720 - 724 (2016)
Methods utilizing continuous flow photochemistry, an enabling synthetic technology, have been developed for the generation of phenanthridinones via an intramolecular photochemical cyclization of 2-chlorobenzamides for the purposes of generating poly(ADP-ribose) polymerase inhibitors. Herein we report 16 examples of a single-step flow photocyclization which produces substituted phenanthridinones in yields up to 99%, while a two-step method leads directly to phenanthridinones from 2-chlorobenzoyl chlorides and anilines via a novel continuous flow amidation/photocyclization protocol. Overall, the flow photocyclization reactions typically progress in good to excellent yields, and in a superior fashion to analogous batch methods, greatly enabling the drug discovery process.
A convenient one-pot access to phenanthridinones via Suzuki-Miyaura cross-coupling reaction
Tanimoto, Kouichi,Nakagawa, Naomichi,Takeda, Kazutaka,Kirihata, Mitsunori,Tanimori, Shinji
, p. 3712 - 3714 (2013)
A convenient one-step access to biologically important phenanthridinones 1 has been realized based upon Suzuki-Miyaura cross-coupling reaction. Reactions of 2-aminophenylboronic acid 2 with 2-halobenzoate 3 took place smoothly to afford substituted phenanthridinones 1 in excellent yields in the presence of palladium(II) acetate and 2-dicyclohexylphosphino-2′,6′- dimethoxybiphenyl (SPhos) as pre-catalysts. A natural product phenaglydon 1b was synthesized in one-pot manner from readily available starting materials in 95% yield.
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Badger,Pettit
, p. 3211,3215 (1951)
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Design, synthesis and evaluation of 6-(4-((substituted-1H-1,2,3-triazol-4- yl)methyl)piperazin-1-yl)phenanthridine analogues as antimycobacterial agents
Nagesh, Hunsur Nagendra,Naidu, Kalaga Mahalakshmi,Rao, Damarla Harika,Sridevi, Jonnalagadda Padma,Sriram, Dharmarajan,Yogeeswari, Perumal,Chandra Sekhar, Kondapalli Venkata Gowri
, p. 6805 - 6810 (2013)
Focus in this Letter is made to design and synthesize a series of nineteen new 6-(4-((substituted-1H-1,2,3-triazol-4-yl)methyl)piperazin-1-yl) phenanthridine analogues employing click chemistry and evaluated for their anti-tubercular activity against Mycobacterium tuberculosis H37Rv. Among the tested compounds, 7f and 7j exhibited good activity (MIC = 3.125 μg/mL), while 8a displayed excellent activity (MIC = 1.56 μg/mL) against the growth of M. tuberculosis H37Rv. In addition, 7f, 7j and 8a compounds were subjected to cytotoxic studies against mouse macrophage (RAW264.7) cell lines and the selectivity index values are >15 indicating suitability of compounds for further drug development.
Lewis Acid Catalysed Cyclisation and Halogen Exchange Reactions of 1,1'-Biphenyl-2-yl Isocyanide Dihalides
Currie, Kevin S.,Tennant, George
, p. 2295 - 2296 (1995)
1,1'-Biphenyl-2-yl isocyanide dichloride and dibromide undergo unprecedented intramolecular Friedel-Crafts type cyclisation reactions catalysed by various Lewis acids affording useful synthetic methods for otherwise difficult to access 6-chloro- and 6-bromo-phenanthridines; nucleophilic displacement reactions of the latter and halogen exchange reactions of 1,1'-biphenyl-2-yl isocyanide dichloride and dibromide are also described.
Utilization of Polyphosphoric Acid in the Presence of a Co-solvent
Guy, Alain,Guette, Jean-Paul,Lang, Gerard
, p. 222 - 223 (1980)
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Butler
, p. 2578 (1949)
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Photoinduced Annulation of N-Phenylbenzamides for the Synthesis of Phenanthridin-6(5H)-Ones
Wang, Nana,Wang, Ding,He, Yun,Xi, Jin,Wang, Tao,Liang, Yong,Zhang, Zunting
, p. 1150 - 1155 (2022/02/25)
A general concise method for the synthesis phenanthridin-6(5H)-ones via photoinduced intramolecular annulation of N-phenylbenzamides was developed. Under argon atmosphere and room temperature, phenanthridin-6(5H)-ones were obtained via irradiation N-phenylbenzamides with a 280 nm UV lamp in the presence of methanesulfonic acid in toluene. The mechanism is illustrated and believed to proceed in the order of amides tautomerization, 6π-electric cyclization, [1,5]-H shift, amide-imidine tautomerization, keto-enol tautomerism and evolution hydrogen. (Figure presented.).
Synthesis of Aza[ n]phenacenes (n = 4-6) via Photocyclodehydrochlorination of 2-Chloro- N-aryl-1-naphthamides
Váňa, Lubomír,Jakubec, Martin,Sykora, Jan,Císa?ová, Ivana,Storch, Jan,Církva, Vladimír
, p. 13252 - 13264 (2021/10/01)
A novel methodology for the synthesis of aza[n]phenacenes was successfully developed utilizing photocyclodehydrochlorination reaction of 2-chloro-N-aryl-1-naphthamides. In these key intermediates, the factors influencing the photoreaction were studied. The target aza[n]phenacenes were obtained by triflation or chlorination from prepared phenanthridinones, followed by hydrogenation. The introduction of a nitrogen atom into a phenacene skeleton induced changes in the physicochemical properties. The important properties of prepared aza[n]phenacenes (n = 4-6) were studied experimentally and by density functional theory calculations and were compared to those of their carbo analogues. Furthermore, some important features of the crystalline aza[n]phenacenes were investigated, including intermolecular interaction in the crystal lattice and the increased solubility or decreased melting points.
Tetrabutylammonium Iodide (TBAI) Catalyzed Electrochemical C-H Bond Activation of 2-Arylated N -Methoxyamides for the Synthesis of Phenanthridinones
Subramanian, Kripa,Yedage, Subhash L.,Sethi, Kashish,Bhanage, Bhalchandra M.
, p. 999 - 1003 (2021/04/19)
An electrochemical method for the synthesis of phenanthridinones through constant-potential electrolysis (CPE) mediated by Bu 4 NI (TBAI) is reported. The protocol is metal and oxidant free, and proceeds with 100% current efficiency. TBAI plays a dual role as both a redox catalyst and a supporting electrolyte. The intramolecular C-H activation proceeds under mild reaction conditions and with a short reaction time through electrochemically generated amidyl radicals. The reaction has been scaled up to a gram level, showing its practicability, and the synthetic utility and applicability of the protocol have been demonstrated by a direct one-step synthesis of the bioactive compound phenaglaydon.
