Photoinduced in situ generation of DNA-targeting ligands: DNA-binding and DNA-photodamaging properties of benzo[c]quinolizinium ions

• Julika Schlosser,
• Olga Fedorova,
• Yuri Fedorov and
• Heiko Ihmels

Beilstein J. Org. Chem. 2024, 20, 101–117, doi:10.3762/bjoc.20.11

• [7], quinoxalines [8], naphthalimides [9], phenanthridines [10], cyanines [11], or indoles [12], as well as metal-organic complexes [13], and several others [1][2][4]. In this context, benzoquinolizinium derivatives and resembling polycyclic azoniahetarenes are an established class of DNA-binding

Quinoxaline derivatives as attractive electron-transporting materials

• Zeeshan Abid,
• Liaqat Ali,
• Sughra Gulzar,
• Faiza Wahad,
• Raja Shahid Ashraf and
• Christian B. Nielsen

Beilstein J. Org. Chem. 2023, 19, 1694–1712, doi:10.3762/bjoc.19.124

• transport applications. Furthermore, ongoing research efforts aimed at enhancing their performance and addressing key challenges in various applications are presented. Keywords: electron transport materials; non-fullerene acceptors; n-type semiconductors; organic electronics; quinoxalines; Introduction

• -emitting diodes (OLEDs), and bio/chemo-sensing devices. The movement of charge carriers through these materials occurs via a complex interplay of electronic, structural, and energetic phenomena, presenting intriguing challenges and opportunities for scientific exploration [3][4]. Quinoxalines (Qxs) have

• applications. Secondly, the feasibility of synthesizing quinoxalines contributes immensely to their appeal. Qxs can be readily prepared through simple condensation reactions, enabling convenient experimental studies and cost-effective bulk production [5]. The availability of inexpensive and accessible starting

Enabling artificial photosynthesis systems with molecular recycling: A review of photo- and electrochemical methods for regenerating organic sacrificial electron donors

• Grace A. Lowe

Beilstein J. Org. Chem. 2023, 19, 1198–1215, doi:10.3762/bjoc.19.88

Scope of tetrazolo[1,5-a]quinoxalines in CuAAC reactions for the synthesis of triazoloquinoxalines, imidazoloquinoxalines, and rhenium complexes thereof

• Laura Holzhauer,
• Chloé Liagre,
• Olaf Fuhr,
• Nicole Jung and
• Stefan Bräse

Beilstein J. Org. Chem. 2022, 18, 1088–1099, doi:10.3762/bjoc.18.111

• , Germany 10.3762/bjoc.18.111 Abstract The conversion of tetrazolo[1,5-a]quinoxalines to 1,2,3-triazoloquinoxalines and triazoloimidazoquinoxalines under typical conditions of a CuAAC reaction has been investigated. Derivatives of the novel compound class of triazoloimidazoquinoxalines (TIQ) and rhenium(I

• ; tetrazole; triazole; Introduction Quinoxalines are amongst the most versatile N-heterocyclic compounds, combining a straightforward synthesis with a diverse set of possible functionalizations and a wide range of applications in drug development and materials sciences [1]. Different quinoxaline derivatives

• possess antibacterial [2], antifungal [3], and antiviral properties [4] and form the core structure of commercially available drugs like brimonidine, varenicline, and quinacillin [5]. Quinoxalines can also be used in organic solar cell polymers [1][6] and have been described as donor moieties in many TADF

A study of the photochemical behavior of terarylenes containing allomaltol and pyrazole fragments

• Constantine V. Milyutin,
• Andrey N. Komogortsev,
• Boris V. Lichitsky and
• Valeriya G. Melekhina

Beilstein J. Org. Chem. 2022, 18, 588–596, doi:10.3762/bjoc.18.61

• -phenylenediamine. The general method for the preparation of the corresponding quinoxalines on the basis of the aforementioned condensation was implemented. It was demonstrated that the studied photoreaction does not depend on the type of pyrazole bridge. The structures of three of synthesized products were

• -hydroxy-1,2-diketones 2 is the condensation with 1,2-phenylenediamine resulting in the formation of fused quinoxalines 3 (Scheme 1A) [22]. Another variant of similar catching reaction is reduction by NaBH3CN with the formation of diols 4 (Scheme 1A) [23]. Thus, the introduction of additional reagents

• convert the labile α-hydroxy-1,2-diketone 14 into stable derivatives. A convenient method for the transformation of α-hydroxy-1,2-diketone into the corresponding substituted quinoxalines by reaction with 1,2-phenylenediamine was described in the literature [22]. The application of this protocol allowed

Aldehydes as powerful initiators for photochemical transformations

• Maria A. Theodoropoulou,
• Nikolaos F. Nikitas and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2020, 16, 833–857, doi:10.3762/bjoc.16.76

• ]. Benzaldehyde (8) was tested as an alternative to tertiary amines, which are commonly employed in radical-mediated reactions due to their ability to bind to atmospheric oxygen, which inhibits such reactions. The quinoxalines 32 were used as the prime photoinitiators, and the reaction was placed in a

• photoreactor equipped with a cooling fan and lamps emitting at 350 nm at room temperature. The polymerization reaction led to good results. As depicted in Scheme 9, the postulated reason for the successful polymerization was that after the irradiation of benzaldehyde (8) with the quinoxalines 32, the benzoyl

• polymerization of monomeric MMA (26) using the quinoxalines 32 and benzaldehyde (8). Acetone (4) and formaldehyde (35) as photografting initiators. Photografting by employing acetaldehyde (36) as the photoinitiator. Proposed photolysis mechanism for aliphatic ketones 44 and formaldehyde (35). Initiator 50

One-pot activation–alkynylation–cyclization synthesis of 1,5-diacyl-5-hydroxypyrazolines in a consecutive three-component fashion

• Christina Görgen,
• Katharina Boden,
• Guido J. Reiss,
• Walter Frank and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2019, 15, 1360–1370, doi:10.3762/bjoc.15.136

• –alkynylation (GA) [48] and an activation–alkynylation (AA) [49] sequence, which both take advantage of a copper-catalyzed alkynylation of the intermediary formed (hetero)arylglyoxyl chloride (Scheme 1). The alkynediones can be subsequently transformed, still in the same reaction vessel, to quinoxalines [48][50

The LANCA three-component reaction to highly substituted β-ketoenamides – versatile intermediates for the synthesis of functionalized pyridine, pyrimidine, oxazole and quinoxaline derivatives

• Tilman Lechel,
• Roopender Kumar,
• Mrinal K. Bera,
• Reinhold Zimmer and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2019, 15, 655–678, doi:10.3762/bjoc.15.61

• acid treatment leads to acylamido-substituted 1,2-diketones DK that could be converted into quinoxalines QU. All classes of heterocycles accessed through the key β-ketoenamides show a unique substitution pattern – not easily accomplishable by alternative methods – and therefore many subsequent

• reactions are possible. Keywords: allenes; condensations; multicomponent reactions; oxazoles; pyrimidines; quinoxalines; Introduction Multicomponent reactions are known to create unique product skeletons in an atom economic, efficient and time saving fashion. In many cases, compounds bearing functional

• particular heterocyclic compounds. The synthesis of pyrimidines PM, pyrimidine N-oxides PO, oxazoles OX, 1,2-diketones DK and quinoxalines QU starting from β-ketoenamides KE is the topic of the present review. Review Scope of the LANCA three-component synthesis of β-ketoenamides The scope of the LANCA three

Synthesis of pyrimido[1,6-a]quinoxalines via intermolecular trapping of thermally generated acyl(quinoxalin-2-yl)ketenes by Schiff bases

• Svetlana O. Kasatkina,
• Ekaterina E. Stepanova,
• Maksim V. Dmitriev,
• Ivan G. Mokrushin and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2018, 14, 1734–1742, doi:10.3762/bjoc.14.147

• 3-acylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones react regioselectively with Schiff bases under solvent-free conditions to form pyrimido[1,6-a]quinoxaline derivatives in good yields. Keywords: acyl(quinoxalin-2-yl)ketenes; cycloaddition; pyrimido[1,6-a]quinoxalines; Schiff bases; thermolysis

• intraocular pressure (IOP) [8] etc. (Figure 1). Pyrimido[1,6-a]quinoxalines are one of the most intriguing and unexplored structures representing isosteres of this scaffold. Only few synthetic procedures towards these compounds are described in the literature: heterocyclizations of α-chloroisocyanates with

• synthetic approach towards pyrimido[1,6-a]quinoxalines we looked through the procedures to their closest analogues – pyrido[1,2-a]quinoxalines, the synthesis of which has been explored more frequently [3][4][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36

[3 + 2]-Cycloaddition reaction of sydnones with alkynes

• Veronika Hladíková,
• Jiří Váňa and
• Jiří Hanusek

Beilstein J. Org. Chem. 2018, 14, 1317–1348, doi:10.3762/bjoc.14.113

• -phenylbut-1-yne [119] tridentate tris(benzimidazole) ligands completely failed and tris(triazole) ligands gave only poor to moderate yields (16–65%) even at 100 °C, whereas all the bidentate ligands (phenanthrolines L1, L2 and diimidazo[1,2-a:2',1'-c]quinoxalines L3–L6) were found to be more efficient both

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

• Hélène Guyon,
• Hélène Chachignon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272

• metals found in Langlois’ reagent could be responsible for reaction initiation. The scope was evaluated on pyridines, pyrroles, indoles, pyrimidines, pyrazines, phthalazines, quinoxalines, deazapurine, thiadiazoles, uracils, xanthenes and pyrazolino-pyrimidines (Scheme 35). The combination of previous

Reagent-controlled regiodivergent intermolecular cyclization of 2-aminobenzothiazoles with β-ketoesters and β-ketoamides

• Irwan Iskandar Roslan,
• Kian-Hong Ng,
• Gaik-Khuan Chuah and
• Stephan Jaenicke

Beilstein J. Org. Chem. 2017, 13, 2739–2750, doi:10.3762/bjoc.13.270

• bromination of the α-carbon using CBrCl3 as the Br source. This in situ halogenation strategy has been employed for the synthesis of quinoxalines [23], oxazoles [24][25], pyrido[1,2-a]benzimidazoles [26], imidazo[1,2-a]pyridines [27][28][29][30], thiazoles [31][32] and benzothiazoles [33][34]. With weak

Oxidative dehydrogenation of C–C and C–N bonds: A convenient approach to access diverse (dihydro)heteroaromatic compounds

• Santanu Hati,
• Ulrike Holzgrabe and
• Subhabrata Sen

Beilstein J. Org. Chem. 2017, 13, 1670–1692, doi:10.3762/bjoc.13.162

• of the optimized reaction conditions tetrahydroquinoxalines were also converted into quinoxalines in excellent yields. The high activity and broad substrate scope of this catalytic system make this protocol very promising for laboratory and industrial applications. The use of catalytic palladium on

Three-component synthesis of highly functionalized aziridines containing a peptide side chain and their one-step transformation into β-functionalized α-ketoamides

• Lena Huck,
• Juan F. González,
• Elena de la Cuesta and
• J. Carlos Menéndez

Beilstein J. Org. Chem. 2016, 12, 1772–1777, doi:10.3762/bjoc.12.166

• corresponding compounds 11, which were then transformed into pyrazines 12 and quinoxalines 13 via straightforward cyclocondensation reactions with ethylenediamine and o-phenylenediamine, respectively (Scheme 6 and Table 3). The transformation of 2 into 11 can be explained by the mechanism summarized in Scheme 7

A convenient route to symmetrically and unsymmetrically substituted 3,5-diaryl-2,4,6-trimethylpyridines via Suzuki–Miyaura cross-coupling reaction

• Dariusz Błachut,
• Joanna Szawkało and
• Zbigniew Czarnocki

Beilstein J. Org. Chem. 2016, 12, 835–845, doi:10.3762/bjoc.12.82

• teams in the construction of polyarylated benzenes [56], pyridines [57][58][59][60], thiophenes [61][62], quinoxalines [63], pyrazoles [64] pyrroles [65], pyrimidines [66][67], benzofuranes [68], imidazo[1,2-a]pyridines [69], diaryl/heteroaryl methanes [70], and indoles [71], bearing differently

New highlights of the syntheses of pyrrolo[1,2-a]quinoxalin-4-ones

• Emilian Georgescu,
• Alina Nicolescu,
• Florentina Georgescu,
• Florina Teodorescu,
• Daniela Marinescu,
• Ana-Maria Macsim and
• Calin Deleanu

Beilstein J. Org. Chem. 2014, 10, 2377–2387, doi:10.3762/bjoc.10.248

• quinoxalines [6] have been recently reviewed. Among other synthetic routes, the 1,3-dipolar cycloaddition of heterocyclic N-ylides with various activated alkynes or alkenes is an important method for constructing fused heterocyclic systems such as pyrrolo[1,2-a]quinoxaline and pyrrolo[1,2-a]benzimidazole [7][8

• ][9][10][11][12][13]. The development of more efficient synthetic methods towards these compounds is an active research area [14][15][16]. Recently, we reported on the formation of pyrrolo[1,2-a]benzimidazoles along with pyrrolo[1,2-a]quinoxalines in the one-pot three-component reaction of 1

• 1H NMR spectra of pyrrolo[1,2-a]quinoxalines and pyrrolo[1,2-a]benzimidazoles the protons from the phenyl ring and the annelated benzo ring are overlapping in the region of 7–8 ppm. Based on a less used undecoupled H,C-HSQC type of spectrum we assigned for the first time the individual aromatic

Novel supramolecular affinity materials based on (−)-isosteviol as molecular templates

• Christina Lohoelter,
• Malte Brutschy,
• Daniel Lubczyk and
• Siegfried R. Waldvogel

Beilstein J. Org. Chem. 2013, 9, 2821–2833, doi:10.3762/bjoc.9.317

• construction of novel (−)-isosteviol-based C3-symmetric scaffolds. For the elaboration of optimal condensation conditions to form quinoxalines and to obtain model compounds representing subunits for the triptycene architectures o-phenylenediamines were employed (Scheme 2). It turned out that 5b forms the

• File 1). Screening of protic analytes with affinity materials 3, 8, 14 and 15. Functionalization of triphenylene ketal 2a. Quinoxalines based on diketone 5b. Condensation of 5b with hexaammoniumtriptycene hexachloride. Synthesis of nitrobenzylic ester derivatives 10 and 11, starting from (−)-isosteviol

Microwave-assisted synthesis of 5,6-dihydroindolo[1,2-a]quinoxaline derivatives through copper-catalyzed intramolecular N-arylation

• Fei Zhao,
• Lei Zhang,
• Hailong Liu,
• Shengbin Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2013, 9, 2463–2469, doi:10.3762/bjoc.9.285

• received much attention because of their applications in medicinal chemistry [7][8][9][10][11]. Among them, the tetracyclic ring system of 5,6-dihydroindolo[1,2-a]quinoxalines forms an important class of compounds because of their diverse range of pharmacological properties (Figure 1). For example

• incorporate the bioactive indole motif may find their pharmaceutical applications after further investigations. Experimental General procedure for the synthesis of 5,6-dihydroindolo[1,2-a]quinoxalines: A high-pressure microwave vessel was loaded with 1 (0.25 mmol, 1.0 equiv), CuI (0.025 mmol, 4.8 mg, 0.1

• [1,2-a]quinoxalines by CuI-catalyzed intramolecular N-arylation.a Supporting Information Supporting Information File 530: General information, experimental details, characterization data and copies of 1H and 13C NMR spectra. Acknowledgements We gratefully acknowledge financial support from the

Mild and efficient cyanuric chloride catalyzed Pictet–Spengler reaction

• Ashish Sharma,
• Mrityunjay Singh,
• Nitya Nand Rai and
• Devesh Sawant

Beilstein J. Org. Chem. 2013, 9, 1235–1242, doi:10.3762/bjoc.9.140

• -withdrawing aldehydes to yield the 6-endo product indolo[1,2-a]quinoxalines 8 (Table 2). It is interesting to note that the cyclized products of the modified Pictet–Spengler substrate 4 are fully aromatized. This is probably because the cyclized dihydro derivatives formed in situ are prone to oxidation

• . We demonstrated application of this methodology for the synthesis of tetrahydro-β-carbolines 3 and indolo[1,2-a]quinoxalines 8. These scaffolds are present in numerous biologically active compounds. Nevertheless, TCT is inexpensive and readily available. Therefore, this methodology can be easily

Amyloid-β probes: Review of structure–activity and brain-kinetics relationships

• Todd J. Eckroat,
• Abdelrahman S. Mayhoub and
• Sylvie Garneau-Tsodikova

Beilstein J. Org. Chem. 2013, 9, 1012–1044, doi:10.3762/bjoc.9.116

A one-pot catalyst-free synthesis of functionalized pyrrolo[1,2-a]quinoxaline derivatives from benzene-1,2-diamine, acetylenedicarboxylates and ethyl bromopyruvate

• Mohammad Piltan,
• Loghman Moradi,
• Golaleh Abasi and
• Seyed Amir Zarei

Beilstein J. Org. Chem. 2013, 9, 510–515, doi:10.3762/bjoc.9.55

• ; pyrrolo[1,2-a]pyrazine; pyrrolo[1,2-a]quinoxaline; Introduction Among the various classes of heterocyclic compounds, quinoxalines, a class of N-containing heterocycles, form an important component of many pharmacologically active compounds [1][2][3][4]. For example, the quinoxaline ring is a constituent

• ], antifungal, and antidepressant activities [9][10]. Two commercially available antibiotic families of quinoxalines, echinomycin [11][12] and triostins [13], are well known. Hence, the synthesis of quinoxaline derivatives is currently of significant interest in organic synthesis. As an important quinoxaline

• )anilines with alkynes to form 4,5-dihydropyrrolo[1,2-a]quinoxalines [23][24]. Kobayashi and co-workers have described the Lewis acid catalyzed cyclization of 1-(2-isocyanophenyl)pyrroles to give pyrrolo[1,2-a]quinoxalines in good yields; however, the isocyanide substrates required multistep synthesis [25

Continuous-flow catalytic asymmetric hydrogenations: Reaction optimization using FTIR inline analysis

• Magnus Rueping,
• Teerawut Bootwicha and
• Erli Sugiono

Beilstein J. Org. Chem. 2012, 8, 300–307, doi:10.3762/bjoc.8.32

• Magnus Rueping Teerawut Bootwicha Erli Sugiono Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany 10.3762/bjoc.8.32 Abstract The asymmetric organocatalytic hydrogenation of benzoxazines, quinolines, quinoxalines and 3H-indoles in continuous-flow

• decided to extend its scope to the reduction of quinoxalines 7 (Table 5) [107]. The asymmetric reduction of quinoxalines is typically more difficult to achieve. Using the optimized conditions for the fast inline reaction, we found that the continuous-flow reduction could be performed using 10 mol

• continuous-flow hydrogenations of benzoxazines, quinolines, quinoxalines and 3H-indoles. Following a real-time continuous-flow optimization, the corresponding products were obtained in good yields and with excellent enantioselectivities. By applying the FTIR inline monitoring, reaction parameters can be

Gold-catalyzed oxidation of arylallenes: Synthesis of quinoxalines and benzimidazoles

• Dong-Mei Cui,
• Dan-Wen Zhuang,
• Ying Chen and
• Chen Zhang

Beilstein J. Org. Chem. 2011, 7, 860–865, doi:10.3762/bjoc.7.98

• to form α-diketones and aldehydes in good yields is presented. Further directed synthesis of quinoxalines and benzimidazoles, via the condensation of the resulting α-diketones and aldehydes with benzene-1,2-diamine, was achieved in high yields. Keywords: allene; benzimidazole; gold-catalysis

• /hydration and oxidative cleavage of allenes to form α-diketones and aldehydes, and the synthesis of quinoxalines and benzimidazoles via the condensation of the resulting α-diketones and aldehydes with benzene-1,2-diamine [45][46][47][48][49][50][51][52][53][54][55][56]. Results and Discussion Our initial

• oxidative transformation under the same reaction conditions. Having prepared a variety of α-diketones and aldehydes successfully, we then undertook the synthesis of quinoxalines and benzimidazoles (Scheme 2). Thus, the treatment of the corresponding mixture of α-diketone 2 and aldehyde 3 with benzene-1,2

One-pot three-component synthesis of quinoxaline and phenazine ring systems using Fischer carbene complexes

• Priyabrata Roy and
• Binay Krishna Ghorai

Beilstein J. Org. Chem. 2010, 6, No. 52, doi:10.3762/bjoc.6.52

• parent organisms [2][3]. These compounds show diverse biological activities such as antibacterial, antifungal, antiviral and antitumor properties [4][5][6][7][8]. While rarely found in nature, quinoxalines are well known in the pharmaceutical industry and have been shown to possess a broad spectrum of

Preparation, structures and preliminary host–guest studies of fluorinated syn-bis-quinoxaline molecular tweezers

• Markus Etzkorn,
• Jacob C. Timmerman,
• Matthew D. Brooker,
• Xin Yu and
• Michael Gerken

Beilstein J. Org. Chem. 2010, 6, No. 39, doi:10.3762/bjoc.6.39

• , host–guest NMR studies of compound 16c in solution show chemical exchange between the unbound and bound electron-rich guest, N,N,N′,N′-tetramethyl-p-phenylenediamine. Keywords: crystal structure; fluorine; molecular tweezers; quinoxalines; self-association; Introduction A broad variety of

• potentials of belt-shaped compounds 2a–c and predicted the complexation of halide anions in the cavity of 2c [16][17][18]. Intrigued by Chou’s communication on the spectroscopic properties of non-fluorinated bis-quinoxalines of type 3 and 4a [19], we targeted on the corresponding fluorinated derivatives – in

• association with electron-rich guest compounds. Results and Discussion Synthesis of fluorinated bis-quinoxalines The general route [19] to bis-quinoxaline targets (Scheme 2) utilizes a twofold Diels–Alder reaction of a cycloalkadiene (5,6) with cyclopentadienone derivatives (7), subsequent oxidation of the