Synthesis, structure, ionochromic and cytotoxic properties of new 2-(indolin-2-yl)-1,3-tropolones

• Yurii A. Sayapin,
• Eugeny A. Gusakov,
• Inna O. Tupaeva,
• Alexander D. Dubonosov,
• Igor V. Dorogan,
• Valery V. Tkachev,
• Anna S. Goncharova,
• Gennady V. Shilov,
• Natalia S. Kuznetsova,
• Svetlana Y. Filippova,
• Tatyana A. Krasnikova,
• Yanis A. Boumber,
• Alexey Y. Maksimov,
• Sergey M. Aldoshin and
• Vladimir I. Minkin

Beilstein J. Org. Chem. 2025, 21, 358–368, doi:10.3762/bjoc.21.26

• ; Introduction 1,2-Benzoquinones represent unique building blocks for various classes of heterocyclic systems. Their structure depends on the reactivity of the initial heterocycles and 1,2-benzoquinones, as well as on the reaction conditions. In the series of 2-methylquinolines [1], 2-methylquinoxalines [2], 2

• -methylquinazolinones [3], 2-methylbenzoxazinones [4], and 2-methylbenzoxa(thia)zoles [5] the interaction with sterically hindered 1,2-benzoquinones and 3,4,5,6-tetrachloro-1,2-benzoquinone proceeds with the expansion of the o-quinone ring and results in 2-hetaryl-substituted 1,3-tropolones 1 (Scheme 1), which exhibit

Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments

• Daria A. Burmistrova,
• Andrey Galustyan,
• Nadezhda P. Pomortseva,
• Kristina D. Pashaeva,
• Maxim V. Arsenyev,
• Oleg P. Demidov,
• Mikhail A. Kiskin,
• Andrey I. Poddel’sky,
• Nadezhda T. Berberova and
• Ivan V. Smolyaninov

Beilstein J. Org. Chem. 2024, 20, 2378–2391, doi:10.3762/bjoc.20.202

• changes. This is confirmed by the appearance of an absorption maximum in the UV–visible spectrum at λ = 490 nm, which is characteristic of thiolated o-benzoquinones. This absorption band corresponds to intramolecular charge transfer between the thioether group and the o-benzoquinone fragment [36][62][63

• reverse CV branch of 9, characteristic of compounds with a catechol fragment (Figure S24 in Supporting Information File 1). The second anodic peak for 9 is not observed due to the narrow electrochemical window of the solvent in the positive CV region. The formation of o-benzoquinones at the first stage of

• maximum at λ = 412 nm which is characteristic for sterically hindered o-benzoquinones. The proposed scheme for the electrooxidation of catechols 6–9 is presented in Scheme 3. Based on the current intensities of the second anodic peaks for compounds 6–8 with a 1,3,4-oxadiazole-2-thione ring (Figure 8 for 7

Using the phospha-Michael reaction for making phosphonium phenolate zwitterions

• Matthias R. Steiner,
• Max Schmallegger,
• Larissa Donner,
• Johann A. Hlina,
• Christoph Marschner,
• Judith Baumgartner and
• Christian Slugovc

Beilstein J. Org. Chem. 2024, 20, 41–51, doi:10.3762/bjoc.20.6

• = 3.9 Hz) [30]. Compared to the parent phosphine 1 (155.9 ppm, 2JPC = 19.3 Hz) [35] a pronounced down-field shift occurred upon adduct formation, which suggests a considerable contribution of a quinonic resonance structure as benzoquinones exhibit 13C NMR shifts of about 188 ppm and hydroquinones of

Non-noble metal-catalyzed cross-dehydrogenation coupling (CDC) involving ether α-C(sp³)–H to construct C–C bonds

• Hui Yu and
• Feng Xu

Beilstein J. Org. Chem. 2023, 19, 1259–1288, doi:10.3762/bjoc.19.94

• , pyrazines, pyridines, quinolines, isoquinolines, benzothiazoles, benzoquinones, etc. Under the reaction conditions, various ethers such as 1,4-dioxane, tetrahydropyran, tetrahydrofuran, diethyl ether, etc. are suitable substrates. Immediately thereafter, various photocatalytic catalysts were developed for

Synthesis of N-phenyl- and N-thiazolyl-1H-indazoles by copper-catalyzed intramolecular N-arylation of ortho-chlorinated arylhydrazones

• Yara Cristina Marchioro Barbosa,
• Guilherme Caneppele Paveglio,
• Claudio Martin Pereira de Pereira,
• Sidnei Moura,
• Cristiane Storck Schwalm,
• Gleison Antonio Casagrande and
• Lucas Pizzuti

Beilstein J. Org. Chem. 2022, 18, 1079–1087, doi:10.3762/bjoc.18.110

• reaction of hydrazones and p-benzoquinones [16], and Co3+/Cu2+-catalyzed C−N/N−N coupling of imidates with anthranils as both aminating reagents and organic oxidants [17]. Additional established routes to 1H-indazoles comprise transition metal‐catalyzed [18][19][20] and metal-free [21][22] intramolecular

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

• -benzoquinones and p-hydroquinones or the synthesis of menadione (10). The furan derivative 34 was used as a diene and 2-iodophenyltrifluoromethanesulfonate (35) as a dienophile, in the presence of n-butyllithium, forming 10 in 55% yield (Scheme 8) [92]. In the same year, Gogin and and co-workers developed a

• source was made after preliminary studies demonstrated the occurrence of reactions with benzoquinones using the compact fluorescent lamp (Scheme 18). Reduction and acylation reactions Menadione reduction reactions are one of the most important types of reactions and are directly related to some of its

A visible-light-induced, metal-free bis-arylation of 2,5-dichlorobenzoquinone

• Pieterjan Winant and
• Wim Dehaen

Beilstein J. Org. Chem. 2021, 17, 2315–2320, doi:10.3762/bjoc.17.149

• splitting of boronic acids in a useful radical CH mono-arylation of benzoquinones [16]. Later research demonstrated that the metal catalyst can be replaced by a less expensive iron catalyst [17][18] or even be omitted at higher temperatures [19]. Despite their reputation as unstable intermediates

• eosin Y and green light as a reducing agent an array of substrates were functionalized. Common among reports on the radical CH-arylation of benzoquinones is the use of multiple equivalents of starting material to prevent bis-arylation. The latter inherently relies on the use of an excess of radical

A straightforward conversion of 1,4-quinones into polycyclic pyrazoles via [3 + 2]-cycloaddition with fluorinated nitrile imines

• Greta Utecht-Jarzyńska,
• Karolina Nagła,
• Grzegorz Mlostoń,
• Heinz Heimgartner,
• Marcin Palusiak and
• Marcin Jasiński

Beilstein J. Org. Chem. 2021, 17, 1509–1517, doi:10.3762/bjoc.17.108

• -quinones, competitive reaction courses involving either ethylenic C=C or carbonyl C=O bonds were observed. For example, the more polar arylnitrile oxides and 1,4-benzoquinones reacted via addition to the C=C bond to give fused isoxazole derivatives [10][11][12] as well as with the C=O bond yielding

Application of the Meerwein reaction of 1,4-benzoquinone to a metal-free synthesis of benzofuropyridine analogues

• Rashmi Singh,
• Tomas Horsten,
• Rashmi Prakash,
• Swapan Dey and
• Wim Dehaen

Beilstein J. Org. Chem. 2021, 17, 977–982, doi:10.3762/bjoc.17.79

• . Electrophilic substitution and further condensations give polycyclic systems, including oxazolo- and chromeno-fused analogues. Keywords: benzofuropyridines; benzoquinones; dibenzofurans; Meerwein reaction; metal-free synthesis; Introduction Dibenzofurans are important oxygen-containing heterocycles present in

Annulation of a 1,3-dithiole ring to a sterically hindered o-quinone core. Novel ditopic redox-active ligands

• Sergey V. Norkov,
• Anton V. Cherkasov,
• Andrey S. Shavyrin,
• Maxim V. Arsenyev,
• Viacheslav A. Kuropatov and
• Vladimir K. Cherkasov

Beilstein J. Org. Chem. 2021, 17, 273–282, doi:10.3762/bjoc.17.26

• 300–400 nm region. Very similar bands were previously observed for p-quinone malononitrile derivatives [11]. Conclusion In conclusion, a new and effective synthesis pathway to chelating ditopic ligands – 3,6-di-tert-butyl-o-benzoquinones annulated at the 4,5-positions with a 2-substituted 1,3-dithiole

Synthesis and optoelectronic properties of benzoquinone-based donor–acceptor compounds

• Daniel R. Sutherland,
• Nidhi Sharma,
• Georgina M. Rosair,
• Ifor D. W. Samuel,
• Ai-Lan Lee and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2019, 15, 2914–2921, doi:10.3762/bjoc.15.285

• chemistry; physical organic chemistry; spectroscopy; thermally activated delayed fluorescence; Introduction Substituted benzoquinones and derivatives [1] have generated great interest, in particular due to their redox-active nature and their importance in biological mechanisms [2]. Compounds bearing

• benzoquinones have found utility in a variety of different fields, such as medicinal chemistry [3], natural products [4], dyes [5], ligands [6][7][8][9], oxidation chemistry [10], functional materials [11], and molecular electronics [12][13]. Due to their myriad applications, one of our groups recently

An overview of the cycloaddition chemistry of fulvenes and emerging applications

• Ellen Swan,
• Kirsten Platts and
• Anton Blencowe

Beilstein J. Org. Chem. 2019, 15, 2113–2132, doi:10.3762/bjoc.15.209

• reaction, causing the formation of complex products. Examples of dienes that have previously been used include cyclic diketones (o-benzoquinones) (Scheme 15, reaction pathways (i)) [60][89][156][157][158][160][161][162][163][164][165][211][215][226], o-quinone methides [87], o-xylylenes [125][153

• (i) maleimide derivatives, (ii) dimethyl acetylenedicarboxylate (DMAD) and (iii) p-benzoquinones. Generic schemes showing pentafulvenes participating as dienophiles in Diels–Alder cycloadditions with (i) o-benzoquinones and (ii) polyhalogenated cyclopentadienes. Reaction of 8,8-dicyanoheptafulvene

Oxidative cycloaddition of hydroxamic acids with dienes or guaiacols mediated by iodine(III) reagents

• Hisato Shimizu,
• Akira Yoshimura,
• Keiichi Noguchi,
• Victor N. Nemykin,
• Viktor V. Zhdankin and
• Akio Saito

Beilstein J. Org. Chem. 2018, 14, 531–536, doi:10.3762/bjoc.14.39

• moderate to high yields. The present method could be applied to the HDA reactions of acylnitroso species with o-benzoquinones generated by the oxidative dearomatization of guaiacols. Keywords: acylnitroso; benzoquinone; cycloaddition; dearomatization; iodine(III); Introduction The hetero-Diels–Alder (HDA

• , we report the HDA reaction of acylnitroso species generated from hydroxamic acids by [bis(trifluoroacetoxy)iodo]benzene (BTI) or DIB. The present method could be applied to HDA reactions with not only simple dienes but also with masked o-benzoquinones (MOBs) generated by the oxidative dearomatization

• NMR analysis). As a further application of the iodine(III)-mediated oxidative cycloaddition reactions, the present method was extended to HDA reactions with masked o-benzoquinones (MOBs) generated by the oxidative dearomatization [26][27][28][29] of guaiacols with methanol (Scheme 2). Liao’s and other

Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

• Lucie Brulíková,
• Aidan Harrison,
• Marvin J. Miller and
• Jan Hlaváč

Beilstein J. Org. Chem. 2016, 12, 1949–1980, doi:10.3762/bjoc.12.184

• nitroso dienophiles with masked o-benzoquinones [128]. For instance, they synthesized synthon 152 from 2-methoxyphenol (150) and the chiral auxiliary 151 with 99% de, which was further utilized for the synthesis of (+)-conduramine E-1 (153, Scheme 30). The hetero-Diels–Alder reaction of chloronitroso

Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes

• Norbert Vida,
• Jiří Václavík and
• Petr Beier

Beilstein J. Org. Chem. 2016, 12, 110–116, doi:10.3762/bjoc.12.12

• . Maleic acid 4 was identified in the mixture (25% 19F NMR yield, Scheme 4) but chromatographic separation, crystallization or derivatization (CH2N2) attempts were not successful. Nevertheless, these results show that SF5-substituted para-benzoquinones are most likely intermediates in the formation of 4 by

2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties

• Yury A. Sayapin,
• Inna O. Tupaeva,
• Alexandra A. Kolodina,
• Eugeny A. Gusakov,
• Vitaly N. Komissarov,
• Igor V. Dorogan,
• Nadezhda I. Makarova,
• Anatoly V. Metelitsa,
• Valery V. Tkachev,
• Sergey M. Aldoshin and
• Vladimir I. Minkin

Beilstein J. Org. Chem. 2015, 11, 2179–2188, doi:10.3762/bjoc.11.236

• the other hand, the low energy barrier transformation (8∙AcOH) → (9∙AcOH) does not reasonably depends on the nature of X. It is worth noting that the structure of products of the reaction of 2-methylbenzazoles with 1,2-benzoquinones can be affected by various factors. Among the important ones, that

• significantly higher than those displayed by the parent 2-(2-hydroxyphenyl)benzoxazole (0.02) and 2-(2-hydroxyphenyl)benzothiazole (0.005) [34]. Conclusion The ring expansion of the 3,4,5,6-tetrachloro-1,2-benzoquinones occuring under coupling with 2-methylbenzoxazoles, 2-methylbenzothiazoles and 2,3,3

Recent applications of ring-rearrangement metathesis in organic synthesis

• Sambasivarao Kotha,
• Milind Meshram,
• Priti Khedkar,
• Shaibal Banerjee and
• Deepak Deodhar

Beilstein J. Org. Chem. 2015, 11, 1833–1864, doi:10.3762/bjoc.11.199

• ). Liao and co-workers [65] have employed the RRM protocol with the DA adduct derived from masked o-benzoquinones (MOBs). Here, they demonstrated an efficient RRM protocol for the synthesis of cis-hydrindenols starting with a readily available starting material such as 2-methoxyphenols. To this end, 2

Recent advances in the electrochemical construction of heterocycles

• Robert Francke

Beilstein J. Org. Chem. 2014, 10, 2858–2873, doi:10.3762/bjoc.10.303

• generated 1,2-benzoquinones via sequential Michael addition/ring closure An electrochemical method for the synthesis of benzofuran and indol derivatives is based on the oxidation of catechol in presence of 1,3-dicarbonyl compounds or analogous C,H-acidic compounds 62 (Scheme 24) [69][70][71][72]. The

Synthesis of 2,3-dihydronaphtho[2,3-d][1,3]thiazole-4,9-diones and 2,3-dihydroanthra[2,3-d][1,3]thiazole-4,11-diones and novel ring contraction and fusion reaction of 3H-spiro[1,3-thiazole-2,1'-cyclohexanes] into 2,3,4,5-tetrahydro-1H-carbazole-6,11-diones

• Lidia S. Konstantinova,
• Kirill A. Lysov,
• Ljudmila I. Souvorova and
• Oleg A. Rakitin

Beilstein J. Org. Chem. 2013, 9, 577–584, doi:10.3762/bjoc.9.62

• -naphthoquinone structure is common for various natural products. It is associated with numerous biological activities, such as enzyme-inhibitory, antifungal, antibacterial, anticancer, antiproliferative, antiplatelet, anti-inflammatory, antiallergic, and antimalarial ones. Benzoquinones fused with heterocycles

About the activity and selectivity of less well-known metathesis catalysts during ADMET polymerizations

• Hatice Mutlu,
• Lucas Montero de Espinosa,
• Oĝuz Türünç and
• Michael A. R. Meier

Beilstein J. Org. Chem. 2010, 6, 1149–1158, doi:10.3762/bjoc.6.131

• temperature, C2 showed a considerably lower degree of isomerization of 9.91%; however only oligomers (Mn 1700 Da) were obtained. Another goal of this research was to suppress the isomerization side reaction and thus to synthesize well-defined polyesters. Benzoquinones are very effective additives for the

Variations in product in reactions of naphthoquinone with primary amines

• Marjit W. Singh,
• Anirban Karmakar,
• Nilotpal Barooah and
• Jubaraj B. Baruah

Beilstein J. Org. Chem. 2007, 3, No. 10, doi:10.1186/1860-5397-3-10

• -benzoquinone reacts with primary amines to give 2,5-diamino 1,4-benzoquinones; similar reaction of 1,4-naphthoquinone with primary amines results in the formation of 2-amino 1,4-naphthoquinones. [13] However, the product formed from such simple reaction of amine with various quinones has much scope for