Chemical and biosynthetic potential of Penicillium shentong XL-F41

• Ran Zou,
• Xin Li,
• Xiaochen Chen,
• Yue-Wei Guo and
• Baofu Xu

Beilstein J. Org. Chem. 2024, 20, 597–606, doi:10.3762/bjoc.20.52

• . Researchers have identified numerous compounds with anticancer properties, including mycophenolic acid, brefeldin A, and wortmannin [3], as well as compounds with antibacterial properties like xestodecalactones A–C, penicifurans A, and anthraquinone-citrinin [4]. From 2010 to 2022, researchers have identified

Selective and scalable oxygenation of heteroatoms using the elements of nature: air, water, and light

• Damiano Diprima,
• Hannes Gemoets,
• Stefano Bonciolini and
• Koen Van Aken

Beilstein J. Org. Chem. 2023, 19, 1146–1154, doi:10.3762/bjoc.19.82

• more popular as oxidants due to their low cost and minimal side products. However, these reagents have practical limitations. Hydrogen peroxide is typically produced off-site and requires transportation and storage, and is commonly obtained through the non-sustainable anthraquinone process (Scheme 1B

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

Complementarity of solution and solid state mechanochemical reaction conditions demonstrated by 1,2-debromination of tricyclic imides

• Petar Štrbac and
• Davor Margetić

Beilstein J. Org. Chem. 2022, 18, 746–753, doi:10.3762/bjoc.18.75

• , small amounts of another cycloadduct were obtained. It was found that this is the product arising from anthraquinone (32), which was present as an impurity in 31. Independent milling of 10 with anthraquinone afforded dihydroxy cycloadduct 33 (in 35% yield) indicating that in the reaction conditions of

• the anthraquinone ↔ 9,10-dihydroxyanthracene (DHA) equilibrium is shifted towards DHA [34][35]. To prove this premise, anthraquinone alone was ball milled, however, unreacted material was recovered and the formation of 9,10-dihydroxyanthracene was not spectroscopically detected. An analogous hydroxy

• adduct 35 was produced in the reaction with anthrone (34). When the reaction of anthraquinone was carried in THF solution (reflux, 1 h), dibromide 10 remained unchanged. However, a small amount of 33 was formed in refluxing THF by the use of the Zn/Ag couple in the case of anthraquinone. These results

1,2-Naphthoquinone-4-sulfonic acid salts in organic synthesis

• Ruan Carlos B. Ribeiro,
• Patricia G. Ferreira,
• Amanda de A. Borges,
• Luana da S. M. Forezi,
• Fernando de Carvalho da Silva and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 53–69, doi:10.3762/bjoc.18.5

• catecholamines and other compounds, but they can also be ingested as exogenous products of air and water. The most common quinones, such as benzoquinone, naphthoquinone, anthraquinone, and phenanthrenequinone, can be formed by incomplete combustion or photooxidation of their respective polycyclic aromatic

Recent advances in the syntheses of anthracene derivatives

• Giovanni S. Baviera and
• Paulo M. Donate

Beilstein J. Org. Chem. 2021, 17, 2028–2050, doi:10.3762/bjoc.17.131

• years (2008–2020) and focuses on direct and indirect methods to construct anthracene and anthraquinone frameworks. Keywords: anthracenes; anthraquinones; Friedel–Crafts cyclization; intramolecular cyclization; metal-catalyzed; Introduction Anthracene is an important aromatic hydrocarbon consisting of

• , anthracene derivatives display useful biological activities; for instance, the anthraquinone derivatives 5 and 6 exert antimicrobial and anti-inflammatory activity, respectively (Figure 1) [15][16]. Despite some difficulties and limitations, a number of synthetic methods for preparing anthracene derivatives

• methods into three general categories: synthesis of substituted anthracene frameworks, synthesis of benzanthracene and dibenzanthracene derivatives, and synthesis of anthraquinone derivatives. We will focus on the construction of the anthracene and anthraquinone frameworks published in the last twelve

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

• anthraquinone moiety to give synthetic Cellulose I [94]. Overall, enzymatic synthesis is an established procedure to obtain non-uniform cellulose oligo- and polysaccharides. Some success was achieved using additives and molecular crowding conditions; however, this approach remains limited by product

Natural products in the predatory defence of the filamentous fungal pathogen Aspergillus fumigatus

• Jana M. Boysen,
• Nauman Saeed and
• Falk Hillmann

Beilstein J. Org. Chem. 2021, 17, 1814–1827, doi:10.3762/bjoc.17.124

• , comparable to how Trichoderma virens protects cotton seedlings from its pathogen Pythium ultimum [122]. Trypacidin The spore-born toxin trypacidin (8) is a polyketide that belongs to an anthraquinone-derived class of secondary metabolites (Figure 4) [107]. In A. fumigatus, the trypacidin biosynthetic cluster

Chemical approaches to discover the full potential of peptide nucleic acids in biomedical applications

• Nikita Brodyagin,
• Martins Katkevics,
• Venubabu Kotikam,
• Christopher A. Ryan and
• Eriks Rozners

Beilstein J. Org. Chem. 2021, 17, 1641–1688, doi:10.3762/bjoc.17.116

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

• naphthoquinone-derived products and low-intensity bands in the visible region (≈400 nm) for the anthraquinone series. Keywords: [3 + 2]-cycloadditions; fluorinated compounds; fused pyrazoles; N-heterocycles; nitrile imines; 1,4-quinones; Introduction The 1,4-quinone scaffold belongs to the most important

• 1,4-naphthoquinone (1a) and 1,4-anthraquinone (1b), which were selected as model dipolarophiles. In addition, an important issue of the work was the examination of the chemoselectivity governing the formation of five-membered rings via competitive cycloaddition of the in-situ-generated 1,3-dipoles

• ]-cycloadducts by air oxidation were isolated exclusively. Additionally, the X-ray structure of 9d is shown in Figure 2. Similar results were obtained starting with 1,4-anthraquinone (1b) and selected hydrazonoyl bromides 8. In this series, fused pyrazoles 9i–l were obtained in high yield (63–92%, Scheme 3

Photosensitized direct C–H fluorination and trifluoromethylation in organic synthesis

• Shahboz Yakubov and
• Joshua P. Barham

Beilstein J. Org. Chem. 2020, 16, 2151–2192, doi:10.3762/bjoc.16.183

• photocatalytic direct fluorination of unactivated C(sp3)–H bonds by employing Selectfluor® and anthraquinone (AQN, T1 = 61.9 kcal⋅mol−1) as a photosensitizer. Control experiments showed that, under their conditions, both light and AQN were necessary for the reaction to proceed. A variety of different compounds

Synthesis of 6,13-difluoropentacene

• Matthias W. Tripp and
• Ulrich Koert

Beilstein J. Org. Chem. 2020, 16, 2136–2140, doi:10.3762/bjoc.16.181

• subsequent reduction of the anthraquinone gave 1,4-difluoroanthracene. After ortho-lithiation and reaction with phthalic anhydride a carboxylic acid was obtained whose Friedel–Crafts acylation and subsequent reductive removal of the oxygen-functionalities resulted in the formation of the target compound. The

• acid precursor could be prepared by reaction of the anthracenyllithium 7 with phthalic anhydride (8). Intermediate 7 could be accessed by ortho-lithiation of anthracene 9. The synthesis of 9 by two consecutive Friedel–Crafts acylation reactions and reduction of the resulting anthraquinone could start

• –Crafts acylation is then performed in polyphosphoric acid at 140 °C, giving anthraquinone 11 in 53% yield over two steps. Reduction of 11 to the anthracene 9 proceeded smoothly using zinc powder in 1,4-dioxane and aqueous ammonia under copper catalysis [15]. To achieve good yields, it was crucial to

Diversity-oriented synthesis of 17-spirosteroids

• Benjamin Laroche,
• Thomas Bouvarel,
• Martin Louis-Sylvestre and
• Bastien Nay

Beilstein J. Org. Chem. 2020, 16, 880–887, doi:10.3762/bjoc.16.79

• cytotoxic anthraquinone moiety and obtained positive, yet limited, cytotoxic activities [63][64]. Furthermore, a steroidal anti-estrogen–doxorubicin conjugate was synthesized by Hanson, showing a 70-fold increase of activity compared to doxorubicin in inhibiting cell proliferation and promoting cell death

Efficient synthesis of 3,6,13,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes by selective C–H/C–O arylations of anthraquinone derivatives

• Seiya Terai,
• Yuki Sato,
• Takuya Kochi and
• Fumitoshi Kakiuchi

Beilstein J. Org. Chem. 2020, 16, 544–550, doi:10.3762/bjoc.16.51

• alkyl and alkoxy substituents at the 3, 6, 13, and 16-positions was achieved based on the ruthenium-catalyzed coupling reactions of anthraquinone derivatives with arylboronates via C–H and C–O bond cleavage. The reaction sequence involving the arylation, carbonyl methylenation, and oxidative cyclization

• ]. Anthraquinone was chosen as a convenient template for the PAH syntheses, because various anthraquinone derivatives possessing zero to four oxygen substituents at the ortho-positions are readily available and the regioselective arylation at the positions of either C–H or C–O bonds provided a variety of

• multiarylated anthraquinone derivatives [16][17][18][19][20]. Using this method, we have synthesized various π-extended aromatic compounds such as multiarylated acenes [16][18][20], dibenzo[h,rst]pentaphenes and dibenzo[fg,qr]pentacenes [19]. In the course of our reaction development, it was found that an

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

• Rafia Siddiqui and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 248–280, doi:10.3762/bjoc.16.26

• reported on photocatalytic brominations using a stronger oxidizing photocatalyst, viz, sodium anthraquinone-2-sulfonate (SAS, 7a, 2.3 V vs SCE) [161][162]. In their studies, they did not only observe excellent regioselectivities but also great functional group tolerance under mild reaction conditions. For

• of substituted phenols using QuCN. Synthesis of substituted phenols with DDQ (5). Aerobic bromination of arenes using an acridinium-based photocatalyst. Aerobic bromination of arenes with anthraquinone. Chlorination of benzene derivatives with Mes-Acr-MeClO4 (2). Chlorination of arenes with 4CzIPN

Two new aromatic polyketides from a sponge-derived Fusarium

• Mada Triandala Sibero,
• Tao Zhou,
• Keisuke Fukaya,
• Daisuke Urabe,
• Ocky K. Karna Radjasa,
• Agus Sabdono,
• Agus Trianto and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2019, 15, 2941–2947, doi:10.3762/bjoc.15.289

• between the two rings to complete the anthraquinone skeleton in consideration of the UV spectrum and the molecular formula, providing two possible structures a and b for 1 (Figure 2): the methoxy group is positioned at C7 in structure a and at C5 in structure b. In order to eliminate one of the two

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

• is difficult to realize highly efficient TADF emitters, which is especially the case for red emitters where nonradiative rates are high due to the well-known energy gap law [28]. While anthraquinone-based charge-transfer compounds have recently been shown to exhibit TADF that then translated to their

• behavior of the four compounds was disappointing, especially compared to the high ΦPL values and deep red emission reported for anthraquinone-based TADF emitters [29]. For the nonemissive complexes, it is possible that this was due to ISC being much faster than RISC. For benzoquinone, ISC occurs within 10

Mechanochemical Friedel–Crafts acylations

• Mateja Đud,
• Anamarija Briš,
• Iva Jušinski,
• Davor Gracin and
• Davor Margetić

Beilstein J. Org. Chem. 2019, 15, 1313–1320, doi:10.3762/bjoc.15.130

• leading to the anthraquinone core in a single reaction pot in solid state [57][58]. Indeed, milling of p-xylene, AlCl3 and phthaloyl chloride led to the formation of a mixture of 10 and intramolecular FC product 29 [59] in a 1:3 ratio (Scheme 6). The ratio of 1,4-dimethylanthraquinone (29) did not

First thia-Diels–Alder reactions of thiochalcones with 1,4-quinones

• Grzegorz Mlostoń,
• Katarzyna Urbaniak,
• Paweł Urbaniak,
• Anna Marko,
• Anthony Linden and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2018, 14, 1834–1839, doi:10.3762/bjoc.14.156

• initially formed [4 + 2] cycloadducts. In general, the yields of the isolated products were high. With 5-chloro-10-hydroxy-1,4-anthraquinone, the thia-Diels–Alder reaction occurred with complete regioselectivity. In the case of the reaction of vitamin K3 (menadione) with diphenylthiochalcone, the initial

• 1,4-benzoquinone, 1,4-naphthoquinone, and 1,4-anthraquinone were investigated as a route to novel 4H-thiochromene-5,8-dione derivatives. Results and Discussion Aryl and hetary lthiochalcones 1a–d are easily obtained by treatment of the corresponding chalcones with Lawesson′s reagent in THF solution

• [15]. Along with the commercially available 1,4-benzoquinone (2a) and 1,4-naphthoquinone (2b), 1,4-anthraquinone (2c) and 5-chloro-10-hydroxy-1,4-anthraquinone (2d) were prepared from quinizarine according to known procedures [27][28]. First experiments were performed with 2b and thiochalcones 1a–d in

An overview of recent advances in duplex DNA recognition by small molecules

• Sayantan Bhaduri,
• Nihar Ranjan and
• Dev P. Arya

Beilstein J. Org. Chem. 2018, 14, 1051–1086, doi:10.3762/bjoc.14.93

• anthraquinone–chalcone hybrids were synthesized using Claisen–Schmidt reaction in order to test their anticancer potential against human cancer cell lines and DNA binding affinity and specificity. It has been observed that three conjugates 32–34 exhibited significant cytotoxicity against LS174 and HeLa cancer

An air-stable bisboron complex: a practical bidentate Lewis acid catalyst

• Longcheng Hong,
• Sebastian Ahles,
• Andreas H. Heindl,
• Gastelle Tiétcha,
• Andrey Petrov,
• Zhenpin Lu,
• Christian Logemann and
• Hermann A. Wegner

Beilstein J. Org. Chem. 2018, 14, 618–625, doi:10.3762/bjoc.14.48

• efficiently promotes the IEDDA reaction of 1,2,4,5-tetrazine (6) with 1,4-naphthaquinone (7a) [21]. Therefore, complex B was also tested as catalyst in the IEDDA reaction of 1,2,4,5-tetrazine (6) with 1,4-naphthaquinonic dienophiles 7a–7d. As shown in Table 2, the product 2,3-diaza-9,10-anthraquinone (8a) was

• obtained in 93% yield catalyzed by B while the yield with A was only 76% (Table 2, entry 1). Furthermore, the air-stable bisboron complex B successfully catalyzed the reactions and allowed the synthesis of 2,3-diaza-5,12-naphthacenedione (8b), 6-methoxy-2,3-diaza-9,10-anthraquinone (8c), and 6,7-dimethoxy

• -2,3-diaza-9,10-anthraquinone (8d) in excellent yields (82%, 88%, 95%, respectively) supporting the practicality of this catalyst for IEDDA reactions (Table 2, entry 2–4). Conclusion In summary, we report an air-stable bidentate Lewis acid bisboron complex as an efficient catalyst for IEDDA reaction of

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

• used CF3SO2Na as source of the trifluoromethyl group and a catalytic amount of anthraquinone-2-carboxylic acid (AQN-2-CO2H). The scope was achieved on arenes and heteroarenes (10 examples). Once more, electron-rich aromatic compounds were converted into the corresponding trifluoromethylated products in

Pd- and Cu-catalyzed approaches in the syntheses of new cholane aminoanthraquinone pincer-like ligands

• Nikolay V. Lukashev,
• Gennadii A. Grabovyi,
• Dmitry A. Erzunov,
• Alexey V. Kazantsev,
• Gennadij V. Latyshev,
• Alexei D. Averin and
• Irina P. Beletskaya.

Beilstein J. Org. Chem. 2017, 13, 564–570, doi:10.3762/bjoc.13.55

• ). Consequently, this system was used for the synthesis of bis-steroidal arylamines 5a and 5b starting from 24-aminocholanol 3a. Activated chlorinated substrates, such as 1,8- and 1,5-dichloroanthraquinones, are very promising substrates for nucleophilic substitution. For instance, 1,8-dichloro-9,10-anthraquinone

• . Though 5a was not observed in the reaction with 1,3-diiodobenzene, a good yield was obtained with 1,3-dibromobenzene. In fact, the Pd-catalyzed coupling was more efficient [43] than Ullmann-type chemistry (61% from 1,3-dibromobenzene vs 40% from 1,3-diiodobenzene). Since the anthraquinone skeleton is

• yield of 5d (22%). We speculated that the low yield was caused by the presence of an additional hydroxy group in 3b. The formation of the alkoxide anion on the substrate due to the thermodynamically unfavorable equilibrium with Cs2CO3 might promote the destruction of the anthraquinone scaffold. Indeed

A versatile route to polythiophenes with functional pendant groups using alkyne chemistry

• Xiao Huang,
• Li Yang,
• Rikard Emanuelsson,
• Jonas Bergquist,
• Maria Strømme,
• Martin Sjödin and
• Adolf Gogoll

Beilstein J. Org. Chem. 2016, 12, 2682–2688, doi:10.3762/bjoc.12.265

• . The synthetic utility of pyEDOT is demonstrated by the following examples involving a range of pendant groups. The electron acceptor units diethyl terephthalate (DET) and 9,10-anthraquinone (AQ) are of particular interest for their redox chemistry in energy storage applications [34]. Their ester and

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162