Mono or double Pd-catalyzed C–H bond functionalization for the annulative π-extension of 1,8-dibromonaphthalene: a one pot access to fluoranthene derivatives

• Nahed Ketata,
• Linhao Liu,
• Ridha Ben Salem and
• Henri Doucet

Beilstein J. Org. Chem. 2024, 20, 427–435, doi:10.3762/bjoc.20.37

• these reactions require high catalyst or base loadings, and offer a very limited scope regarding the use of reagents featuring functional groups useful in organic synthesis. Consequently, the discovery of simpler and more efficient synthetic procedures for the preparation of fluoranthene derivatives

Green and sustainable approaches for the Friedel–Crafts reaction between aldehydes and indoles

• Periklis X. Kolagkis,
• Eirini M. Galathri and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2024, 20, 379–426, doi:10.3762/bjoc.20.36

Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters

• Carlos R. Azpilcueta-Nicolas and
• Jean-Philip Lumb

Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35

• chemistry is well documented [1][2]. Traditional approaches for radical generation relied on hazardous reagents and harsh conditions, resulting in low reaction efficiency and undesired byproduct formation [3][4][5][6]. As a consequence, the utility of radicals in organic synthesis remained limited for many

Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments

• Aissam Okba,
• Pablo Simón Marqués,
• Kyohei Matsuo,
• Naoki Aratani,
• Hiroko Yamada,
• Gwénaël Rapenne and
• Claire Kammerer

Beilstein J. Org. Chem. 2024, 20, 287–305, doi:10.3762/bjoc.20.30

• photoextrusion of S and SO2 fragments are classical methods in organic synthesis [54][58][59], whereas photoextrusion of SO from bisaryl sulfoxide moieties has been evidenced more recently by Wolf et al. [60][61]. Solutions of dinaphthothiepine 3a and its sulfoxide analogue 4a in dichloromethane were irradiated

Nucleophilic functionalization of thianthrenium salts under basic conditions

• Xinting Fan,
• Duo Zhang,
• Xiangchuan Xiu,
• Bin Xu,
• Yu Yuan,
• Feng Chen and
• Pan Gao

Beilstein J. Org. Chem. 2024, 20, 257–263, doi:10.3762/bjoc.20.26

• ][5][6][7][8][9][10] have been extensively utilized as readily accessible synthetic building blocks in organic synthesis, particularly in the ipso-functionalization of C–S bonds. Of the sulfonium salts, organothianthrenium salts exhibit distinct structural properties and reactivities, thereby offering

• further potential in organic synthesis. Despite establishing a few preliminary methods for preparing organothianthrenium salts, their application potential is historically thwarted by harsh synthetic conditions and the poor durability of the resulting products [7]. Recently, Ritter and co-workers have

Catalytic multi-step domino and one-pot reactions

• Svetlana B. Tsogoeva

Beilstein J. Org. Chem. 2024, 20, 254–256, doi:10.3762/bjoc.20.25

• atom efficiency, step and pot economies, decreased number of purification steps, or protecting-group-free synthesis. Multi-step domino [1][2] and one-pot [3] reactions represent a new powerful toolbox in organic synthesis to install molecular complexity economically and sustainably, starting from

• steps, which is superior to conventional organic synthesis. The Thematic Issue “Catalytic multi-step domino and one-pot reactions” in the Beilstein Journal of Organic Chemistry, which I had the pleasure to edit, covers the recent strategies of domino reactions and one-pot syntheses and presents the

Substitution reactions in the acenaphthene analog of quino[7,8-h]quinoline and an unusual synthesis of the corresponding acenaphthylenes by tele-elimination

• Ekaterina V. Kolupaeva,
• Narek A. Dzhangiryan,
• Alexander F. Pozharskii,
• Oleg P. Demidov and
• Valery A. Ozeryanskii

Beilstein J. Org. Chem. 2024, 20, 243–253, doi:10.3762/bjoc.20.24

• of the corresponding monoprotonated forms are given). Meanwhile, the very synthesis of polycondensed quinoline bases with a certain arrangement of nitrogen atoms is often a challenge for a synthetic scientist [9][10]. This greatly limits the possible use of such polynuclear azaarenes in organic

• synthesis and the study of their properties. For example, quinoquinoline 3 is synthesized in six steps from diamine 2 with a total yield not exceeding 10% [9]. This azaarene still remains a poorly available compound despite the rich chemistry of its functional derivatives, the interesting tautomeric, proton

Copper-catalyzed multicomponent reaction of β-trifluoromethyl β-diazo esters enabling the synthesis of β-trifluoromethyl N,N-diacyl-β-amino esters

• Youlong Du,
• Haibo Mei,
• Ata Makarem,
• Ramin Javahershenas,
• Vadim A. Soloshonok and
• Jianlin Han

Beilstein J. Org. Chem. 2024, 20, 212–219, doi:10.3762/bjoc.20.21

• organic synthesis, as they can be used as diazo intermediates or carbene precursors for the rapid construction of complex molecules along with the introduction of fluoroalkyl groups [14][15][16]. Although the reaction of trifluorodiazoethane [17][18][19][20][21][22][23][24][25][26][27] as well as α-diazo

• esters [28][29][30] have been widely explored, β-trifluoromethyl β-diazo esters have been less investigated, mainly due to the instability of such structures. Therefore, methods for the synthesis of β-trifluoromethyl β-diazo esters and their applications in organic synthesis are needed but remain

Chiral phosphoric acid-catalyzed transfer hydrogenation of 3,3-difluoro-3H-indoles

• Yumei Wang,
• Guangzhu Wang,
• Yanping Zhu and
• Kaiwu Dong

Beilstein J. Org. Chem. 2024, 20, 205–211, doi:10.3762/bjoc.20.20

• great attention in organic synthesis. Various methods [9], including reductive hydrogenation [10][11], kinetic resolution [12][13][14], functionalization of indole [15], and de novo construction of chiral 2-substituted indolines, have been developed [16][17][18][19][20]. In recent years, the metal

Identification of the p-coumaric acid biosynthetic gene cluster in Kutzneria albida: insights into the diazotization-dependent deamination pathway

• Seiji Kawai,
• Akito Yamada,
• Yohei Katsuyama and
• Yasuo Ohnishi

Beilstein J. Org. Chem. 2024, 20, 1–11, doi:10.3762/bjoc.20.1

• Inc. (Shiga, Japan). Primers were purchased from Thermo Fisher Scientific (Waltham, MA, USA). Chemicals for the enzymatic assay were purchased from Sigma-Aldrich (St. Louis, MO, USA). Chemicals for organic synthesis were purchased from Tokyo Chemical Industry (Tokyo, Japan). 3-Aminocoumaric acid (3

1-Butyl-3-methylimidazolium tetrafluoroborate as suitable solvent for BF₃: the case of alkyne hydration. Chemistry vs electrochemistry

• Marta David,
• Elisa Galli,
• Richard C. D. Brown,
• Marta Feroci,
• Fabrizio Vetica and
• Martina Bortolami

Beilstein J. Org. Chem. 2023, 19, 1966–1981, doi:10.3762/bjoc.19.147

• commercially available BF3 diethyl etherate (BF3·Et2O), commonly used in organic synthesis. Indeed, the main advantages of the developed system are: 1) in situ generation of BF3, which avoids its storage and handling, 2) the possibility to control the amount of electrogenerated BF3 using current by simply

Construction of diazepine-containing spiroindolines via annulation reaction of α-halogenated N-acylhydrazones and isatin-derived MBH carbonates

• Xing Liu,
• Wenjing Shi,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2023, 19, 1923–1932, doi:10.3762/bjoc.19.143

• the synthesis of spirooxindole derivatives continues to be a highly active subject in organic synthesis [31][32][33][34][35]. In recent years, the readily available isatin-derived Morita–Baylis–Hillman (MBH) carbonates have become one of the most powerful reagents for the construction of diverse

Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides

• Kan Tang,
• Megan R. Brown,
• Chad Risko,
• Melissa K. Gish,
• Garry Rumbles,
• Phuc H. Pham,
• Oana R. Luca,
• Stephen Barlow and
• Seth R. Marder

Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142

• ; reduction; reductive dimerization; Introduction Reductive dehalogenation reactions of organic halides can be used in organic synthesis as a means of generating carbon-centered radical or anion intermediates and could have relevance to the treatment of waste halogenated polymers. While such reactions can be

Anion–π catalysis on carbon allotropes

• M. Ángeles Gutiérrez López,
• Mei-Ling Tan,
• Giacomo Renno,
• Augustina Jozeliūnaitė,
• J. Jonathan Nué-Martinez,
• Javier Lopez-Andarias,
• Naomi Sakai and
• Stefan Matile

Beilstein J. Org. Chem. 2023, 19, 1881–1894, doi:10.3762/bjoc.19.140

• . Currently, anion–π catalysis on carbon allotropes gains momentum because the combination with electric-field-assisted catalysis promises transformative impact on organic synthesis. Keywords: anion–π interactions; autocatalysis; catalysis; carbon nanotubes; Diels–Alder reactions; electric-field-induced

• -covalently electrify organic synthesis in the broadest sense. (A) Anion–π catalysis: Stabilization of anionic transition states from substrate S to product P on π-acidic aromatic surfaces. (B) Anion–(π)n–π catalysis: Stabilization of anionic transition states by polarization of π stacks to induce oriented

• conversion of interfaced substrates 68 and 73 on pristine MWCNTs 3 was of particular interest with regard to catalysis initiated by oriented external electric fields (OEEFs, Figure 9B). The idea of OEEF catalysis has been around for a long time as a promising, bioinspired concept to revolutionize organic

Aromatic systems with two and three pyridine-2,6-dicarbazolyl-3,5-dicarbonitrile fragments as electron-transporting organic semiconductors exhibiting long-lived emissions

• Karolis Leitonas,
• Brigita Vigante,
• Dmytro Volyniuk,
• Audrius Bucinskas,
• Pavels Dimitrijevs,
• Sindija Lapcinska,
• Pavel Arsenyan and
• Juozas Vidas Grazulevicius

Beilstein J. Org. Chem. 2023, 19, 1867–1880, doi:10.3762/bjoc.19.139

• Organic Synthesis, Aizkraukles 21, LV-1006, Riga, Latvia 10.3762/bjoc.19.139 Abstract The pyridine-3,5-dicarbonitrile moiety has gained significant attention in the field of materials chemistry, particularly in the development of heavy-metal-free pure organic light-emitting diodes (OLEDs). Extensive

Recent advancements in iodide/phosphine-mediated photoredox radical reactions

• Tinglan Liu,
• Yu Zhou,
• Junhong Tang and
• Chengming Wang

Beilstein J. Org. Chem. 2023, 19, 1785–1803, doi:10.3762/bjoc.19.131

• , numerous remarkable breakthroughs and notable progresses have been achieved in the realm of photoredox catalysis [1][2][3]. This domain has profoundly transformed modern organic synthesis, resulting in a considerable surge in research efforts centered on free radical reactions [4]. Presently, photoredox

• in organic synthesis would provide new insights and novel concepts for the exploration of other metallaphotoredox catalytic systems, thus greatly speeding up the process of new reaction findings. An elegant NaI/PPh3/CuBr metallaphotoredox dual-catalytic system was responsible for the aforementioned

Trifluoromethylated hydrazones and acylhydrazones as potent nitrogen-containing fluorinated building blocks

• Zhang Dongxu

Beilstein J. Org. Chem. 2023, 19, 1741–1754, doi:10.3762/bjoc.19.127

• pharmacological activities [86][87]. Acylhydrazones can exist in either E or Z forms in solution, and they can exhibit good optical properties for applications as photoswitches, in luminescence sensing, and as metallo-assemblies [88][89]. In organic synthesis, acylhydrazones have served as stable imine

Lewis acid-promoted direct synthesis of isoxazole derivatives

• Dengxu Qiu,
• Chenhui Jiang,
• Pan Gao and
• Yu Yuan

Beilstein J. Org. Chem. 2023, 19, 1562–1567, doi:10.3762/bjoc.19.113

• derivatives; sodium nitrite; transition metals; Introduction The isoxazole derivatives not only exist in many natural products [1][2][3] and pharmaceutical intermediates [4][5][6][7], but also have great application values in organic synthesis [8][9] (Figure 1). In the past decades, many methods have been

• environmentally friendly catalysts, our laboratory recently developed an alternative approach to the synthesis of isooxazoles starting from 2-methylquinoline and alkynes mediated by Brønsted acids in good yields (Scheme 1, reaction 3) [20]. The utilization of main element metal aluminum salts in organic synthesis

N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations

• Fatemeh Doraghi,
• Seyedeh Pegah Aledavoud,
• Mehdi Ghanbarlou,
• Bagher Larijani and
• Mohammad Mahdavi

Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106

• field of organic synthesis. These compounds are readily accessible, safe, and more stable than toxic, unstable, and foul-smelling thiols. These electrophilic sulfur sources have deserved particular interest for the C–S bond formation via the reaction with various nucleophiles. Their preparation is

• article, we focus on the application of these alternative sulfenylating reagents in organic transformations. Keywords: electrophile; N-(sulfenyl)succinimides/phthalimides; organic transformations; organosulfur; sulfenylation; Introduction Sulfur-containing compounds are of high importance in organic

• synthesis, medicinal chemistry, and materials science [1][2][3][4][5]. For example, they are used in the treatment of cancer [6][7][8], inflammation [9][10][11], human immunodeficiency virus [12][13], Alzheimer’s and Parkinson’s diseases [14][15]. Scheme 1 shows selected examples of sulfur-containing

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

• diversity, low cost, and versatile applications. This article overviews applications of NHC–Cu(I) complexes as catalysts in organic synthesis over the last 12 years, which include hydrosilylation reactions, conjugate addition, [3 + 2] cycloaddition, A3 reaction, boration and hydroboration, N–H and C(sp2)–H

• employed as catalysts in a variety of organic reactions. In this section, a brief review on the use of NHC–Cu(I) complexes as catalysts in organic synthesis is presented. 2.1 Hydrosilylation reactions Hydrosilylation reactions involve the addition of a silicon–hydrogen (Si–H) moiety across a carbon–carbon

• reactive and difficult to isolate. The NHC–Cu complex also helps to control the regioselectivity and stereoselectivity of the reaction, which are of high importance in organic synthesis. Overall, the use of NHC–Cu complexes as catalysts for conjugate addition reactions offers a highly efficient and

Consecutive four-component synthesis of trisubstituted 3-iodoindoles by an alkynylation–cyclization–iodination–alkylation sequence

• Nadia Ledermann,
• Alae-Eddine Moubsit and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2023, 19, 1379–1385, doi:10.3762/bjoc.19.99

• [9][10][11] and their preparation is an evergreen in organic synthesis [12][13][14][15]. Although the classical Fischer indole synthesis provides a very reliable and broadly applicable access to indole derivatives [16][17][18], striving for new indole syntheses is ongoing. In particular, metal

Visible-light-induced nickel-catalyzed α-hydroxytrifluoroethylation of alkyl carboxylic acids: Access to trifluoromethyl alkyl acyloins

• Feng Chen,
• Xiu-Hua Xu,
• Zeng-Hao Chen,
• Yue Chen and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2023, 19, 1372–1378, doi:10.3762/bjoc.19.98

• ; Introduction Acyloins (also known as α-hydroxy ketones) are widely found as structural motif in natural products [1][2][3][4][5][6][7] and bioactive molecules [8][9][10][11] (Figure 1). They can also be used as building blocks in organic synthesis [12][13][14], involved in numerous transformations to other

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

• synthetic strategy for the construction of C–C bonds in organic synthesis (Scheme 1b). Compared with traditional coupling reactions, the CDC strategy has the following advantages: 1) atom economy, 2) green and efficient reaction, 3) a wide range of substrate sources. Therefore, organic chemists consider the

• ]. Conclusion In summary, Li et al. first proposed the concept of CDC, which now plays an essential role in organic synthesis. The atom- and step-economic CDC reaction can directly construct various C–C bonds from unreactive C–H substrates, including functionalized ethers. By reviewing these reactions, it can

Acetaldehyde in the Enders triple cascade reaction via acetaldehyde dimethyl acetal

• Alessandro Brusa,
• Debora Iapadre,
• Maria Edith Casacchia,
• Alessio Carioscia,
• Giuliana Giorgianni,
• Giandomenico Magagnano,
• Fabio Pesciaioli and
• Armando Carlone

Beilstein J. Org. Chem. 2023, 19, 1243–1250, doi:10.3762/bjoc.19.92

• organic synthesis to build complex scaffolds starting from simple starting materials. The Enders three-component cascade reaction was a cornerstone in the field and a plethora of organocatalyzed cascade reactions followed. However, acetaldehyde was not shown as a successful reaction partner, probably

• reason, the use of MCRs is appealing in the construction of natural or synthetic products [2][3][4][5] or libraries of compounds [2], and is generally considered an advantage in organic synthesis for atom economy, waste reduction and time saving. Cascade reactions are defined as chemical processes in

Cyanothioacetamides as a synthetic platform for the synthesis of aminopyrazole derivatives

• Valeriy O. Filimonov,
• Alexandra I. Topchiy,
• Vladimir G. Ilkin,
• Tetyana V. Beryozkina and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2023, 19, 1191–1197, doi:10.3762/bjoc.19.87

• Valeriy O. Filimonov Alexandra I. Topchiy Vladimir G. Ilkin Tetyana V. Beryozkina Vasiliy A. Bakulev Technology of Organic Synthesis Department, Ural Federal University named after the first President of Russia B. N. Yeltsin, 19 Mira st. Yekaterinburg 620002, Russia Department of Organic Chemistry