A deep-red fluorophore based on naphthothiadiazole as emitter with hybridized local and charge transfer and ambipolar transporting properties for electroluminescent devices

• Suangsiri Arunlimsawat,
• Patteera Funchien,
• Pongsakorn Chasing,
• Atthapon Saenubol,
• Taweesak Sudyoadsuk and
• Vinich Promarak

Beilstein J. Org. Chem. 2023, 19, 1664–1676, doi:10.3762/bjoc.19.122

• , EQEmax of 3.32%, and EUE of 47%. This work successfully established that an ambipolar D–A–D-type fluorophore having combined AIE–HLCT features could be a promising design to develop future deep-red or near-infrared OLEDs. Experimental Materials and Methods All chemical reagents and solvents were

Tying a knot between crown ethers and porphyrins

• Maksym Matviyishyn and
• Bartosz Szyszko

Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120

• macrocycles in systems designed for reaction-centre-like processes and their usage as potential energy transduction devices [51][76][77]. meso-Crowned porphyrins One of the conceptually most straightforward methods to introduce a crown ether unit into the porphyrin is functionalising the meso-substituents

• ) and Co(II), into the porphyrin core introduced a probe, which enabled ESR spectroscopy methods as a means of the analysis of the assembled complexes with cationic guests bound within the crown ether pockets. Over the years, several groups have shown interesting chemistry of meso-crowned porphyrins

Synthesis of 7-azabicyclo[4.3.1]decane ring systems from tricarbonyl(tropone)iron via intramolecular Heck reactions

• Aaron H. Shoemaker,
• Elizabeth A. Foker,
• Elena P. Uttaro,
• Sarah K. Beitel and
• Daniel R. Griffith

Beilstein J. Org. Chem. 2023, 19, 1615–1619, doi:10.3762/bjoc.19.118

• these motifs have attracted considerable interest. The synthesis of azapolycycles containing a seven-membered carbocyclic ring is particularly challenging in contrast to comparable skeletons containing only five- or six-membered rings [3]. Thus, comparatively few general methods exist for accessing

• best among those screened, yields remained modest (44%). X-ray analysis provided confirmation of the structure of bicycle 8 (CCDC No. 2263675). While searching for methods to improve the yield of our desired azabicycle, we came across the observation of Andrade and Kokkonda that vinylic halides with

Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• Zixiao Wang Feichen Cui Yang Sui Jiajun Yan School of Physical Science and Technology, ShanghaiTech University, 393 Middle Huaxia Rd., Shanghai, 201210, China 10.3762/bjoc.19.116 Abstract Radical chemistry is one of the most important methods used in modern polymer science and industry. Over the

• , solution, emulsion, and suspension; and (iv) inexpensive and facile set-ups compared to other polymerization techniques [20]. There are four common industrial methods of radical polymerization [2] as shown in Table 1. The only components of a bulk polymerization mixture are monomers, the initiator, and

• materials [74]. In 2000, they received the Nobel Prize in Chemistry. Typical conductive polymer structures have π-conjugation (Scheme 9A) [75]. They can be synthesized by various methods such as electrochemical and chemical methods. Oxidative polymerization and chain-growth polymerization are also good ways

Cyclodextrins permeabilize DPPC liposome membranes: a focus on cholesterol content, cyclodextrin type, and concentration

• Ghenwa Nasr,
• Hélène Greige-Gerges,
• Sophie Fourmentin,
• Abdelhamid Elaissari and
• Nathalie Khreich

Beilstein J. Org. Chem. 2023, 19, 1570–1579, doi:10.3762/bjoc.19.115

• towards membrane lipids, the CD–phospholipid molar ratio, and the CHOL content in the membrane. Experimental Materials and methods Materials α-CD, β-CD, γ-CD, and randomly methylated-β-CD (RAMEB, DS = 12.9), were provided by Wacker Chemie (Germany). Low methylated-β-CD (CRYSMEB, DS = 4.9) and

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

• developed to prepare isoxazole derivatives [10][11][12][13]. However, most of the starting materials for these methods are oximes and hydroximinoyl chlorides [4][13][14][15]. Recently, the sp3 C–H bond functional group transformation of 2-methylquinoline derivatives into isoxazole derivatives has been

• nitrogen source (Scheme 1, reaction 2). In 2017, Xu and co-workers [19] developed a copper-mediated annulation reaction to synthesize isoxazoles from two different alkynes. In fact, most methods mostly used highly toxic transition-metal catalysts such as copper metals. In order to develop cheaper and more

Secondary metabolites of Diaporthe cameroonensis, isolated from the Cameroonian medicinal plant Trema guineensis

• Bel Youssouf G. Mountessou,
• Élodie Gisèle M. Anoumedem,
• Blondelle M. Kemkuignou,
• Yasmina Marin-Felix,
• Frank Surup,
• Marc Stadler and
• Simeon F. Kouam

Beilstein J. Org. Chem. 2023, 19, 1555–1561, doi:10.3762/bjoc.19.112

• and its meanwhile invalid synonymic anamorphic state Phomposis. Likewise, the other, known co-metabolites like the cytochalasins that were concurrently obtained are presently being studied in-depth by methods of cell biology. However, this activity is beyond the scope of the current study

Morpholine-mediated defluorinative cycloaddition of gem-difluoroalkenes and organic azides

• Tzu-Yu Huang,
• Mario Djugovski,
• Sweta Adhikari,
• Destinee L. Manning and
• Sudeshna Roy

Beilstein J. Org. Chem. 2023, 19, 1545–1554, doi:10.3762/bjoc.19.111

• ][12], inflammation [13], bacterial [14][15], and viral infections [16]. Hence, new ways to rapidly and efficiently access 1,2,3-triazole heterocyclic motifs are still in demand. However, methods for the direct synthesis of 1,4,5-trisubstituted-1,2,3-triazoles are limited [17]. This is highly desirable

• regioselective reaction that does not rely on carbonyl- or alkyne-based methods or late-stage modifications to access 1,4,5-trisubstituted-1,2,3-triazoles. However, carbonyl chemistry was utilized to synthesize the gem-difluoroalkene starting material [30]. In fact, our findings offer a straightforward direct

Synthesis of 5-arylidenerhodanines in L-proline-based deep eutectic solvent

• Stéphanie Hesse

Beilstein J. Org. Chem. 2023, 19, 1537–1544, doi:10.3762/bjoc.19.110

• for 24 h at 60 °C. Comparison of physicochemical properties of selected DES used in this study. Optimization of Knoevenagel conditions.a Comparison to other reported methods for 5-benzylidenerhodanine synthesis. Structures and observed antioxidant activity expressed as % DPPH scavenging.a Supporting

Complexes of resorcin[4]arene with secondary amines: synthesis, solvent influence on “in-out” structure, and theoretical calculations of non-covalent interactions

• Waldemar Iwanek

Beilstein J. Org. Chem. 2023, 19, 1525–1536, doi:10.3762/bjoc.19.109

• atoms, presenting a challenging and time-consuming task for geometry optimization calculations and screening via DFT methods. Recent advancements have introduced fast semi-empirical DFT methods such as xTB [15], which enable their use in preliminary screening for molecular dynamics or searching for

• reactive sites (aISS), for example, in the formation of supramolecular complexes [16]. The particularly fast GFN-xTB methods work well in geometry optimization, which is the most time-consuming step of the DFT calculation. There have also been developments in DFT methods concerning the energy distribution

• geometries of the complexes were calculated using DFT methods. To evaluate the energy stability of the formed complexes, the HFLD method was employed to quantify the contributions of different non-covalent interactions. As shown below, the combination of two types of interactions, one of which is hydrophobic

Synthesis and biological evaluation of Argemone mexicana-inspired antimicrobials

• Jessica Villegas,
• Bryce C. Ball,
• Katelyn M. Shouse,
• Caleb W. VanArragon,
• Ashley N. Wasserman,
• Hannah E. Bhakta,
• Allen G. Oliver,
• Danielle A. Orozco-Nunnelly and
• Jeffrey M. Pruet

Beilstein J. Org. Chem. 2023, 19, 1511–1524, doi:10.3762/bjoc.19.108

• derivatives, compound B8 represents the natural compound pseudopalmatine [39]. The synthesis of this compound has been reported, albeit through alternative methods [33][38][40]. Reports indicated that unlike most other plant-derived protoberberines, pseudopalmatine has had far less pharmacological

• all variants and berberine is shown in Figure 3. Having assessed the antimicrobial effects of the berberine variants, we then turned to the construction of chelerythrine variants. Numerous methods of synthesizing chelerythrine and other benzophenanthridines have been reported, but unlike with the

• (R3/R4). Compound C4 is the known compound O-methylfagaronine, which has previously been synthesized through a variety of methods [50][51][52]. The antileukemia activity, antitumor activity, and inhibition of reverse transcriptase of O-methylfagaronine (C4) have previously been explored [51][52][53

Unraveling the role of prenyl side-chain interactions in stabilizing the secondary carbocation in the biosynthesis of variexenol B

• Moe Nakano,
• Rintaro Gemma and
• Hajime Sato

Beilstein J. Org. Chem. 2023, 19, 1503–1510, doi:10.3762/bjoc.19.107

• biosynthesis of trichobrasilenol [22], by combined methods of computational and experimental chemistry. Recently, Dickschat et al. reported the synthesis of a novel diterpene compound, variexenol B, using a substrate analogue called iso-GGPP (Scheme 1) [23]. This biosynthetic pathway has two interesting

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

• traditional heating methods. In the meanwhile, Qiu and Xu et al. reported the coupling reaction between diazo compounds 163 and N-sulfenylsuccinimides 1 under catalyst-, base-, and additive-free conditions (Scheme 71) [101]. The reaction proceeded via a radical pathway, in which a free carbene was generated

Functions of enzyme domains in 2-methylisoborneol biosynthesis and enzymatic synthesis of non-natural analogs

• Binbin Gu,
• Lin-Fu Liang and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2023, 19, 1452–1459, doi:10.3762/bjoc.19.104

• for sodorifen [38] – potentially allow for an evolution towards a natural biosynthetic pathway for C12 monoterpenoids. Experimental General synthetic methods Chemicals were purchased from Sigma-Aldrich Chemie GmbH (Steinheim, Germany), Carbolution Chemicals GmbH (St. Ingbert, Germany), or Carl Roth

α-(Aminomethyl)acrylates as acceptors in radical–polar crossover 1,4-additions of dialkylzincs: insights into enolate formation and trapping

• Angel Palillero-Cisneros,
• Paola G. Gordillo-Guerra,
• Fernando García-Alvarez,
• Olivier Jackowski,
• Franck Ferreira,
• Fabrice Chemla,
• Joel L. Terán and
• Alejandro Perez-Luna

Beilstein J. Org. Chem. 2023, 19, 1443–1451, doi:10.3762/bjoc.19.103

• . Furthermore, our protocol provides a complement to existing literature, as none of the previously reported methods to convert α-(aminomethyl)acrylates into enantioenriched β-amino acids is applicable for the preparation of β2,2-amino acids [27][28][29][30][31]. Experimental 1. Procedure for the monoallylation

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

• carboxylation, C(sp2)–H alkenylation and allylation, C(sp2)–H arylation, C(sp2)–H amidation, and C(sp2)–H thiolation. Preceding the section of applications, a brief description of the structure of NHCs, nature of NHC–metal bond, and methods of preparation of NHC–Cu complexes is provided. Keywords: conjugate

• , Cazin and co-workers reported the synthesis of Cu(I) complexes 61, 63, and 65 of the so-called ‘abnormal’ NHCs (Scheme 21) [35]. Thus, the conventional heating method as well as microwave irradiation methods were employed. The structures of the synthesized complexes were confirmed by X-ray analysis

• compounds, including diaryl- and dialkyl ketones and prochiral ketones, respectively (Scheme 36) [50]. Riant, Leyssens and co-workers investigated the mechanism of the hydrosilylation reaction of ketones using DFT, in situ FTIR, NMR, and kinetic methods [51][52]. The catalytic characteristics of sterically

One-pot nucleophilic substitution–double click reactions of biazides leading to functionalized bis(1,2,3-triazole) derivatives

• Hans-Ulrich Reissig and
• Fei Yu

Beilstein J. Org. Chem. 2023, 19, 1399–1407, doi:10.3762/bjoc.19.101

• situ are possible [23]. Later, examples were published showing that these methods are also compatible with the conditions of CuAAC. The earliest case was probably published by Fokin et al. [24][25], one of the inventors of the original copper-catalyzed (3 + 2) cycloaddition. Many examples of

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

• the scientific community for different reasons: 1) to have an overview on the methods already available, 2) to invite scientists that are working on synthesis methodology to apply their works to the design of ELs analogues, 3) the methods reported in this review can be useful tools for the scientific

• to prepare alkyl ether lipids. The synthesis methods specifically designed for the preparation of alkenyl ether lipids (plasmalogen) are not reviewed herein. For each compound, their synthesis is reported jointly, when appropriate, with some elements relative to their biological activity. The next

• have done a selection, which is based on the methodology employed in order to have an overview of the most useful methods employed for the synthesis of PAF and PAF-analogues. The synthesis of alkyl EL involves the chemistry of glycerol or its direct precursors (e.g., glycidol, solketal, epichlorohydrin

Organic thermally activated delayed fluorescence material with strained benzoguanidine donor

• Alexander C. Brannan,
• Elvie F. P. Beaumont,
• Nguyen Le Phuoc,
• George F. S. Whitehead,
• Mikko Linnolahti and
• Alexander S. Romanov

Beilstein J. Org. Chem. 2023, 19, 1289–1298, doi:10.3762/bjoc.19.95

• methods (SCALE3 ABSPACK) based upon symmetry-equivalent reflections combined with measurements at different azimuthal angles. For the final refinement, the contribution of severely disordered CH2Cl2 molecules in the crystals of 4BGIPN was accounted for by applying a solvent void mask calculated using

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

• interest in developing novel methodologies in this field of organic chemistry. Keywords: alkylation; cross-dehydrogenation coupling; ether; non-noble metals; Introduction Since the 1970s, organic chemists have developed many selective cross-coupling methods for the construction of C–C bonds, such as the

• , noble metals have been extensively studied as photocatalysts for CDC reactions [116][117][118][119][120][121] and these methods fill the gap of traditional thermocatalytic CDC reactions. In 2017, Ryu et al. developed tetrabutylammonium decatungstate (TBADT, (n-Bu4N)4[W10O32] as a photocatalyst to

Metal catalyst-free N-allylation/alkylation of imidazole and benzimidazole with Morita–Baylis–Hillman (MBH) alcohols and acetates

• Olfa Mhasni,
• Jalloul Bouajila and
• Farhat Rezgui

Beilstein J. Org. Chem. 2023, 19, 1251–1258, doi:10.3762/bjoc.19.93

• bifonazole have become well-established drugs for the treatment of numerous mycotic infections (Figure 1) [9][10]. Therefore, the development of new methods for the preparation of such compounds is highly required. The MBH acetates, instead of the corresponding alcohols, have been extensively used as

• these substrates and the formation of water as the sole non-toxic byproduct in the reaction [11]. In general, the previous methods for the amination of MBH alcohols needed catalysts or additives such as FeCl3 [12][13], In(OTf)3 [14], MoCl5 [15], AuCl3 [16], and I2 [17] as Lewis acids. Alternatively

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

• complete enantiocontrol (Scheme 1). This elegantly designed example established a new direction in asymmetric aminocatalysis, leading to an impressive growth of methods based on organocascade processes [8][10][13][14][15][16]. The experimental simplicity of the strategy offers the potential of rapidly

Radical ligand transfer: a general strategy for radical functionalization

• David T. Nemoto Jr,
• Kang-Jie Bian,
• Shih-Chieh Kao and
• Julian G. West

Beilstein J. Org. Chem. 2023, 19, 1225–1233, doi:10.3762/bjoc.19.90

• challenging-to-generate “uncontrollable” species prone to side reactions to versatile reactive intermediates enabling construction of myriad C–C and C–X bonds. This maturation of free radical chemistry has been enabled by several advances, including the proliferation of efficient radical generation methods

• , such as hydrogen atom transfer (HAT), alkene addition, and decarboxylation. At least as important has been innovation in radical functionalization methods, including radical–polar crossover (RPC), enabling these intermediates to be engaged in productive and efficient bond-forming steps. However, direct

• driven by several key features of RLT catalysis, including the ability to form diverse bonds (including C–X, C–N, and C–S), the use of simple earth abundant element catalysts, and the intrinsic compatibility of this approach with varied radical generation methods, including HAT, radical addition, and

Unravelling a trichloroacetic acid-catalyzed cascade access to benzo[f]chromeno[2,3-h]quinoxalinoporphyrins

• Chandra Sekhar Tekuri,
• Pargat Singh and
• Mahendra Nath

Beilstein J. Org. Chem. 2023, 19, 1216–1224, doi:10.3762/bjoc.19.89

• study is potentially useful for the development of highly conjugated π-electron rich porphyrinoids with improved light harvesting properties. Experimental Materials and instrumentation methods All reagents and solvents used in this study were purchased from Sigma-Aldrich (Merck) and were used as

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

• potential of such compounds. The most common method for obtaining 3,5-disubstituted pyrazoles is the cyclocondensation of 1,3-bielectrophilic reagents with hydrazine, which acts as a 1,2-dinucleophile [15][16]. It is worthy to note that a small number of methods for the synthesis of 3,5-diaminopyrazoles are

• presented in the literature. These syntheses are multistage [17] or are essentially a transformation of the structure of the previously obtained pyrazoles [18] (Scheme 1A). Methods for the synthesis of pyrazoles containing thioamide and amino groups in a molecule are even less developed than methods for

• obtaining 3,5-diaminopyrazoles, and presented in the literature by two examples only [19][20][21] (Scheme 1B). Thus, the development of effective methods for the production of 3,5-diaminopyrazoles and 3,5-diaminothiocarbamoylpyrazoles is an actual task which was chosen the aim of current study. Here, we