Phenotellurazine redox catalysts: elements of design for radical cross-dehydrogenative coupling reactions

• Alina Paffen,
• Christopher Cremer and
• Frederic W. Patureau

Beilstein J. Org. Chem. 2024, 20, 1292–1297, doi:10.3762/bjoc.20.112

• -substrate interaction. Phenotellurazine-catalyzed cross-dehydrogenative couplings. Screening of new Te(II)-catalyst candidates. ODCB: ortho-dichlorobenzene. Phenotellurazine-catalyzed cross-dehydrogenative indole dimerization. Supporting Information Supporting Information File 84: Experimental section and

Domino reactions of chromones with activated carbonyl compounds

• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 1256–1269, doi:10.3762/bjoc.20.108

• for long chained 2-fluoro-1,3-bis(silyloxy)-1,3-butadienes. In conclusion, the interaction of activated carbonyl compounds with chromones offer a great variety of different reaction pathways leading to various types of products with potential applications in materials science and medicinal chemistry

Synthesis and optical properties of bis- and tris-alkynyl-2-trifluoromethylquinolines

• Stefan Jopp,
• Franziska Spruner von Mertz,
• Peter Ehlers,
• Alexander Villinger and
• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 1246–1255, doi:10.3762/bjoc.20.107

• electronic push–pull interaction of the thiophene and the quinoline moieties via the alkyne. Finally, we focussed on the synthesis of tris-alkynylated quinolines starting from 3,4,8-tribromo-2-(trifluoromethyl)quinoline (11). Starting material 11 was synthesized in very good yield from quinolone 3 by

Competing electrophilic substitution and oxidative polymerization of arylamines with selenium dioxide

• Vishnu Selladurai and
• Selvakumar Karuthapandi

Beilstein J. Org. Chem. 2024, 20, 1221–1235, doi:10.3762/bjoc.20.105

• structure, it self-organized through π–π interaction between the oxamide motif and the aryl π-framework. Further, the CH…O=C interaction facilitated the formation of ladder-like packing in the solid state (Figure S36, Supporting Information File 1). The molecular structure of oxamide 13 is shown in Figure 3

• methyl anthranilate structure from the ideal Lewis structure. The lone pair electron of nitrogen was donated to the non-Lewis orbital (i.e., LP*) of the adjacent carbon C(4) (see Figure 8), with a high interaction energy of 93.62 kcal⋅mol−1. Such an interaction was not found for aniline and o-anisidine

• . Instead, for o-anisidine and aniline, the lone pair electrons were delocalized into the antibonding NBO (i.e., BD*) with a smaller interaction energy of ≈26 kcal⋅mol−1. In other words, as shown in Scheme 8, the lone electron pair present at the nitrogen atom was delocalized into the π-conjugated system

Stability trends in carbocation intermediates stemming from germacrene A and hedycaryol

• Naziha Tarannam,
• Prashant Kumar Gupta,
• Shani Zev and
• Dan Thomas Major

Beilstein J. Org. Chem. 2024, 20, 1189–1197, doi:10.3762/bjoc.20.101

• interaction is even more distinct when inspecting the electronic energies (Figure S1, Supporting Information File 1), where we observe a significant stabilizing effect of the hydroxyl–cation interaction for F-OH and H-OH. This is clearly discernible from the C+···OH distances (Figure 4, Table 1) and visible

• from the NCI plots. In general, stabilization of some 5-7 bicyclic carbocations (e.g., F-OH and H-OH) are via C+···OH interactions, which are facilitated by the carbocation and hydroxyl functionality being located in the relatively flexible 7-membered ring. This type of interaction is absent in case of

• . Additionally, we carried out NBO analysis for other hedycaryol cations, and due to large bond distances between C+···OH, no such charge transfer is observed, i.e., E(2) = 0. In these cases, the interaction is likely of a classical electrostatic nature. Next, to better understand the influence of carbocation

Two-fold addition reaction of silylene to C₆₀: structural and electronic properties of a bis-adduct

• Masahiro Kako,
• Masato Kai,
• Masanori Yasui,
• Michio Yamada,
• Yutaka Maeda and
• Takeshi Akasaka

Beilstein J. Org. Chem. 2024, 20, 1179–1188, doi:10.3762/bjoc.20.100

• . The regioselectivity in the addition reaction of 1 with C70 was explained earlier in terms of the interaction between the HOMO of 1 and the LUMO of C70 [16]. The reaction mechanism of ethylene with a silylene substituted with thiolate ligands has been studied using theoretical calculations, in which

• 3 may involve the interaction of 1 with the LUMO of 2a. The HOMO of 2a is observed mainly around the cis-1 and e′′ bonds among the 6,6-bonds, although the cis-1 bond would not be susceptible to the second silylene addition because of its steric hindrance. Alternatively, the interaction of the LUMO

• . Also, the HOMO of 2a is observed around the cis-1 and e′′ bonds, although the cis-1 bond would be sterically protected from the second silylene addition. Alternatively, the interaction of the LUMO of 1 with e′′ bonds of 2 should be considered. Electrochemical measurements (CV and DPV) were taken to

Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer

• Mohd Farhan Ansari,
• Atul Kumar Maurya,
• Abhishek Kumar and
• Saravanakumar Elangovan

Beilstein J. Org. Chem. 2024, 20, 1111–1166, doi:10.3762/bjoc.20.98

• indicates that the cation-coordinative interaction with the catalyst plays a significant role. Moreover, the mechanistic investigation suggested that the observed selectivity is due to the more reactive potassium manganate hydride towards the hydrogenation of imines to amines than the sodium manganate

Light on the sustainable preparation of aryl-cored dibromides

• Fabrizio Roncaglia,
• Alberto Ughetti,
• Nicola Porcelli,
• Biagio Anderlini,
• Andrea Severini and
• Luca Rigamonti

Beilstein J. Org. Chem. 2024, 20, 1076–1087, doi:10.3762/bjoc.20.95

• economy of the overall process. A pertinent example of this technique is represented by the Wohl–Ziegler halogenation protocol, which is based on the stable and easily handled N-bromosuccinimide (NBS), which is able to slowly deliver molecular bromine through its interaction with bromide ions [17][25

Structure–property relationships in dicyanopyrazinoquinoxalines and their hydrogen-bonding-capable dihydropyrazinoquinoxalinedione derivatives

• Tural N. Akhmedov,
• Ajeet Kumar,
• Daken J. Starkenburg,
• Kyle J. Chesney,
• Khalil A. Abboud,
• Novruz G. Akhmedov,
• Jiangeng Xue and
• Ronald K. Castellano

Beilstein J. Org. Chem. 2024, 20, 1037–1052, doi:10.3762/bjoc.20.92

• their profound implications on device performance [1]. Among these interactions, hydrogen bonding (H-bonding, HB) as a highly directional noncovalent interaction can influence the structural, electronic, and optoelectronic properties of bulk materials [2][3]. Hydrogen bonding plays a crucial role in

Spin and charge interactions between nanographene host and ferrocene

• Akira Suzuki,
• Yuya Miyake,
• Ryoga Shibata and
• Kazuyuki Takai

Beilstein J. Org. Chem. 2024, 20, 1011–1019, doi:10.3762/bjoc.20.89

• Fe2p peaks and the increase in shake-up peak intensity of the C1s in the XPS spectrum proved the emergence of charge-transfer host–guest interaction in FeCp2-ACFs-150, supported by the red-shift of the G-band in the Raman spectrum. The six-times enhancement in the spin concentration in FeCp2-ACFs-150

• compared with ACFs indicates the spin magnetism of the non-magnetic guest FeCp2+ molecule induced by a charge-transfer host–guest interaction in the nanographene host. The larger ESR linewidth than that expected from the dipolar interaction estimated by the localized spin concentration suggests the

• exchange interaction between the nanographene and FeCp2 spins. The narrowing of the ESR linewidth of FeCp2-ACFs-55 upon higher excitation microwave power suggests the inhomogeneity of the environment for FeCp2+ molecules in the nanographene host. The observed induction of spin magnetism by the interfacial

Carbonylative synthesis and functionalization of indoles

• Alex De Salvo,
• Raffaella Mancuso and
• Xiao-Feng Wu

Beilstein J. Org. Chem. 2024, 20, 973–1000, doi:10.3762/bjoc.20.87

• the catalyst undergoes reduction, therefore, rather using only CO, a mixture of CO–air (12:48 bar) was used with the aim of oxidizing the Pd(0) species in order to restore the catalyst able to catalyze the process again. The reaction mechanism proceeds with an initial interaction between the Pd(II

Synthesis and properties of 6-alkynyl-5-aryluracils

• Ruben Manuel Figueira de Abreu,
• Till Brockmann,
• Alexander Villinger,
• Peter Ehlers and
• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 898–911, doi:10.3762/bjoc.20.80

• result, the overall absorption intensity in the short-wavelength region was drastically reduced. This leads to the assumption that this absorption band is highly influenced by the dimethylamino group on the 5-phenyl group, even though the phenyl ring is twisted out of the plane. Interaction between the

• two π-systems is rather unlikely due to the twisted position of the phenyl ring. It is therefore reasonable to assume that this behavior is more likely to be related to a possible interaction of the dimethylamino group with the rest of the system. However, the combination of two dimethylamino groups

Activity assays of NnlA homologs suggest the natural product N-nitroglycine is degraded by diverse bacteria

• Kara A. Strickland,
• Brenda Martinez Rodriguez,
• Ashley A. Holland,
• Shelby Wagner,
• Michelle Luna-Alva,
• David E. Graham and
• Jonathan D. Caranto

Beilstein J. Org. Chem. 2024, 20, 830–840, doi:10.3762/bjoc.20.75

• activity even in the presence of millimolar concentrations of 2-NAE (Table S4, Supporting Information File 1). This observation suggests that binding in the substrate pocket is dependent on an electrostatic interaction with the NNG α-carboxylate, most likely from a lysine, arginine, histidine side chain or

Synthesis of new representatives of A₃B-type carboranylporphyrins based on meso-tetra(pentafluorophenyl)porphyrin transformations

• Victoria M. Alpatova,
• Evgeny G. Rys,
• Elena G. Kononova and
• Valentina A. Ol'shevskaya

Beilstein J. Org. Chem. 2024, 20, 767–776, doi:10.3762/bjoc.20.70

• properties and to modify the profile of biological activity due to optimum fluorine lipophylic properties, and enhanced interaction with lipid membranes [12][13][14]. Pentafluorophenyl-substituted porphyrin systems are especially useful for the connection of various functionalities capable for coupling with

Methodology for awakening the potential secondary metabolic capacity in actinomycetes

• Shun Saito and
• Midori A. Arai

Beilstein J. Org. Chem. 2024, 20, 753–766, doi:10.3762/bjoc.20.69

• . xanthus, which enhances the iron-scavenging capacity of M. xanthus and places S. coelicolor A3(2) M145 under iron starvation conditions. This chemical interaction activates the actinorhodin (8) biosynthetic gene cluster in S. coelicolor A3(2) M145. Onaka’s group reported that co-cultivation of

• , a unique case of activation of secondary metabolite biosynthetic genes by co-culture of actinomycetes and animal cells has been reported, which we outline in detail below. If microorganisms and animal cells are used, one might first imagine the interaction between humans and intestinal bacteria

• that substances that affect Wnt signaling can be produced in response to the interaction between animal cells and microorganisms. In addition, dehydropropylpantothenamide (53) was also identified using the same co-culture combination [123]. The second group of compounds identified included uniformides

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

• over 260 secondary metabolites from Penicillium [5], exhibiting not only antibacterial and anticancer activities but also potent antioxidant properties, inhibition of GSK-3β and α-glucosidase activities, and interaction with the pregnane X receptor (PXR). These compounds are categorized into

A myo-inositol dehydrogenase involved in aminocyclitol biosynthesis of hygromycin A

• Michael O. Akintubosun and
• Melanie A. Higgins

Beilstein J. Org. Chem. 2024, 20, 589–596, doi:10.3762/bjoc.20.51

• peptidyl transferase activity while the furanose group does not appear to be important for target inhibition [6][7]. In addition, hygromycin A contains a unique methylenedioxy group found on the aminocyclitol that is not required for ribosome interaction and in vitro inhibition [8]. Instead, it is

Possible bi-stable structures of pyrenebutanoic acid-linked protein molecules adsorbed on graphene: theoretical study

• Yasuhiro Oishi,
• Motoharu Kitatani and
• Koichi Kusakabe

Beilstein J. Org. Chem. 2024, 20, 570–577, doi:10.3762/bjoc.20.49

• (1.63 eV), than that of conformation 2, which is about 1.28 eV. The stabilization of conformation 1 partly comes from interaction between the succinimidyl ester part and graphene. There are other C–C single bonds in the alkyl chain, such as those shown by the dashed and dotted lines in Figure 1a

• the DFT calculation realized by the PWscf code of Quantum ESPRESSO [30][31][32], the DFT-D3 correlation [33] together with PBEsol functional [34] for the exchange-correlation functional described van der Waals interaction between graphene and pyrene fragment in PASE. Ultrasoft pseudopotentials [35

• ] with the energy cutoff of 35 (350) Ry for the expansion of wavefunction (charge density) described the electron-nuclear interaction. Using the 2 × 4 × 1 k-point mesh of Monkhorst–Pack [36], the Brillouin zone sampling was safely performed. Additional details of calculation conditions may be found in a

Entry to new spiroheterocycles via tandem Rh(II)-catalyzed O–H insertion/base-promoted cyclization involving diazoarylidene succinimides

• Alexander Yanovich,
• Anastasia Vepreva,
• Ksenia Malkova,
• Grigory Kantin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2024, 20, 561–569, doi:10.3762/bjoc.20.48

• of compound 4b has been confirmed by single crystal X-ray data. The next step was to investigate the possibility of obtaining six-membered oxygen-containing spiroheterocycles by interaction of DAS 1 with 2-(bromomethyl)benzyl alcohol (15) (Scheme 6). The synthesis was carried out under the conditions

Synthesis of photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2Н)-ones with a terminal phenanthroline group

• Vladimir P. Rybalkin,
• Sofiya Yu. Zmeeva,
• Lidiya L. Popova,
• Irina V. Dubonosova,
• Olga Yu. Karlutova,
• Oleg P. Demidov,
• Alexander D. Dubonosov and
• Vladimir A. Bren

Beilstein J. Org. Chem. 2024, 20, 552–560, doi:10.3762/bjoc.20.47

• change of the solutions from yellow to dark orange. Subsequent selective interaction with AcO− led to the restoration of the initial absorption and emission properties. Thus, the obtained compounds represent dual-mode “on–off–on” switches of optical and fluorescent properties under sequential exposure to

• the phenanthroline unit was also involved in a π–π-stacking interaction (blue plane–green plane in Figure 4), with the plane centroid–plane centroid distance being 3.6998(8) Å (plane shift 1.4919(17) Å, twist and fold angles 1.54° and 1.92°, respectively). Cation-induced transformations of the

• series method, compounds 2a–c formed the 2:1 complexes 4a–c with Fe2+ (Scheme 3 and Figure 7). It was found that selective interaction of the resulting in situ complex 4a with AcO− led to restoration of the initial absorption and emission properties [31][32]. Other tetra-n-butylammonium salts (TBAX, X

Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

• proximity, either by direct interaction or via a small intercalating molecule. Therefore, switchable molecular tweezers can be considered a prototype of a mechanical molecular device capable of allosteric regulation and dual control through switching and guest binding. While the primary application of

• distance of 21 Å between the two Cu(II) complexes results in an independent paramagnetic behavior. However, in the closed form, the metal centers are much closer to each other (4.03 Å) resulting in a weak antiferromagnetic coupling via through-space exchange interaction. This demonstrates the value of

• by the addition of zinc(II) which opens the tweezers, releasing the guest and leading to the disappearance of the photosensitizing properties of the system. In an extension of this work, discrete tetranuclear Pt complexes with Pt–Pt interaction were obtained by self-assembly between 21 and

Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

• Ruichen Lan,
• Brock Yager,
• Yoonsun Jee,
• Cynthia S. Day and
• Amanda C. Jones

Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43

• 23–27) [53], thus rates do not correlate with N–H acidity either (the least acidic urea is the most active). Interaction of gold(I) with the two functional group types (carbonyl versus sulfonamide) is predicted to differ in a key aspect. Lithiated carbanions alpha to carbonyl functional groups are O

• support the argument that faster reactions are associated with greater kinetic interaction with the carbonyl nucleophile. Sulfonamide hydroamination has also distinguished itself from urea and carbamate hydroamination in demonstrating productive reactivity with HOTf as a catalyst [31][58]. A few things

• -workers, it was found that in chlorination reactions, activation of alkenes is not driven by the electrophilicity of the reagent being attacked by an alkene, but instead depends on nucleophile assistance: the alkene becomes more nucleophilic upon interaction with the pendant attacking nucleophile [81]. In

(E,Z)-1,1,1,4,4,4-Hexafluorobut-2-enes: hydrofluoroolefins halogenation/dehydrohalogenation cascade to reach new fluorinated allene

• Nataliia V. Kirij,
• Andrey A. Filatov,
• Yurii L. Yagupolskii,
• Sheng Peng and
• Lee Sprague

Beilstein J. Org. Chem. 2024, 20, 452–459, doi:10.3762/bjoc.20.40

• oxirane [14]. A related study has demonstrated that (E)-butene 1a reacts with potassium persulfate to form 4,5-bistrifluoromethyl)-1,3,2-dioxathiolane 2,2-dioxide [15]. In 2021 Petrov published an article on the interaction of fluorinated olefins with fluorinated thioketones. In this publication it was

• continues to be relevant. One of the methods for the synthesis of allenes was based on the interaction of bromoolefins with organolithium compounds, followed by the elimination of lithium fluoride [29][30][31]. It was logical to assume that in our case a similar reaction of the Grignard reagent 12 with

Enhanced host–guest interaction between [10]cycloparaphenylene ([10]CPP) and [5]CPP by cationic charges

• Eiichi Kayahara,
• Yoshiyuki Mizuhata and
• Shigeru Yamago

Beilstein J. Org. Chem. 2024, 20, 436–444, doi:10.3762/bjoc.20.38

• suggested the partial electron transfer from [10]CPP to [5]CPP2+ in the complex, and this charge-transfer (CT) interaction is most likely the origin of the higher association constant of the dicationic complex than the neutral one. Keywords: charge-transfer; cycloparaphenylene; dication; host–guest

• photophysical and electrochemical analyses and DFT calculations. Therefore, this CT is most likely the origin of the increased Ka value. We also discuss the charged double-layer structure, as determined by X-ray crystallographic analysis. Results and Discussion The size-complementary interaction between CPP2

• -complementary interaction between [5]CPP2+ and [10]CPP. The same size selectivity was observed for the complex formation between neutral CPPs [31]. As the protons in the 1H NMR of [10]CPP2+ and neutral [5]CPP resonate at 4.72 and 7.84 ppm, respectively [21], the observed chemical shifts of the complex indicate

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

• interesting alternative to hydrogen bonding, which constitute an indispensable type of non-covalent interaction utilized in several catalytic approaches [81][82][83][84][85][86][87][88]. In 2008, Bolm introduced the use of perfluoroiodoalkanes as XB catalysts and the field gained widespread attention as an