1,4,6,10-Tetraazaadamantanes (TAADs) with N-amino groups: synthesis and formation of boron chelates and host–guest complexes

• Artem N. Semakin,
• Ivan S. Golovanov,
• Yulia V. Nelyubina and
• Alexey Yu. Sukhorukov

Beilstein J. Org. Chem. 2022, 18, 1424–1434, doi:10.3762/bjoc.18.148

• ) Host–guest motif in the X-ray structure of 4c·HCl·3.5MeOH (guest molecule is shown in “spacefill” representation). (e) Hirshfeld surface of the TAAD cation in 4a·HCl·H2O·MeOH. (e) Hirshfeld surface of the TAAD cation in 4c·HCl·3.5MeOH. (a) Dynamic processes in TAADs 4 and complexation with ROH. (b

• subsequent complexation with phenylboronic acid. Quaternization of TAADs 4c, 4e, 6a, and 8a followed by deprotection of N-Boc groups. DFT calculated binding energies for the guest–host complexes ROH@4. Supporting Information Supporting Information File 277: Experimental procedures, NMR spectra, infrared

Cyclodextrin-based Schiff base pro-fragrances: Synthesis and release studies

• Attila Palágyi,
• Jindřich Jindřich,
• Juraj Dian and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2022, 18, 1346–1354, doi:10.3762/bjoc.18.140

• various organic molecules have been described so far. It was proved that the complexation of volatile organic compounds, such as aldehydes, into the CD’s cavity reduces the volatility and increases the solubility and bioavailability of these compounds [5][6][7][8][9][10][11][12][13][14]. The release of

Polymer and small molecule mechanochemistry: closer than ever

• José G. Hernández

Beilstein J. Org. Chem. 2022, 18, 1225–1235, doi:10.3762/bjoc.18.128

• transduce mechanical energy to the mechanophores. Typically, polymers were the force transmission medium of choice, but in a recent study, Potrzebowski, Szumna, and co-workers have shown that molecular capsules can behave as stress-sensitive units [65]. The authors demonstrated the effective complexation of

• the covalent capsule 5 (made from resorcinarene caps connected by four dihydrazone units of ʟ-cysteine) with C60 and C70 fullerenes upon neat ball milling in a planetary ball mill (Figure 6). The mechanochemical complexation is remarkable since the porous capsule does not possess large enough openings

• . Mechanochemical solid-state complexation of organic capsule 5 with fullerenes C70 in a planetary ball mill. Figure 6 was adapted from [65], H. Jędrzejewska et al., “Porous Molecular Capsules as Non- Polymeric Transducers of Mechanical Forces to Mechanophores”, Chem. Eur. J., with permission from John Wiley and

Heterogeneous metallaphotoredox catalysis in a continuous-flow packed-bed reactor

• Wei-Hsin Hsu,
• Susanne Reischauer,
• Peter H. Seeberger,
• Bartholomäus Pieber and
• Dario Cambié

Beilstein J. Org. Chem. 2022, 18, 1123–1130, doi:10.3762/bjoc.18.115

• long-run experiment, after seven days of continuous reaction 0.42 mg of nickel (25% of the 1.66 mg initially complexed, see Figure 5) leached into the reaction solution. However, performing another round of complexation with NiCl2∙glyme did not restore the original activity of the catalyst in the

Scope of tetrazolo[1,5-a]quinoxalines in CuAAC reactions for the synthesis of triazoloquinoxalines, imidazoloquinoxalines, and rhenium complexes thereof

• Laura Holzhauer,
• Chloé Liagre,
• Olaf Fuhr,
• Nicole Jung and
• Stefan Bräse

Beilstein J. Org. Chem. 2022, 18, 1088–1099, doi:10.3762/bjoc.18.111

• reactions and denitrogenative annulation according to Roy et al. [11]. Copper-catalyzed azide–alkyne cycloadditions are initiated via the (dual) complexation of the alkyne, whereas denitrogenative annulation on 1,2,3,4-tetrazoles is assumed to start via complexation of the open-form azide 18 (see Scheme 4

• confirmed via single crystal X-ray crystallography. Several other byproducts, such as the bistriazolo product were isolated (see Supporting Information File 1). The obtained triazoloquinoxaline and TIQ products are promising ligands for complexation with different metals. The formation of organometallic

• especially used as CO2 reduction catalysts [38][39][40] and noninvasive imaging probes [12][41]; examples for the application in organic light-emitting diodes [35] and as photoactive CO-releasing molecule [42][43] have been reported as well. For the complexation experiments, compounds with three different

Post-synthesis from Lewis acid–base interaction: an alternative way to generate light and harvest triplet excitons

• Hengjia Liu and
• Guohua Xie

Beilstein J. Org. Chem. 2022, 18, 825–836, doi:10.3762/bjoc.18.83

• –base interaction mechanisms Chemical essence of Lewis acid–base interaction All the above discussed fluorescent materials share the common characteristics of Lewis basicity. Therefore, the changes in band gaps and colors of the donor materials is essentially attributed to a Lewis acid–base complexation

A trustworthy mechanochemical route to isocyanides

• Francesco Basoccu,
• Federico Cuccu,
• Federico Casti,
• Rita Mocci,
• Claudia Fattuoni and
• Andrea Porcheddu

Beilstein J. Org. Chem. 2022, 18, 732–737, doi:10.3762/bjoc.18.73

• , they are often used in heterocycles formation [8][9], multicomponent strategies [10][11], polymers production [12][13], and metal complexation [14][15]. The molecular structure is composed of an N–C planar triple bond where the nitrogen atom assumes a positive charge due to the fourth bond with a

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• Prodip Howlader Michael Schmittel Center of Micro- and Nanochemistry and (Bio)Technology, Universität Siegen, Organische Chemie I, Adolf-Reichwein-Str. 2, D-57068 Siegen, Germany 10.3762/bjoc.18.62 Abstract Supramolecular catalysis is reviewed with an eye on heteroleptic aggregates/complexation

• chemistry and information science. Keywords: heteroleptic complexation; information science; supramolecular catalysis; switching catalysis; systems chemistry; Introduction Supramolecular catalysis [1][2][3] for most chemists is associated with a catalytically active capsule providing either activating

• Switchable catalysis due to reversible assembly/disassembly Toggling between intra- and intermolecular complexation in nanoswitches Review Catalysis using heteroleptic discrete supramolecular architectures In its early years, supramolecular chemistry mainly focused on host–guest interactions, primarily on

Synthesis of a new water-soluble hexacarboxylated tribenzotriquinacene derivative and its competitive host–guest interaction for drug delivery

• Man-Ping Li,
• Nan Yang and
• Wen-Rong Xu

Beilstein J. Org. Chem. 2022, 18, 539–548, doi:10.3762/bjoc.18.56

• synthesized compounds were fully characterized by 1H and 13C NMR spectroscopy and mass spectrometry (see Supporting Information File 1) and the data were found to be consistent with the proposed structures. Host–guest complexation of TBTQ-CB6 with dimethyl viologen (MV). The host–guest complexation between

• -rich cavity of TBTQ-CB6 [32]. In addition, the proton resonances became broadened caused by the complexation dynamics, indicating the successful host–guest complexation between TBTQ-CB6 and MV. Subsequently, the association stoichiometry of the complex was studied by the Job plot method using

• association constant was determined to be Ka = (7.67 ± 0.34) × 104 M−1 by nonlinear curve fitting [33] (Figure 1d). Host–guest complexation of TBTQ-CB6 with doxorubicin (DOX). The host–guest complexation between TBTQ-CB6 and DOX was studied by methods similar to those used for TBTQ-CB6 and MV. The 1H NMR

Bioinspired tetraamino-bisthiourea chiral macrocycles in catalyzing decarboxylative Mannich reactions

• Hao Guo,
• Yu-Fei Ao,
• De-Xian Wang and
• Qi-Qiang Wang

Beilstein J. Org. Chem. 2022, 18, 486–496, doi:10.3762/bjoc.18.51

• -derived bisisothiocyanate fragments 5e,f afforded the desired hetero-combination macrocycles M7–M12 without additional difficulties. It should be noted that the incorporation of CF3 groups on the aryl moieties was to increase the acidity of thiourea so as to provide better hydrogen-bonding complexation

Tetraphenylethylene-embedded pillar[5]arene-based orthogonal self-assembly for efficient photocatalysis in water

• Zhihang Bai,
• Krishnasamy Velmurugan,
• Xueqi Tian,
• Minzan Zuo,
• Kaiya Wang and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2022, 18, 429–437, doi:10.3762/bjoc.18.45

• were significantly increased with respect to G concentrations and no considerable changes were observed when further increasing the G concentration (1.2 equiv). The above results corroborated that the free rotation of m-TPEWP5 rings was arrested during the complexation with G, thus further leads to the

Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions

• Surendran Amrutha,
• Sankaran Radhika and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 262–285, doi:10.3762/bjoc.18.31

• clearly shown that the complex of Co-N-heterocyclic ligand exhibits a higher activity. Sonogashira cross-coupling reactions were also reported by making use of a heterogeneous, efficient and green cobalt catalyst obtained through complexation of cobalt with methyl salicylate-functionalized chitosan fibres

Synthesis of a novel aminobenzene-containing hemicucurbituril and its fluorescence spectral properties with ions

• Qingkai Zeng,
• Qiumeng Long,
• Jihong Lu,
• Li Wang,
• Yuting You,
• Xiaoting Yuan,
• Qianjun Zhang,
• Qingmei Ge,
• Hang Cong and
• Mao Liu

Beilstein J. Org. Chem. 2021, 17, 2840–2847, doi:10.3762/bjoc.17.195

• constants for 1:1 complexation between the host 4 and the guest cations were calculated by Equation 1 [47], where Ka is the association constant of the host–guest interaction, while ΔI is the change in the fluorescence intensity of the host upon gradual addition of the guest, and Δa refers to the different

Biological properties and conformational studies of amphiphilic Pd(II) and Ni(II) complexes bearing functionalized aroylaminocarbo-N-thioylpyrrolinate units

• Samet Poyraz,
• Samet Belveren,
• Sabriye Aydınoğlu,
• Mahmut Ulger,
• Abel de Cózar,
• Maria de Gracia Retamosa,
• Jose M. Sansano and
• H. Ali Döndaş

Beilstein J. Org. Chem. 2021, 17, 2812–2821, doi:10.3762/bjoc.17.192

• complexation. NH (amide) protons of the ligands located at 8.30–7.65 ppm were not detected in the metallic structure spectra. Signals in the ranges of 5.84–5.64 and 4.40–4.17 ppm, corresponding to H5 and H6 protons, respectively, were shifted to 5.44 (H5) and 4.19 (H6) ppm for L1-Ni, and to 5.56–5.48 and 4.29

Synthetic strategies toward 1,3-oxathiolane nucleoside analogues

• Umesh P. Aher,
• Dhananjai Srivastava,
• Girij P. Singh and
• Jayashree B. S

Beilstein J. Org. Chem. 2021, 17, 2680–2715, doi:10.3762/bjoc.17.182

• stereoselective N-glycosylation. We hypothesize that because of the Lewis acid character, ZrCl4 could most likely form a precomplex with the sulfur atom of the oxathiolane ring, as in IV. The presence of the chiral ʟ-menthyl ester auxiliary function assists the complexation with ZrCl4 in a specific orientation

α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions

• Scott Benz and
• Andrew S. Murkin

Beilstein J. Org. Chem. 2021, 17, 2570–2584, doi:10.3762/bjoc.17.172

• with diverse biological activities [17]. The key step first involved the rhodium carbenoid-mediated OH insertion/Claisen rearrangement following complexation of diazoester 56 and allylic alcohol 57 to produce intermediate 58 (Figure 13). Addition of BF3·OEt2 to the reaction mixture then catalyzed the α

Targeting active site residues and structural anchoring positions in terpene synthases

• Anwei Hou and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2021, 17, 2441–2449, doi:10.3762/bjoc.17.161

• activity, while for the wildtype no GGPP conversion is observed. These findings will assist in future protein engineering for improved activity and functional switches in other microbial terpene synthases. Highly conserved residues in the active site of SdS for Mg2+ complexation, substrate recognition and

Halides as versatile anions in asymmetric anion-binding organocatalysis

• Lukas Schifferer,
• Martin Stinglhamer,
• Kirandeep Kaur and
• Olga García Macheño

Beilstein J. Org. Chem. 2021, 17, 2270–2286, doi:10.3762/bjoc.17.145

• enantioselectivity, but the catalyst itself accommodates the anion by adopting a helical conformation upon complexation (Scheme 18a) [84][85][86]. Initial studies proved these systems highly effective for the enantioselective Reissert reaction of quinolines with silyl ketene acetals [22], which could be later

Constrained thermoresponsive polymers – new insights into fundamentals and applications

• Patricia Flemming,
• Alexander S. Münch,
• Andreas Fery and
• Petra Uhlmann

Beilstein J. Org. Chem. 2021, 17, 2123–2163, doi:10.3762/bjoc.17.138

• irradiation as well as by host molecule (α-cyclodextrin) complexation [278]. Due to the high number of proton acceptor/donor sites, ureido-modified copolymers such as poly(allylamine-co-allylurea) are also becoming more and more important. The critical phase transition temperature can often be finely tuned

Development of N-F fluorinating agents and their fluorinations: Historical perspective

• Teruo Umemoto,
• Yuhao Yang and
• Gerald B. Hammond

Beilstein J. Org. Chem. 2021, 17, 1752–1813, doi:10.3762/bjoc.17.123

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

• Joseane A. Mendes,
• Paulo R. R. Costa,
• Miguel Yus,
• Francisco Foubelo and
• Camilla D. Buarque

Beilstein J. Org. Chem. 2021, 17, 1096–1140, doi:10.3762/bjoc.17.86

• ) to promote the complexation with the Grignard reagent. Products 147 and 149 were obtained in excellent yields and high diastereoselectivity and when 4-methylmorpholine (NMM) was used as additive, the heterocycle 151 was obtained in one pot addition–cyclization–deprotection of imine 150 (Scheme 40

Recent advances in palladium-catalysed asymmetric 1,4–additions of arylboronic acids to conjugated enones and chromones

• Jan Bartáček,
• Jan Svoboda,
• Martin Kocúrik,
• Jaroslav Pochobradský,
• Alexander Čegan,
• Miloš Sedlák and
• Jiří Váňa

Beilstein J. Org. Chem. 2021, 17, 1048–1085, doi:10.3762/bjoc.17.84

• . At first, they tested in situ-generated complexes of L14 and Pd(TFA)2 in methanol or acetone, but the reduction to catalytically inactive Pd(0) occurred faster. The reoxidation by Cu(BF4)2·6H2O led to the loss of enantioselectivity presumably because of the complexation of the bisoxazoline by Cu(II

Synthetic accesses to biguanide compounds

• Oleksandr Grytsai,
• Cyril Ronco and
• Rachid Benhida

Beilstein J. Org. Chem. 2021, 17, 1001–1040, doi:10.3762/bjoc.17.82

• chemical function, which has attracted much attention a century ago and is showing resurgent interest in recent years after a long period of dormancy. This class of compounds has found broad applications such as reaction catalysts, organic strong bases, ligands for metal complexation, or versatile starting

• ], superbases [6], and as ligands for metal complexation [7]. In organic synthesis, biguanides are precursors to several heterocycles [1] such as 1,3,5-triazines, pyrimidines, boron heterocycles, and benzo[f]quinazolines. The application of biguanides as catalysts has been reported mostly for the

• structures to handle: their hydrogen-bonding and complexation properties complicate their isolation and purification, and the numerous tautomeric forms and partially exchangeable protons render the analysis sometimes tricky. Mostly, biguanides suffer from an evident lack of knowledge and efficient procedures

Synthesis of 10-O-aryl-substituted berberine derivatives by Chan–Evans–Lam coupling and investigation of their DNA-binding properties

• Peter Jonas Wickhorst,
• Mathilda Blachnik,
• Denisa Lagumdzija and
• Heiko Ihmels

Beilstein J. Org. Chem. 2021, 17, 991–1000, doi:10.3762/bjoc.17.81

• DNA (Kb = 3–5 × 104 M−1) and exhibited a fluorescence light-up effect upon complexation to both DNA forms, with slightly higher intensity in the presence of the quadruplex DNA. Furthermore, the CD- and LD-spectroscopic studies revealed that the title compounds intercalate into ct DNA and bind to G4

• , it has been found that berberine (1a) exhibits a selective cytotoxicity against cancer cells [12][13], which is mainly based on its DNA-binding properties [14]. Since the complexation with DNA leads to significant changes of the fluorescent quantum yields of the bound berberine, it can also be used

• between DNA base pairs and the isoquinolinium unit pointing into the groove. This model is further supported by the relatively low fluorescence quantum yields of all ligands upon complexation to duplex DNA because in this structure the aryl substituent still has some conformational flexibility in the

Enhanced target cell specificity and uptake of lipid nanoparticles using RNA aptamers and peptides

• Roslyn M. Ray,
• Anders Højgaard Hansen,
• Maria Taskova,
• Bernhard Jandl,
• Jonas Hansen,
• Citra Soemardy,
• Kevin V. Morris and
• Kira Astakhova

Beilstein J. Org. Chem. 2021, 17, 891–907, doi:10.3762/bjoc.17.75

• average sizes of 57.3 nm and 91.9 nm, respectively, as well as a more negative ZP (−11 mV and −9.4 mV, respectively, Table 2). These ZP values indicate that complexation leads from a neutral to anionic LNP product [39], a property that typically confers with low to no cytotoxicity in vivo [40]. Further

• complexation with cluster of differentiation 4 (CD4) and CCR5 or C-X-C motif chemokine receptor 4 (CXCR4) host cell surface receptors [35]. As such, gp160 expression on the host cell surface receptor may not be as adept at facilitating cell entry via receptor-mediated endocytosis. Although in 2009, Zhou et al