Metal-free synthesis of biarenes via photoextrusion in di(tri)aryl phosphates

• Hisham Qrareya,
• Lorenzo Meazza,
• Stefano Protti and
• Maurizio Fagnoni

Beilstein J. Org. Chem. 2020, 16, 3008–3014, doi:10.3762/bjoc.16.250

• intermediates (triplet aryl cations [28][29] or aryl radicals [30][31]). As for the former case, the intermolecular formation of a biaryl arose from the photoheterolysis of an Ar–N bond (in arene diazonium salts or their derivatives [32][33]), of an Ar–Cl bond [34][35], of an Ar–O bond (in aryl phosphates [36

• ], aryl sulfonates [36], and in aryl trifluoroethyl sulfate [37], Scheme 1a) followed by the reaction of the thus formed aryl cation with an aromatic substrate. In an alternative approach, aryl radicals may be generated under photoredox catalysis conditions (mostly from arene diazonium salts or aryl

• iodides) [30][31] or by the direct photolysis of arylazo sulfones [38][39][40] and employed for the desired arylations. These reactions have the advantage of being applied to non-functionalized arenes but have the drawback to require a large excess of the nucleophilic reagent (the arene Ar–H) in up to 10

Chiral anion recognition using calix[4]arene-based ureido receptors in a 1,3-alternate conformation

• Tereza Horáčková,
• Jan Budka,
• Vaclav Eigner,
• Wen-Sheng Chung,
• Petra Cuřínová and
• Pavel Lhoták

Beilstein J. Org. Chem. 2020, 16, 2999–3007, doi:10.3762/bjoc.16.249

• of calix[4]arene immobilised in the 1,3-alternate conformation led to a system possessing a preorganised ureido cavity hemmed with chiral alkyl units in the near proximity. As shown by the 1H NMR titration experiments, these compounds can be used as receptors for chiral anions in DMSO-d6. The chiral

• highly sophisticated molecules, including anionic receptors [27][28][29][30][31][32][33][34][35][36][37][38][39]. During our ongoing research on anion complexation, we have reported various calix[4]arene receptors based mainly on amide, urea, or thiourea groups [40][41], some of which are available in

• exemplified by our previously published receptors C1 based on a calix[4]arene moiety or by C2 using thiacalix[4]arene as the core scaffold [44][45]. Moreover, the introduction of the tert-butyl groups into the 1,3-alternate conformer should lead to the overall increase rigidity of the molecule, possibly

Construction of pillar[4]arene[1]quinone–1,10-dibromodecane pseudorotaxanes in solution and in the solid state

• Xinru Sheng,
• Errui Li and
• Feihe Huang

Beilstein J. Org. Chem. 2020, 16, 2954–2959, doi:10.3762/bjoc.16.245

• 450001, P. R. China 10.3762/bjoc.16.245 Abstract We report novel pseudorotaxanes based on the complexation between pillar[4]arene[1]quinone and 1,10-dibromodecane. The complexation is found to have a 1:1 host–guest complexation stoichiometry in chloroform but a 2:1 host–guest complexation stoichiometry

• in the solid state. From single crystal X-ray diffraction, the linear guest molecules thread into cyclic pillar[4]arene[1]quinone host molecules in the solid state, stabilized by CH∙∙∙π interactions and hydrogen bonds. The bromine atoms at the periphery of the guest molecule provide convenience for

• the further capping of the pseudorotaxanes to construct rotaxanes. Keywords: host–guest chemistry; pillar[4]arene[1]quinones; pillararenes; pseudorotaxanes; supramolecular chemistry; Introduction Relying on the research of basic science, supramolecular chemistry has become an important mean for

Water-soluble host–guest complexes between fullerenes and a sugar-functionalized tribenzotriquinacene assembling to microspheres

• Si-Yuan Liu,
• Xin-Rui Wang,
• Man-Ping Li,
• Wen-Rong Xu and
• Dietmar Kuck

Beilstein J. Org. Chem. 2020, 16, 2551–2561, doi:10.3762/bjoc.16.207

• offer various possibilities for functionalization. Therefore, TBTQ derivatives have attracted much attention since the first synthesis reported in 1984 [21][22][23][24]. The arene periphery of the TBTQ framework bears a great and variable potential for the efficient expansion of the small and relatively

• , the 1H NMR spectrum of TBTQ-(OAcG)6 exhibits two singlet resonances at δ = 8.62 and δ = 8.58 ppm, each of which indicates three equivalent protons of the six triazole rings. Likewise, two singlets at δ = 7.33 and δ = 7.30 ppm are due to two sets of three equivalent arene protons of the TBTQ core [40

• ten-fold sugar-functionalized pillar[5]arene [43]. Temperature-dependent 1H NMR spectroscopy of TBTQ-(OAcG)6 in DMSO-d6 was carried out in the range of 20–70 °C and revealed a slight decrease of the splitting of the aromatic proton resonances with increasing temperature, but no coalescence. While most

NMR Spectroscopy of supramolecular chemistry on protein surfaces

• Peter Bayer,
• Anja Matena and
• Christine Beuck

Beilstein J. Org. Chem. 2020, 16, 2505–2522, doi:10.3762/bjoc.16.203

• stabilization of the ligand by additional crystal contacts to neighboring proteins [6][18][20][21][22][26][27][28]. For some supramolecular ligands, like sulfonatocalix[8]arene or phosphonatocalix[6]arene, the tendency to bridge two protein interfaces that do not usually interact in solution goes so far that

• ]arene has been titrated to trimethyl-lysine (KMe3), which yields the largest shifts and most severe line broadening for the methyl protons and Hε resonances, indicating that these atoms are located inside the aromatic bowl of the calixarene [29]. The binding affinities of cucurbituril ligands for

• sulfonato-calix[4]arene binding to Ralstonia solanacearum lectin that was chemically dimethylated on three lysine residues and the N-terminus was studied by 15N-HSQC titrations [50][51]. Both ligands prefer binding to methylated lysines whereby the binding affinity (for the free amino acids) increases with

Palladium nanoparticles supported on chitin-based nanomaterials as heterogeneous catalysts for the Heck coupling reaction

• Tony Jin,
• Malickah Hicks,
• Davis Kurdyla,
• Sabahudin Hrapovic,
• Edmond Lam and
• Audrey Moores

Beilstein J. Org. Chem. 2020, 16, 2477–2483, doi:10.3762/bjoc.16.201

• ChNC or the ChsNC during catalyst fabrication. The lack of metallic Pd peaks present in XRD is indicative of extreme broadening of the reflections of very small Pd NPs within the packets found. Heck coupling is a prominent reaction for arene alkenylation, as the production of stilbene derivatives is

When metal-catalyzed C–H functionalization meets visible-light photocatalysis

• Lucas Guillemard and
• Joanna Wencel-Delord

Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147

• alkylation of arenes. The ruthenium-catalyzed meta-selective C–H functionalization through arene σ-activation was already well established yet limited by harsh reaction conditions and elevated reaction temperatures. Both research groups hence hypothesized that the Ru-metallacyclic intermediate, generated via

Clickable azide-functionalized bromoarylaldehydes – synthesis and photophysical characterization

• Dominik Göbel,
• Marius Friedrich,
• Enno Lork and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2020, 16, 1683–1692, doi:10.3762/bjoc.16.139

• of the alkyl bridge between the arene and the azide are underway in our laboratories. Top: literature examples of organic compounds showing RTP in the crystalline state (a) and in solution (b). Bottom: azide-linked derivatives presented in this work. a) Normalized UV–vis absorption spectra of 3 (blue

Heterogeneous photocatalysis in flow chemical reactors

• Christopher G. Thomson,
• Ai-Lan Lee and
• Filipe Vilela

Beilstein J. Org. Chem. 2020, 16, 1495–1549, doi:10.3762/bjoc.16.125

• -workers to be an effective, stable, and recyclable HPCat for a large scope of arene and heteroarene functionalisation reactions, traditionally performed with transition metal complexes (Scheme 2) [128]. The group were able to bifunctionalise N-phenylpyrrole with a variety of functional groups at room

Photocatalysis with organic dyes: facile access to reactive intermediates for synthesis

• Stephanie G. E. Amos,
• Marion Garreau,
• Luca Buzzetti and
• Jerome Waser

Beilstein J. Org. Chem. 2020, 16, 1163–1187, doi:10.3762/bjoc.16.103

• the C(sp3) radical, which is intercepted by an organometallic intermediate, obtained by the oxidative addition of a nickel catalyst to the (hetero)aryl bromide 5.2. The desired (hetero)arene product 5.3 is obtained after the reductive elimination of the nickel complex. In this method, the reduced

• /desulfonylation of the arylsulfonyl chlorides 14.1 (Scheme 14) [85][86]. The ensuing aryl radical is trapped by an aryl isonitrile 14.2, affording the bisarylation product 14.3. The direct organophotocatalytic activation of the C–H bond of an arene represents an atom-economical and attractive strategy for the

• cations and radical anions) Recently, the exploitation of alkenyl and aryl radical ions has emerged as a platform for the functionalization of small molecules. They appear as attractive intermediates for a direct alkene difunctionalization or arene C–H functionalization. In particular, radical cations are

Direct borylation of terrylene and quaterrylene

• Haruka Kano,
• Keiji Uehara,
• Kyohei Matsuo,
• Hironobu Hayashi,
• Hiroko Yamada and
• Naoki Aratani

Beilstein J. Org. Chem. 2020, 16, 621–627, doi:10.3762/bjoc.16.58

• )-catalyzed direct C–H borylation [22][23][24][25] gives 2,5,8,11-tetraborylated perylene [26]. The regioselectivity of the perylene borylation is determined by the steric factors rather than by the electron distribution in the arene and this regioselectivity complements that of electrophilic substitutions

Room-temperature Pd/Ag direct arylation enabled by a radical pathway

• Amy L. Mayhugh and
• Christine K. Luscombe

Beilstein J. Org. Chem. 2020, 16, 384–390, doi:10.3762/bjoc.16.36

• published results were replicated, then radical traps were introduced. In these cases, BHT completely eliminated the formation of product 12 and partially inhibited the conversion to product 13. In both cases the arene–BHT adduct was observed by GC–MS as shown in the inset of Scheme 4. While more extensive

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

• catalyst for the oxidation of the arenes. The reaction is initiated by the oxidation of 100 through the excited photocatalyst to generate the arene radical cation 102. Here, P(OEt)3 acts as a nucleophile, capturing the radical cation of 102 and generating 103. Concomitant to the reduction of the Co(III

• ) catalyst to Co(II), the arene intermediate 104 is generated via SET, and after deprotonation of 104, the phosphonylated intermediate 105 is formed. The additive CH3COONH4 causes nucleophile displacement, converting the arylphosphonium salt into the phosphonylated product 101. A range of products was

• , the reaction is initiate with the excitation of the photocatalyst, which further oxidizes the aniline derivative 106 to generate the arene radical cation 108. Then, the intermediate 109 is formed by deprotonation, which, upon reaction with a nitrate radical, gives the desired product 107. Aryl C–H

Extension of the 5-alkynyluridine side chain via C–C-bond formation in modified organometallic nucleosides using the Nicholas reaction

• Renata Kaczmarek,
• Dariusz Korczyński,
• James R. Green and
• Roman Dembinski

Beilstein J. Org. Chem. 2020, 16, 1–8, doi:10.3762/bjoc.16.1

• confirmed that the Nicholas reaction can be carried out in a nucleoside presence, leading to a divergent synthesis of novel metallo-nucleosides enriched with alkene, arene, arylketo, and heterocyclic functions, in the deoxy and ribo series. Keywords: alkynes; 5-alkynyluridines; C–C-bond formation; dicobalt

• , has been introduced into the repertoire of nucleosides modifications. The reaction of dicobalt hexacarbonyl propargylic alcohol uridine derivatives has been validated with diverse C-nucleophiles. By this means, alkene, arene, arylketo, and heterocyclic functions can be introduced onto metallo

Acid-catalyzed rearrangements in arenes: interconversions in the quaterphenyl series

• Sarah L. Skraba-Joiner,
• Carter J. Holt and
• Richard P. Johnson

Beilstein J. Org. Chem. 2019, 15, 2655–2663, doi:10.3762/bjoc.15.258

• ][8]. Every student of organic chemistry is taught the importance of arenium ions in the classic two step SEAr mechanism for electrophilic aromatic substitution. Addition of an electrophile to an arene leads to a bound species, sometimes called a σ-complex, which then loses a proton at the site of

• substitution to yield the product [9]. Of course challenges to this simple mechanism exist [10][11][12][13][14][15], including the recent proposal of a one-step process [16]. Reaction dynamics of electrophile–arene π complexes may also play a role in site selectivity [17]. It is less commonly known that

• favoring the 2,2'-isomer 9 (97%) at equilibrium [26]. Aryl shifts occur readily in naphthalene, with beta-substitution favored at equilibrium. Skeletal rearrangements of fused arene rings are also possible and can proceed through several mechanisms. The first example was reported by Dansi and Salvioni in

Anion-driven encapsulation of cationic guests inside pyridine[4]arene dimers

• Anniina Kiesilä,
• Jani O. Moilanen,
• Anneli Kruve,
• Christoph A. Schalley,
• Perdita Barran and
• Elina Kalenius

Beilstein J. Org. Chem. 2019, 15, 2486–2492, doi:10.3762/bjoc.15.241

• to the electron-poor nature of the pyridine ring. Herein, we demonstrate the encapsulation of Me4N+ cations inside a dimeric hydrogen-bonded pyridine[4]arene capsule, which contradicts with earlier assumptions. The complexation of a cationic guest inside the pyridine[4]arene dimer has been detected

• in pyridine[4]arene is an anion-driven process. Keywords: cation binding; DFT calculations; ion mobility mass spectrometry; macrocycles; pyridinearenes; resorcinarenes; Introduction Resorcinarenes and their derivatives are known for the molecular recognition properties of their self-assembled

• -rim alkyl chains [11]. A PF6− anion was bound to the lower rim of the pyridine[4]arene dimer via CH–anion and CH–F interactions, while the neutral guest was hosted inside the dimer. Calculated electrostatic potential (ESP) surfaces revealed that the cavity does not possess any significant partial

Thermal stability of N-heterocycle-stabilized iodanes – a systematic investigation

• Andreas Boelke,
• Yulia A. Vlasenko,
• Mekhman S. Yusubov,
• Boris J. Nachtsheim and
• Pavel S. Postnikov

Beilstein J. Org. Chem. 2019, 15, 2311–2318, doi:10.3762/bjoc.15.223

• reagents of choice as electrophilic aryl group transfer reagents. Thermal decomposition studies indicate that they should be potent electrophilic arene donors. General structure of aryl-λ3-iodanes. Tpeak and ΔHdec-values for a range of N- and O-substituted iodanes. TGA/DSC curves of (a) benziodoxolone 1

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

• electron-rich unsaturated bonds (arene, alkene, or alkyne), or a substrate having a nucleophilic and labile bond (e.g., C−Si, C−Sn, and C−B), while the electrophile is the fluorination reagent (Scheme 1b). As shown in Scheme 1d, many nucleophilic and electrophilic fluorination reagents have been developed

1,2,3-Triazolium macrocycles in supramolecular chemistry

• Mastaneh Safarnejad Shad,
• Pulikkal Veettil Santhini and
• Wim Dehaen

Beilstein J. Org. Chem. 2019, 15, 2142–2155, doi:10.3762/bjoc.15.211

• helped to increase the ability of complexation of 12 with iodide [56]. 2.7. Functional molecular crystal and materials Combining anion–arene interactions and controlling the electron-transfer or charge-transfer process concerning an anionic guest by using a cyclophane is uncommon [57] but can be realized

Multiple threading of a triple-calix[6]arene host

• Veronica Iuliano,
• Roberta Ciao,
• Emanuele Vignola,
• Carmen Talotta,
• Patrizia Iannece,
• Margherita De Rosa,
• Annunziata Soriente,
• Carmine Gaeta and
• Placido Neri

Beilstein J. Org. Chem. 2019, 15, 2092–2104, doi:10.3762/bjoc.15.207

• Fisciano (Salerno), Italy 10.3762/bjoc.15.207 Abstract The synthesis of the triple-calix[6]arene derivative 6 in which three calix[6]arene macrocycles are linked to a central 1,3,5-trimethylbenzene moiety is reported. Derivative 6 is able to give multiple-threading processes in the presence of

• architectures. Historically, the most common components were dialkylammonium ions, as axles, and crown ethers, cyclodextrins, or cucurbiturils, as wheels [1]. With respect to the possible types of wheels, more recently, we have introduced the through-the-annulus threading of simple calix[6]arene hosts with

• -catenanes [25]. On the basis of these results, we were also able to assemble high-order architectures by double-threading of bis-calix[6]arene hosts with ammonium axles [27]. In particular, handcuff (pseudo)rotaxane architectures (e.g., 32+ in Figure 2) [27] were obtained by double-threading of bis-calix[6

Fluorinated azobenzenes as supramolecular halogen-bonding building blocks

• Esther Nieland,
• Oliver Weingart and
• Bernd M. Schmidt

Beilstein J. Org. Chem. 2019, 15, 2013–2019, doi:10.3762/bjoc.15.197

• in the field of crystal engineering [1]. Only few supramolecular capsules were reported so far [29], including the resorcin[4]arene capsules of Diederich and co-workers [21][23], triangular macrocycles assembled by self-complemented halogen bonding [20] and halogen bond templated, polyfluorinated

Attempted synthesis of a meta-metalated calix[4]arene

• Christopher D. Jurisch and
• Gareth E. Arnott

Beilstein J. Org. Chem. 2019, 15, 1996–2002, doi:10.3762/bjoc.15.195

• Christopher D. Jurisch Gareth E. Arnott Department of Chemistry and Polymer Science, Stellenbosch University, Private Bag X1, Matieland, 7602, South Africa 10.3762/bjoc.15.195 Abstract An evidence for the formation of a rare meta-metalated inherently chiral calix[4]arene is described. Our

• whose chiral nature is a result of selective substitution on the calix[4]arene by various functional groups [9]. In particular, we have focused on the less-studied meta-substituted derivatives [10] whose inherent chirality is more commonly introduced by a suitable directing group [11][12][13][14][15

• this using a pyridyl sulfoxide directing group and palladium as the metal, but in this case the palladium caused a double C–H activation and formed an impressive bridge to the adjacent calix[4]arene aromatic ring [14]. The question for us was whether this bridge formation was a general principle or

Synthesis and anion binding properties of phthalimide-containing corona[6]arenes

• Meng-Di Gu,
• Yao Lu and
• Mei-Xiang Wang

Beilstein J. Org. Chem. 2019, 15, 1976–1983, doi:10.3762/bjoc.15.193

• Meng-Di Gu Yao Lu Mei-Xiang Wang MOE Key Laboratory of Bioorganic Phosphorous Chemistry and Chemical Biology, Department of Chemistry, Tsinghua University, Beijing 100084, China 10.3762/bjoc.15.193 Abstract Functionalized O6-corona[3]arene[3]tetrazines were synthesized efficiently and

• adopt the conformation in which three phthalimide units are cis,trans-orientated. Acting as electron-deficient macrocyclic hosts, the synthesized O6-corona[3]arene[3]tetrazines self-regulated conformational structures to complex anions in the gas phase and in the solid state owing to the anion–π

• noncovalent interactions between anions and the tetrazine rings. Keywords: anion–π interactions; coronarenes; host–guest complexation; N-functionalized phthalimides; O6-corona[3]arene[3]tetrazines; Introduction Synthetic macrocycles [1][2] are always attractive and important because they are unique

Complexation of chiral amines by resorcin[4]arene sulfonic acids in polar media – circular dichroism and diffusion studies of chirality transfer and solvent dependence

• Bartosz Setner and
• Agnieszka Szumna

Beilstein J. Org. Chem. 2019, 15, 1913–1924, doi:10.3762/bjoc.15.187

• chemistry. In the present study we demonstrate that resorcin[4]arene sulfonic acid (RSA) interacts with chiral amines (amino acid derivatives and aminocavitands) to form inclusion complexes and capsules based on electrostatic interactions. The complexes were characterized by circular dichroism and DOSY NMR

• disintegrative for these complexes. This result is quite non-intuitive and worth attention in the context of formation of supramolecular complexes in polar environment, for which DMSO is most often a first-choice solvent. Keywords: cavitands; chirality; macrocycle; resorcin[4]arene; self-assembly

• cyclodextrines, which, when unmodified, interact with a wide range of hydrophobic guests albeit with low general selectivity and enantioselectivity in particular [6]. In this paper we present a group of synthetic macrocyclic compounds – resorcin[4]arene sulfonic acids (RSAs) and analyze their interactions with

Halide metathesis in overdrive: mechanochemical synthesis of a heterometallic group 1 allyl complex

• Ross F. Koby,
• Nicholas R. Rightmire,
• Nathan D. Schley,
• Timothy P. Hanusa and
• William W. Brennessel

Beilstein J. Org. Chem. 2019, 15, 1856–1863, doi:10.3762/bjoc.15.181

• centroid distance is 2.99 Å, which is typical for K+…(arene) cation–π interactions [22][23]. The enthalpy of binding (∆H°) of an isolated K…(benzene or toluene) unit is almost 80 kJ mol−1 (see calculated value in Table 1, entry 5); the energy is reduced by about 40% when the ring is bound to the neutral