Fluorine-containing substituents: metabolism of the α,α-difluoroethyl thioether motif

• Andrea Rodil,
• Alexandra M. Z. Slawin,
• Nawaf Al-Maharik,
• Ren Tomita and
• David O’Hagan

Beilstein J. Org. Chem. 2019, 15, 1441–1447, doi:10.3762/bjoc.15.144

• significantly more slowly to the sulfone. When the substrate was (p-OMe)PhSCF2CH3, then the resultant (demethylated) phenol sulfoxide had an enantiomeric excess of 60%, and when the substrate was the β-substituted-SCF2CH3 naphthalene, then the enantiomeric excess of the resultant sulfoxide was 54%. There was no

• very active and outcompetes demethylation, however, that demethylation is significantly more active that the second oxidation of sulfoxides to sulfones. Incubation of naphthalene 5 with C. elegans, generated three new metabolites 11–13 which arose by oxidations at sulphur and hydroxylations of the

• naphthalene ring, as summarised in Scheme 3. These metabolites were isolated by reversed-phase HPLC and characterised by 1H and 19F NMR and mass spectrometry. This identified sulfoxides 11 and 12 as the major metabolites and a trace amount of a minor sulfone which had the general structure 13 as determined by

Complexation of a guanidinium-modified calixarene with diverse dyes and investigation of the corresponding photophysical response

• Yu-Ying Wang,
• Yong Kong,
• Zhe Zheng,
• Wen-Chao Geng,
• Zi-Yi Zhao,
• Hongwei Sun and
• Dong-Sheng Guo

Beilstein J. Org. Chem. 2019, 15, 1394–1406, doi:10.3762/bjoc.15.139

• luminescent dyes. Fluorescein, eosin Y, rose bengal, tetraphenylporphine sulfonate and sulfonated aluminum phthalocyanine were employed as classical aggregation-induced quenching dyes. 2-(p-Toluidinyl)naphthalene-6-sulfonic acid and 1-anilinonaphthalene-8-sulfonic acid were selected as representatives of

• (EY), rose bengal (RB), tetraphenylporphine sulfonate (TPPS), sulfonated aluminum phthalocyanine (AlPcS4), 2-(p-toluidinyl)naphthalene-6-sulfonic acid (2,6-TNS), 1-anilinonaphthalene-8-sulfonic acid (1,8-ANS), phosphated tetraphenylethylene (P-TPE), sulfonated acedan (TPS), and a ruthenium(II) complex

• photons as the excitation source. The fluorescent probe simultaneously absorbs two low energy photons to reach the excited state followed by fluorescence [57]. Acedan (6-acetyl-2-(dimethylamino)naphthalene) is a well-known probe with two-photon absorption that has been utilized in two-photon microscopy

Mechanochemical Friedel–Crafts acylations

• Mateja Đud,
• Anamarija Briš,
• Iva Jušinski,
• Davor Gracin and
• Davor Margetić

Beilstein J. Org. Chem. 2019, 15, 1313–1320, doi:10.3762/bjoc.15.130

• the reaction carried out in solution (40% vs 6% yield). The screening of substrates showed disparate reactivities, ranging from quantitative to low (Scheme 3). Most rewarding are reactions of toluene, o-xylene, naphthalene and tetralin. Interestingly, ball milling of 4-ethylanisole provided phenol 12

• naphthalene were less reactive under the same ball milling conditions and reactions stopped at the stage of formation of product 3 and 15. One-step preparation of quinone 30 [39], was achieved by melting reactants at 140 °C for 10 min. Under these conditions, a mixture of adducts 3 and 30 (1.5:1 ratio) was

Self-assembly behaviors of perylene- and naphthalene-crown macrocycle conjugates in aqueous medium

• Xin Shen,
• Bo Li,
• Tiezheng Pan,
• Jianfeng Wu,
• Yangxin Wang,
• Jie Shang,
• Yan Ge,
• Lin Jin and
• Zhenhui Qi

Beilstein J. Org. Chem. 2019, 15, 1203–1209, doi:10.3762/bjoc.15.117

• Materials & Engineering (IBME), Northwestern Polytechnical University, Xi’an, Shaanxi 710072, P. R. China 10.3762/bjoc.15.117 Abstract The synthesis of conjugates of perylene diimide (PDI) and naphthalene diimide (NDI) modified with two benzo-21-crown-7 ethers (B21C7) are herein described. Their self

• with their linear glycol chain counterparts, B21C7 shows great potential to be an easy-to-accessed building block to probe the non-covalent interactions and chemical transformations influenced by water molecules. Perylene diimide (PDI) and naphthalene diimide (NDI) are polycyclic aromatic chromophores

• × 10−4 M. Synthetic route of perylene- and naphthalene-crown macrocycle conjugates 1 and 2. Supporting Information Supporting Information File 388: Experimental and analytical data. Acknowledgements We gratefully acknowledge financial support from the Thousand Talents Program of China, Postdoctoral

Mechanochemistry of supramolecules

• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2019, 15, 881–900, doi:10.3762/bjoc.15.86

• –acceptor [2]rotaxanes such as 19 through liquid-assisted mechanochemical milling (Figure 9). The donor–acceptor interaction between the electron-deficient naphthalene diimide moiety and the electron-rich naphthalene moieties embedded in the macrocyclic polyethers played the vital role for the construction

Coordination chemistry and photoswitching of dinuclear macrocyclic cadmium-, nickel-, and zinc complexes containing azobenzene carboxylato co-ligands

• Jennifer Klose,
• Tobias Severin,
• Peter Hahn,
• Alexander Jeremies,
• Jens Bergmann,
• Daniel Fuhrmann,
• Jan Griebel,
• Bernd Abel and
• Berthold Kersting

Beilstein J. Org. Chem. 2019, 15, 840–851, doi:10.3762/bjoc.15.81

• physicochemical properties of the bound guest molecules are also greatly affected. Thus, complexation of naphthalene diimide carboxylato ligands leads to a substantial (>95%) quenching of the diimide fluorescence [5], and incorporation of a Fe(CpCO2H)2 unit leads to a significant anodic shift of the metallocene’s

Azologization of serotonin 5-HT₃ receptor antagonists

• Karin Rustler,
• Galyna Maleeva,
• Piotr Bregestovski and
• Burkhard König

Beilstein J. Org. Chem. 2019, 15, 780–788, doi:10.3762/bjoc.15.74

• properties of direct azologization to azo-extension, two additional derivatives of the in vitro most promising naphthalene azopurine 16c were synthesized either by keeping the original thioether (Scheme 5) or replacing it by an amide bond (Scheme 6) known as common structural feature of 5-HT3R antagonists

• , two azo-extended purine derivatives 23 and 28 were synthesized resulting in excellent photochromic properties. Figure 1 compares exemplarily the UV–vis absorption spectra of the naphthalene-azo-purine 16c (left) and its azo-extended azobenzene thioether purine 23 (right). The determination of the

Selective benzylic C–H monooxygenation mediated by iodine oxides

• Kelsey B. LaMartina,
• Haley K. Kuck,
• Linda S. Oglesbee,
• Asma Al-Odaini and
• Nicholas C. Boaz

Beilstein J. Org. Chem. 2019, 15, 602–609, doi:10.3762/bjoc.15.55

• aromatization was observed, suggesting that monooxygenated products are able to react further. We propose that acetoxylated tetrahydronaphthalene eliminates acetic acid to yield dihydronaphthalene, which can be further oxidized by two electrons to yield the stable naphthalene ring. Minisci and co-workers also

Oxidative radical ring-opening/cyclization of cyclopropane derivatives

• Yu Liu,
• Qiao-Lin Wang,
• Zan Chen,
• Cong-Shan Zhou,
• Bi-Quan Xiong,
• Pan-Liang Zhang,
• Chang-An Yang and
• Quan Zhou

Beilstein J. Org. Chem. 2019, 15, 256–278, doi:10.3762/bjoc.15.23

• different amount of NBS (N-bromosuccinimide). The corresponding CF3-substituted naphthalene 32 could be obtained in 69% yield when the product 31a was oxidized by 3 equiv of NBS (Scheme 9, reaction a). When the amount of NBS was increased to 6 equiv under identical conditions, the CF3-substituted

Adhesion, forces and the stability of interfaces

• Robin Guttmann,
• Johannes Hoja,
• Christoph Lechner,
• Reinhard J. Maurer and
• Alexander F. Sax

Beilstein J. Org. Chem. 2019, 15, 106–129, doi:10.3762/bjoc.15.12

1,8-Bis(dimethylamino)naphthyl-2-ketimines: Inside vs outside protonation

• A. S. Antonov,
• A. F. Pozharskii,
• P. M. Tolstoy,
• A. Filarowski and
• O. V. Khoroshilova

Beilstein J. Org. Chem. 2018, 14, 2940–2948, doi:10.3762/bjoc.14.273

• -arylketimines of 1,8-bis(dimethylamonio)naphthalene with a different number of methoxy groups in an aromatic substituent were investigated in solution by NMR (acetone, DMSO, MeCN), in solid state by X-ray analysis and in the gas phase by DFT calculations. Both mono- and diprotonated species were considered. It

• rotation of the NH2+ fragment in dications. Keywords: hydrogen bond; imine; NMR; proton sponge; superbase; Introduction It is well known that the extremely high basicity of 1,8-bis(dimethylamino)naphthalene (1, DMAN; pKa = 12.1 in H2O [1][2], 18.62 in MeCN [3], 7.5 in DMSO [4]) and its derivatives

• of the Z-form through formation of a stronger hydrogen bond between the DMSO molecule and the NHb proton [11], which is sterically unhindered and accessible for the solvent. Indeed, X-ray data and quantum chemical calculations show that phenyl and naphthalene rings are almost perpendicular (Figure 2

An overview on recent advances in the synthesis of sulfonated organic materials, sulfonated silica materials, and sulfonated carbon materials and their catalytic applications in chemical processes

• Hashem Sharghi,
• Pezhman Shiri and
• Mahdi Aberi

Beilstein J. Org. Chem. 2018, 14, 2745–2770, doi:10.3762/bjoc.14.253

• strength, the high surface area may play a role in catalysis. The catalyst was reused up to five cycles [69]. Pourmousavi et al. [70] found that sulfonated polynaphthalene 121 synthesized from naphthalene (119) shows high catalytic activities in the one-pot preparation of amidoalkyl naphthols 50. The

• sulfonated polynaphthalene can be achieved in two steps: (a) polymerization of naphthalene (119) in nitrobenzene using FeCl3 as reagent (b) sulfonation of polynaphthalene (120) with chlorosulfonic acid in dichloromethane (Scheme 22). Amidoalkylnaphthol derivatives 50 were synthesized using catalyst 121 under

Targeting the Pseudomonas quinolone signal quorum sensing system for the discovery of novel anti-infective pathoblockers

• Christian Schütz and
• Martin Empting

Beilstein J. Org. Chem. 2018, 14, 2627–2645, doi:10.3762/bjoc.14.241

• benzimidazole moiety (compound not shown) [80]. In a follow-up patent they generated PqsR inhibitor 45 as a front-runner compound [81], in which the benzimidazole headgroup was replaced by a substituted naphthalene bearing a carboxamide, in analogy to a fragment 44 of Zender et al. [82] and similar to the

Synergistic approach to polycycles through Suzuki–Miyaura cross coupling and metathesis as key steps

• Sambasivarao Kotha,
• Milind Meshram and
• Chandravathi Chakkapalli

Beilstein J. Org. Chem. 2018, 14, 2468–2481, doi:10.3762/bjoc.14.223

• precursor 9 to [Ru-2] catalyst 5 gave the ring-closure product 10 in quantitative yield (Scheme 1). A sequential usage of SM cross coupling and RCM was responsible to construct various naphthalene derivatives such as 15 [31]. The SM coupling product 3,4-diallylbenzene derivative 13 (90%) was obtained from

Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules

• Hendrik V. Schröder and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190

• possibility of orthogonal switching (redox and light) enables an electrochemical “writing” of data which can be subsequently locked by a light stimulus. The TTF-based doubly interlocked crown/ammonium rotaxane 19 recently reported by us consists of a divalent axle with a π-electron-poor central naphthalene

Cobalt-catalyzed peri-selective alkoxylation of 1-naphthylamine derivatives

• Jiao-Na Han,
• Cong Du,
• Xinju Zhu,
• Zheng-Long Wang,
• Yue Zhu,
• Zhao-Yang Chu,
• Jun-Long Niu and
• Mao-Ping Song

Beilstein J. Org. Chem. 2018, 14, 2090–2097, doi:10.3762/bjoc.14.183

• provide the intermediate B. Subsequently, the transfer of ligand OR from the coordinated CoIII to the naphthalene ring led to the formation of intermediate C. Finally, the alkoxylated product 3aa was released accompanied with the deprotonation and the CoII species was transformed into the CoIII species by

A conformationally adaptive macrocycle: conformational complexity and host–guest chemistry of zorb[4]arene

• Liu-Pan Yang,
• Song-Bo Lu,
• Arto Valkonen,
• Fangfang Pan,
• Kari Rissanen and
• Wei Jiang

Beilstein J. Org. Chem. 2018, 14, 1570–1577, doi:10.3762/bjoc.14.134

• macrocycles possess multiple conformers due to the naphthalene flipping in analogy with the phenyl-ring flipping seen in the more common calixarenes. The conformers so formed undergo quick interconversion and each one has a slightly different cavity. Thus, these conformers consist of a complex conformational

• guests and the four naphthalene rings of the host should still be the major driving force as mentioned above. However, it was noticed that the distances between diagonal linker oxygen atoms in the backbone of the host are slightly different for the four complexes. These interactions may be tuned by the

• = −0.13, R2 = 0.9956) and TΔS (right, slope = 0.93, R2 = 0.9976). (a) Chemical structures of ZB4 and the guests involved in this research. The counterions are PF6−. (b) The four representative conformers of ZB4 resulting from naphthalene flipping. Numberings on the structures are used to assign NMR

Hyper-reticulated calixarene polymers: a new example of entirely synthetic nanosponge materials

• Alberto Spinella,
• Marco Russo,
• Antonella Di Vincenzo,
• Delia Chillura Martino and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2018, 14, 1498–1507, doi:10.3762/bjoc.14.127

• (bromocresol green, 8), a bis-indole (indigo carmine, 9) and a naphthalene-bis-diazoic (naphthol blue-black, 10), in order to evaluate the outcome of molecular size, shape and electric charge. Dyes can be considered suitable and easily detectable models of pollutants [43][44][45][46][47], for the removal of

A survey of chiral hypervalent iodine reagents in asymmetric synthesis

• Soumen Ghosh,
• Suman Pradhan and
• Indranil Chatterjee

Beilstein J. Org. Chem. 2018, 14, 1244–1262, doi:10.3762/bjoc.14.107

• new kind of binaphthyl-based chiral I(III) prereagent 19 with the 8 and 8′ positions of the naphthalene substituents being occupied by iodide. Here they have observed that this chiral hypervalent iodine reagent 19 in the presence of co-oxidant m-CBPA is very useful for the dearomatizing

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

• reported that the oxidative amination of 2,3-benzotropone (12) with methylcopperamine sulfate in aqueous methylamine at room temperature afforded 4-methylamino-1-naphthalene carbaldehyde (215) with a trace amount of 4-methylamino-2,3-benzotropone (214) via reaction paths including the dishing of Michael

Synthetic avenues towards a tetrasaccharide related to Streptococcus pneumonia of serotype 6A

• Aritra Chaudhury,
• Mana Mohan Mukherjee and
• Rina Ghosh

Beilstein J. Org. Chem. 2018, 14, 1095–1102, doi:10.3762/bjoc.14.95

• ). Subsequently, 10 was subjected to naphthylmethylation/p-methoxybenzylation [32] with 2-(bromomethyl)naphthalene (NapBr)/p-methoxybenzyl chloride in DMF to afford 6a/11 [32] in 90% and 80% yields, respectively. These derivatives were next subjected to thioglycoside hydrolysis using trichloroisocyanuric acid

An overview of recent advances in duplex DNA recognition by small molecules

• Sayantan Bhaduri,
• Nihar Ranjan and
• Dev P. Arya

Beilstein J. Org. Chem. 2018, 14, 1051–1086, doi:10.3762/bjoc.14.93

• and its cytotoxicity was attributed to DNA minor groove binding ability [105]. Recently, Schmuck et al. have developed a first prototype of cationic oligopeptide-based molecular beacon (conjugate 43) coupled with a FRET pair, a naphthalene donor and a dansyl acceptor, for ratiometric detection of ds

Electrochemically modified Corey–Fuchs reaction for the synthesis of arylalkynes. The case of 2-(2,2-dibromovinyl)naphthalene

• Fabiana Pandolfi,
• Isabella Chiarotto and
• Marta Feroci

Beilstein J. Org. Chem. 2018, 14, 891–899, doi:10.3762/bjoc.14.76

• Fabiana Pandolfi Isabella Chiarotto Marta Feroci Deptartment of Fundamental and Applied Sciences for Engineering (SBAI), Sapienza University of Rome, via Castro Laurenziano, 7, 00161, Rome, Italy 10.3762/bjoc.14.76 Abstract The electrochemical reduction of 2-(2,2-dibromovinyl)naphthalene in a DMF

• solution (Pt cathode) yields selectively 2-ethynylnaphthalene or 2-(bromoethynyl)naphthalene in high yields, depending on the electrolysis conditions. In particular, by simply changing the working potential and the supporting electrolyte, the reaction can be directed towards the synthesis of the terminal

• alkyne (Et4NBF4) or the bromoalkyne (NaClO4). This study allowed to establish that 2-(bromoethynyl)naphthalene can be converted into 2-ethynylnaphthalene by cathodic reduction. Keywords: arylalkyne; carbon–bromine bond cleavage; cathodic reduction; Corey–Fuchs reaction; 2-(2,2-dibromovinyl)naphthalene

Bromide-assisted chemoselective Heck reaction of 3-bromoindazoles under high-speed ball-milling conditions: synthesis of axitinib

• Jingbo Yu,
• Zikun Hong,
• Xinjie Yang,
• Yu Jiang,
• Zhijiang Jiang and
• Weike Su

Beilstein J. Org. Chem. 2018, 14, 786–795, doi:10.3762/bjoc.14.66

• coupling product 3oa (70%). Besides, N-unsubstituted indazole 1n could also be tolerated in this reaction giving 3na (52%) and 3nf (49%) in moderate yield by using 1,8-bis(dimethylamino)naphthalene as a base. To our delight, 3-chloroindazole could also be activated in this reaction, giving the

• 207 stainless-steel balls (dMB = 6 mm, ФMB = 0.293), milling at 800 rpm for 90 min. aN-Boc-3-bromoindazole was used as substrate. b150 min. c700 rpm. d3-chloro-1-methyl-1H-indazole was used as substrate, νrot = 900 rpm. e1,8-Bis(dimethylamino)naphthalene was used as base. Synthesis of axitinib by

An air-stable bisboron complex: a practical bidentate Lewis acid catalyst

• Longcheng Hong,
• Sebastian Ahles,
• Andreas H. Heindl,
• Gastelle Tiétcha,
• Andrey Petrov,
• Zhenpin Lu,
• Christian Logemann and
• Hermann A. Wegner

Beilstein J. Org. Chem. 2018, 14, 618–625, doi:10.3762/bjoc.14.48

• yields of the substituted naphthalene 5e were comparable between the two bidentate Lewis acid catalysts (Table 1, entry 5). The binding of pyridazine (1j) with bisboron compound A, seems to be too strong to engage a fast ligand exchange with phthalazine (3). Recently we have demonstrated that catalyst A