Self-assembled coordination thioether silver(I) macrocyclic complexes for homogeneous catalysis

• Zhen Cao,
• Aline Lacoudre,
• Cybille Rossy and
• Brigitte Bibal

Beilstein J. Org. Chem. 2019, 15, 2465–2472, doi:10.3762/bjoc.15.239

• for 1a, AgOTFA for 1b, AgNO3 for 1c and PPh3AgOTf for 1d. Crystallographic structures of silver complexes Single crystals of 1a, 1c and 1d suitable for X-ray diffraction analysis were grown from the slow diffusion of hexane into a solution of each complex in dichloromethane. Interestingly, each

• )–1 ligands). The X-ray diffraction of monocrystals 1a revealed the formation of (R,S–1)2·(AgOTf)2 macrocycles driven by silver(I) coordination (Figure 1). The two ligands are facing through the coordination of one syn-thioether group to the same silver cation. Two different crystals were isolated and

• ) cation was coordinated to two sulfur atoms with (R)- and (S)-configuration, respectively (head-to-tail ligand coordination mode). These diastereoisomeric crystals presented a slightly different spatial arrangement. The head-to head macrocycle 1a had a parallelepiped shape (Figure 1a): the interplanar

Photochromic diarylethene ligands featuring 2-(imidazol-2-yl)pyridine coordination site and their iron(II) complexes

• Andrey G. Lvov,
• Max Mörtel,
• Anton V. Yadykov,
• Frank W. Heinemann,
• Valerii Z. Shirinian and
• Marat M. Khusniyarov

Beilstein J. Org. Chem. 2019, 15, 2428–2437, doi:10.3762/bjoc.15.235

• . Crystals suitable for X-ray structure were obtained in a fritted U-shape tube by the slow diffusion of methanol solutions of in situ-prepared “Fe(H2B(pz)2)2“ and diarylethene 6. Unexpectedly, we have found that the structure of the product depends on the reaction time. Reproducible crystals isolated after

• growing for 1 month and less – a dinuclear complex 8, and unique crystals after 2-year storage – a tetranuclear complex 9, have different molecular structures (Figure 3). Both complexes represent unusual cyclic complexes, comprising two diarylethene ligands and two or four iron(II) ions in 8 and 9

• ). Apparently, this product is the result of destruction of bis(pyrazolyl)borate moieties of complex 8 by methanol. Species 9 crystallizes as red, block-shaped crystals in the triclinic P−1 space group with one molecule in the unit cell. The crystal structure reveals two pairs of differently substituted iron

Reversible switching of arylazopyrazole within a metal–organic cage

• Anton I. Hanopolskyi,
• Soumen De,
• Michał J. Białek,
• Yael Diskin-Posner,
• Liat Avram,
• Moran Feller and
• Rafal Klajn

Beilstein J. Org. Chem. 2019, 15, 2398–2407, doi:10.3762/bjoc.15.232

• protons are correlated with H1, H3, and H7, whereas the Hc protons are correlated with H4, H8, and H5 (see the partial NOE spectrum in Figure 2; see below for further analysis of this spectrum). Single crystals of (E-1)22 suitable for X-ray diffraction were obtained by slow water evaporation from an

• ; the strongest correlations were found between Ha and H1 and between Hc and H4 (Figure S20, Supporting Information File 1; note that the opposite was found for the E isomer, cf. Figure 2). Despite repeated efforts, we did not succeed in preparing crystals of the (Z-1)2 inclusion complex suitable for X

In water multicomponent synthesis of low-molecular-mass 4,7-dihydrotetrazolo[1,5-a]pyrimidines

• Irina G. Tkachenko,
• Sergey A. Komykhov,
• Vladimir I. Musatov,
• Svitlana V. Shishkina,
• Viktoriya V. Dyakonenko,
• Vladimir N. Shvets,
• Mikhail V. Diachkov,
• Valentyn A. Chebanov and
• Sergey M. Desenko

Beilstein J. Org. Chem. 2019, 15, 2390–2397, doi:10.3762/bjoc.15.231

• Irina G. Tkachenko Sergey A. Komykhov Vladimir I. Musatov Svitlana V. Shishkina Viktoriya V. Dyakonenko Vladimir N. Shvets Mikhail V. Diachkov Valentyn A. Chebanov Sergey M. Desenko State Scientific Institution "Institute for Single Crystals", National Academy of Sciences of Ukraine, Nauky Ave 60

Aggregation-induced emission effect on turn-off fluorescent switching of a photochromic diarylethene

• Luna Kono,
• Yuma Nakagawa,
• Ayako Fujimoto,
• Ryo Nishimura,
• Yohei Hattori,
• Toshiki Mutai,
• Nobuhiro Yasuda,
• Kenichi Koizumi,
• Satoshi Yokojima,
• Shinichiro Nakamura and
• Kingo Uchida

Beilstein J. Org. Chem. 2019, 15, 2204–2212, doi:10.3762/bjoc.15.217

• . In addition, it shows turn-off type fluorescence switching in an aprotic solvent and in crystals. The fluorescence is quenched as the content of closed-ring isomers increases upon UV light irradiation. Conclusions: A diarylethene containing an ESIPT functional group was prepared. It showed

• crystals are inherently capable of photo-reversible luminescence switching because the electronic structures of photochromic molecules reversibly change upon photoisomerization [13][14]. However, such a fluorescent system in condensed phase emits fluorescence often absorbed in adjacent molecules, therefore

• spectrofluorophotometer equipped with ILF-533 integral sphere. KEYENCE VHX-500, VH-S30, VH-Z20 were used to monitor the crystals. For the UV light irradiation, KEYENCE UV-400, UV-50H (λ = 365 nm), Spectronics Corporation Westbury, New York, USA Spectro Line Highest Ultraviolet Intensity Guaranteed (100 V, 40 A, λ = 313

Azologization and repurposing of a hetero-stilbene-based kinase inhibitor: towards the design of photoswitchable sirtuin inhibitors

• Christoph W. Grathwol,
• Nathalie Wössner,
• Sören Swyter,
• Adam C. Smith,
• Enrico Tapavicza,
• Robert K. Hofstetter,
• Anja Bodtke,
• Manfred Jung and
• Andreas Link

Beilstein J. Org. Chem. 2019, 15, 2170–2183, doi:10.3762/bjoc.15.214

• reduced pressure. The formed precipitate was collected by filtration and recrystallized from EtOAc. The product was obtained as colourless crystals (0.55 g, 2.45 mmol, 49%): Rf = 0.25 (cyclohexane/THF 1:1); mp: 196.4 °C; 1H NMR (400 MHz, DMSO-d6) δ (ppm) 8.93 (d, J = 2.0 Hz, 1H), 8.90 (d, J = 2.1 Hz, 1H

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

• −, Br− and I− were found as 4.4 × 101 M−1, 1.7 × 101 M−1, 8.5 M−1, respectively. Thus, the interaction of 1,2,3-triazolium CH is decreasing with increasing halide size. Besides, the complexes of halides with the macrocycles were shown to have visible charge-transfer absorptions in the molecular crystals

• . Thus, these complexes could be useful for designing functional molecular crystals and materials which can be applied for the study of photoinduced electron transfer and energy conversion towards application in the field of molecular electronics. 3. Molecular reactors Designing synthetic host systems

1,2,3,4-Tetrahydro-1,4,5,8-tetraazaanthracene revisited: properties and structural evidence of aromaticity loss

• Arnault Heynderickx,
• Sébastien Nénon,
• Olivier Siri,
• Vladimir Lokshin and
• Vladimir Khodorkovsky

Beilstein J. Org. Chem. 2019, 15, 2059–2068, doi:10.3762/bjoc.15.203

• THTAA Derivative 3 was prepared from 2,5-dihydroxy-p-benzoquinone and ethylenediamine as brownish-yellow solid according to the recommended procedure (Scheme 1) [8]. Crystallization from butyl acetate produced yellow crystals of THTAA (3) in about 50% yield, still slightly brownish, along with the

• observed upon attempts to sublime the brown byproduct about 200–210 °C affording colorless crystals. The NMR spectrum corresponded to 5 (described, sometimes, as light yellow solid [18][19]). It is worth of noting that sublimed 5 does not fluoresce so that previously observed fluorescence [20] and

• -donating ethylenediamino moiety toward the electron-accepting ethylenediimino moiety in 3 and delocalization of the positive charges in 6a and 7a (Scheme 3), and are not artifacts arising from the strong intermolecular interactions within the crystals. Losing aromaticity, the benzene ring is becoming less

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

• the Supporting Information File 1, Figures S6–S8). In addition to that, slow evaporation of an equimolar solution of U1 and A2 in benzene furnished red-orange single crystals suitable for X-ray analysis of a [2 + 2] halogen-bonded box, U1···A2, over the course of a few days in quantitative yield

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

• literature report [32]). This was presumably due to ruthenium undergoing a reductive elimination and the chloride remaining on the triazolium moiety. Crystallization also proved to be futile after many attempts under many different conditions. The only crystals that formed were either found to be the

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

• -corona[6]arenes in the solid state, high quality single crystals of 3a were grown at room temperature from diffusion of diethyl ether vapor into the solution of 3a in acetonitrile. X-ray diffraction analysis revealed that the macrocycle 3a adopted an interesting conformation. As depicted in Figure 1, it

• ability of 3a to bind various anion species in gas phase. To our delight, host molecule 3a co-crystalized with n-Bu4NX (X = Cl, Br) from diffusion of diethyl ether vapor into ethyl acetate solution at ambient temperature to give single crystals of the host–guest complexes (n-Bu4NX)3-3a (X = Cl, Br). X-ray

Archangelolide: A sesquiterpene lactone with immunobiological potential from Laserpitium archangelica

• Silvie Rimpelová,
• Michal Jurášek,
• Lucie Peterková,
• Jiří Bejček,
• Vojtěch Spiwok,
• Miloš Majdl,
• Michal Jirásko,
• Miloš Buděšínský,
• Juraj Harmatha,
• Eva Kmoníčková,
• Pavel Drašar and
• Tomáš Ruml

Beilstein J. Org. Chem. 2019, 15, 1933–1944, doi:10.3762/bjoc.15.189

• period of 72 h during which the crystals were formed. These were collected by filtration over a frit and washed with hexanes obtaining 7.9 g of the matter that was analyzed by TLC and LRMS analyses. We observed that the matter consisted, in particular, of two terpene-type compounds, compound 1 and 2, and

Tautomerism as primary signaling mechanism in metal sensing: the case of amide group

• Vera Deneva,
• Georgi Dobrikov,
• Aurelien Crochet,
• Daniela Nedeltcheva,
• Katharina M. Fromm and
• Liudmil Antonov

Beilstein J. Org. Chem. 2019, 15, 1898–1906, doi:10.3762/bjoc.15.185

• product was purified by column chromatography – 75 g silica gel, phase dichloromethane/petroleum ether 5:2 – to give 0.59 g (43%) of pure c as beige crystals. Mp 87–88 °C; 1H NMR (600.11 MHz, CDCl3, 293 K) δ 8.36 (m, 1H, H-9), 7.74 (m, 1H, H-6), 7.45 (m, 2H, H-7, H-8), 7.33 (d, J = 8.3 Hz, 1H, H-4), 7.13

• purified by column chromatography – 75 g silica gel, phase dichloromethane/methyl tert-butyl ether 10:1. After column chromatography, the product was additionally washed with petroleum ether and dried in vacuum to give 0.720 g (84%) of pure 6 as bright red crystals. Mp 152–153 °C; 1H NMR* (600.11 MHz, DMSO

• (Aldrich). X-ray crystallographic measurements Experimental Single crystals of 6 were crystallized from acetonitrile by slow evaporation. A suitable crystal was selected and was mounted on a loop in oil on a Stoe IPDS2T diffractometer. The crystallographic data of the single crystal were collected with Cu

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

• produced crystals that were yellow-orange; they were highly soluble in C6D6, giving a bright red solution. Single crystal X-ray analysis identified the crystals as the heterometallic complex [KCsA'2] (see below). The 1H NMR spectrum of the products from the 1:1 and 3:1 grinds were identical. It should be

• analogous solvate is obtained, and the resulting crystals are of higher quality than those from toluene. Single crystal X-ray analysis reveals that it has a structure that is qualitatively the same as the toluene solvate, and only the benzene solvate is discussed here. Like the unsolvated complex [KA']∞ [17

Application of chiral 2-isoxazoline for the synthesis of syn-1,3-diol analogs

• Juanjuan Feng,
• Tianyu Li,
• Jiaxin Zhang and
• Peng Jiao

Beilstein J. Org. Chem. 2019, 15, 1840–1847, doi:10.3762/bjoc.15.179

• gave 16 in 87% yield [26][27]. The absolute stereochemistry of 16 was confirmed by crystal structure analysis [72] and the specific rotation [28] of 17. Centimeter-long prismatic single crystals of 17 were obtained by slow evaporation of a petroleum solution. Starting from 9, we tested several

Metal-free mechanochemical oxidations in Ertalyte^® jars

• Andrea Porcheddu,
• Francesco Delogu,
• Lidia De Luca,
• Claudia Fattuoni and
• Evelina Colacino

Beilstein J. Org. Chem. 2019, 15, 1786–1794, doi:10.3762/bjoc.15.172

• l’Ecole Normale, 34296 Montpellier, Cedex 5, France 10.3762/bjoc.15.172 Abstract Aimed at eliminating or at least significantly reducing the use of solvents, sodium hypochlorite pentahydrate crystals (NaOCl·5H2O) in the presence of a catalytic amount of a nitrosyl radical (TEMPO or AZADO) have been

• %, bleach) under mechanical activation conditions [50]. Oxidation of 3-phenyl-1-propanol (1a) with NaOCl·5H2O crystals under mechanical activation conditions using ZrO2 or Ertalyte® jars. Optimization of the reaction conditions. Supporting Information Supporting Information File 76: Experimental procedures

Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D–π–)₂A fluorescent dyes

• Keiichi Imato,
• Toshiaki Enoki,
• Koji Uenaka and
• Yousuke Ooyama

Beilstein J. Org. Chem. 2019, 15, 1712–1721, doi:10.3762/bjoc.15.167

• dye molecules in the solid state, although we could not prepare single crystals of OUY-2, OUK-2 and OUJ-2 for the X-ray structural analysis. Electrochemical properties The electrochemical properties of OUY-2, OUK-2 and OUJ-2 were investigated by cyclic voltammetry (CV) in DMF containing 0.1 M

• . Electrochemical data and HOMO and LUMO energy level of OUY-2, OUK-2 and OUJ-2. Supporting Information Supporting Information File 482: 1H and 13C NMR spectra of OUJ-2. Acknowledgements This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Soft Crystals” (No. 2903) (JSPS KAKENHI

Synthesis, enantioseparation and photophysical properties of planar-chiral pillar[5]arene derivatives bearing fluorophore fragments

• Guojuan Li,
• Chunying Fan,
• Guo Cheng,
• Wanhua Wu and
• Cheng Yang

Beilstein J. Org. Chem. 2019, 15, 1601–1611, doi:10.3762/bjoc.15.164

• symmetrical structures, as well as highly tunable functionality, the studies on pillar[5]arenes have been developed rapidly in various areas, such as artificial transmembrane channels [11][12], molecular complexation [13][14] and nonporous adaptive crystals [15][16][17]. One of the features of pillar[5]arenes

A novel three-component reaction between isocyanides, alcohols or thiols and elemental sulfur: a mild, catalyst-free approach towards O-thiocarbamates and dithiocarbamates

• András György Németh,
• György Miklós Keserű and
• Péter Ábrányi-Balogh

Beilstein J. Org. Chem. 2019, 15, 1523–1533, doi:10.3762/bjoc.15.155

• the work-up, no chromatography was necessary and the crude product was purified by recrystallization from hexane/ethyl acetate. The three collected crops of crystals provided the thiocarbamate 3a in a total of 74% yield. We have envisaged that our multicomponent reaction could be compatible with

Introduction of an isoxazoline unit to the β-position of porphyrin via regioselective 1,3-dipolar cycloaddition reaction

• Xiujun Liu,
• Xiang Ma and
• Yaqing Feng

Beilstein J. Org. Chem. 2019, 15, 1434–1440, doi:10.3762/bjoc.15.143

• –8.95 (m, 4H, β-pyrrolic H), 9.30 (s, 1H, β-pyrrolic H). ESIMS m/z: [M + H]+ calcd for C61H40Cl2N5O3Zn, 1024.1794; found, 1024.1765; UV–vis (CH2Cl2) λmax: 403, 424, 552, 592 nm. Some crystals of C61H39Cl2N5O3Zn were recrystallized from CHCl3/n-hexane. A suitable crystal was selected and mounted on a

Selenophene-containing heterotriacenes by a C–Se coupling/cyclization reaction

• Pierre-Olivier Schwartz,
• Sebastian Förtsch,
• Astrid Vogt,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2019, 15, 1379–1393, doi:10.3762/bjoc.15.138

• accordance with data for selenophene compared to thiophene [35]. Single crystal X-ray structure analysis Single crystals of heterotriacenes DTS 2, DST 3, and DSS 4 suitable for X-ray structure analysis were obtained and details of the refinements are summarized in Tables S1-S3 (Supporting Information File 1

• ). X-ray structure analysis of DTT 1 was already published by Brédas et al. [36][37]. Single crystals of DTS 2 and DSS 4 as very thin crystalline needles were obtainned by careful sublimation. Both heterotriacenes crystallized in the monoclinic space group P21/c with 18 molecules in the unit cell (DTS

• 2: a = 5.978(3), b = 29.005(11), c = 21.173(8) Å; α = 90°, β = 91.903(19)°, γ = 90°, V = 3669(3) Å3; DSS 4: a = 6.108(3), b = 29.049(17), c = 21.949(11) Å; α = 90°, β = 91.815 (12)°, γ = 90°, V = 3892(3) Å3). The molecules in both crystals evidenced some rotational disorder. Single crystals of

Formation of an unexpected 3,3-diphenyl-3H-indazole through a facile intramolecular [2 + 3] cycloaddition of the diazo intermediate

• Andrew T. King,
• Hugh G. Hiscocks,
• Lidia Matesic,
• Mohan Bhadbhade,
• Roger Bishop and
• Alison T. Ung

Beilstein J. Org. Chem. 2019, 15, 1347–1354, doi:10.3762/bjoc.15.134

• the indazole ring. The ambiguity was overcome through the X-ray structural analysis of the compound. The single crystals were easily obtained by recrystallisation from CH2Cl2. Crystal structure analysis The X-ray crystal analysis revealed that the product was not the diazonium intermediate 7, but

• rather the compound 8 containing the 3,3-diphenyl-3H-indazole core structure. The crystals were found to be triclinic, P-1 space group with cell constants a = 9.2107(4), b = 10.0413(5), c = 14.4363(6) Å, α = 78.183(2), β = 87.625(2), γ = 71.975(2)°. The structure of 8 and the atom-labelling scheme are

Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks

• Sebastian Hamer,
• Fynn Röhricht,
• Marius Jakoby,
• Ian A. Howard,
• Xianghui Zhang,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 1331–1338, doi:10.3762/bjoc.15.132

• ., on surfaces and in materials. Different strategies have been employed to prepare ordered arrays of rotors in two dimensions, such as the inclusion of rotors in channels on the surface of particular crystals [3] on metal surfaces [4][5][6] or in Langmuir–Blodgett films [7]. Several strategies have

• also been pursued to implement molecular rotors in the solid state. Crystals of linear molecular rotors [8][9][10][11][12][13], caged rotor crystals and gyroscope like molecules [14][15][16][17][18][19][20] as well as organosilicates [21] and metal-organic frameworks [22][23][24][25] containing

• cross coupling. Using this method, dicarboxylic acids could be obtained from simple aqueous work-up and extraction. Difluoro compound 1 Difluorobenzenes have been employed as dipolar rotors by Garcia-Garibay in crystals [10], as an elongated MOF linker by Blight and Forgan [25] and for the investigation

Synthesis of non-racemic 4-nitro-2-sulfonylbutan-1-ones via Ni(II)-catalyzed asymmetric Michael reaction of β-ketosulfones

• Alexander N. Reznikov,
• Anastasiya E. Sibiryakova,
• Marat R. Baimuratov,
• Eugene V. Golovin,
• Victor B. Rybakov and
• Yuri N. Klimochkin

Beilstein J. Org. Chem. 2019, 15, 1289–1297, doi:10.3762/bjoc.15.127

• presence of complex 7a was carried out under the optimized conditions (Table 3). The dr values for 8:9 are ranged from 1:– to 1:1.13. The formation of а mixture of diastereomers is observed in the presence of substituents in the 2- or 3-position of the aryl ring of sulfones or nitroalkenes. Crystals

Doebner-type pyrazolopyridine carboxylic acids in an Ugi four-component reaction

• Maryna V. Murlykina,
• Oleksandr V. Kolomiets,
• Maryna M. Kornet,
• Yana I. Sakhno,
• Sergey M. Desenko,
• Victoriya V. Dyakonenko,
• Svetlana V. Shishkina,
• Oleksandr A. Brazhko,
• Vladimir I. Musatov,
• Alexander V. Tsygankov,
• Erik V. Van der Eycken and
• Valentyn A. Chebanov

Beilstein J. Org. Chem. 2019, 15, 1281–1288, doi:10.3762/bjoc.15.126

• , State Scientific Institution “Institute for Single Crystals” of National Academy of Sciences of Ukraine, Nauky Ave., 60, 61072, Kharkiv, Ukraine Faculty of Chemistry, V. N. Karazin Kharkiv National University, Svobody sq., 4, 61077, Kharkiv, Ukraine Laboratory for Organic & Microwave-Assisted Chemistry