Formal preparation of regioregular and alternating thiophene–thiophene copolymers bearing different substituents

Atsunori Mori,
Keisuke Fujita,
Chihiro Kubota,
Toyoko Suzuki,
Kentaro Okano,
Takuya Matsumoto,
Takashi Nishino and
Masaki Horie

Full Research Paper
Published 05 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Cross-coupling polymerization of thiophene.
  
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3. Scheme 2: Polymerization of bithiophene.
  
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4. Scheme 3: Preparation of chlorobithiophenes.
  
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5. Scheme 4: Polymerization of chlorobithiophenes.
  
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6. Figure 1: Solubility tests of alternating copolymer 6 (1 mg of material dissolved in 1 mL of the solvent).
  
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7. Figure 2: XRD measurement and prediction of the bilayer lamellar structure of polymer 6c. a) XRD analysis. b)...
  
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Beilstein J. Org. Chem. 2020, 16, 317–324, doi:10.3762/bjoc.16.31

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Synthesis and circularly polarized luminescence properties of BINOL-derived bisbenzofuro[2,3-b:3’,2’-e]pyridines (BBZFPys)

Ryo Takishima,
Yuji Nishii,
Tomoaki Hinoue,
Yoshitane Imai and
Masahiro Miura

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Published 06 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Synthesis of BBFZPys through the Pd-catalyzed C–H/C–H coupling.
  
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3. Scheme 2: Synthesis of 3a–c.
  
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4. Scheme 3: Synthesis of 4a–c through oxidative coupling reaction.
  
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5. Scheme 4: Synthesis of 6.
  
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6. Figure 1: Absorption (dotted line) and fluorescence (solid line) spectra of 3, 4, and 6 measured as CHCl₃ sol...
  
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7. Figure 2: CD and CPL spectra of 3 measured as CHCl₃ solutions (1.0 × 10⁻⁵ M) and in the solid states (dispers...
  
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8. Figure 3: CD and CPL spectra of 4 and 6 measured as CHCl₃ solutions (1.0 × 10⁻⁵ M) and in solid states (dispe...
  
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9. Figure 4: ORTEP drawings of 4b and 4c with 50% thermal probability. Hydrogen atoms and solvent molecules are ...
  
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10. Figure 5: Intramolecular stacking structures of 4b and 4c.
  
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Beilstein J. Org. Chem. 2020, 16, 325–336, doi:10.3762/bjoc.16.32

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

Amy L. Mayhugh and
Christine K. Luscombe

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Published 13 Mar 2020

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1. Graphical Abstract
2. Scheme 1: A high yielding, highly selective room-temperature direct arylation reaction between indole and iod...
  
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3. Figure 1: ¹H NMR (500 MHz, CDCl₃) of (a) 5-iodo-1-octylindole monomer (b) PIn prepared according to condition...
  
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4. Figure 2: MALDI–TOF MS of PIn, indicating octylindole repeat units with three different types of end groups. ...
  
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5. Scheme 2: Commonly discussed mechanisms for C2 selective direct arylation, none containing radical intermedia...
  
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6. Scheme 3: Proposed mechanism for palladium radical involved reaction between indole and iodobenzene.
  
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7. Scheme 4: Radical trap effects on literature methods for the direct arylation at room temperature. A) From re...
  
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Beilstein J. Org. Chem. 2020, 16, 384–390, doi:10.3762/bjoc.16.36

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Six-fold C–H borylation of hexa-peri-hexabenzocoronene

Mai Nagase,
Kenta Kato,
Akiko Yagi,
Yasutomo Segawa and
Kenichiro Itami

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Published 13 Mar 2020

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1. Graphical Abstract
2. Figure 1: C–H functionalization of HBCs. (a) Perchlorinated HBC. (b) Borylated HBC substituted by 2,4,6-trime...
  
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3. Figure 2: Synthesis of hexaborylated HBC 1. (a) Solvent screening of six-fold C–H borylation of unsubstituted...
  
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4. Figure 3: The structure of 1 confirmed by X-ray crystallographic analysis. (a) ORTEP drawing of 1 with therma...
  
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5. Figure 4: Photophysical properties of 1. (a) UV–vis absorption (solid lines) spectra, fluorescence (dotted li...
  
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Beilstein J. Org. Chem. 2020, 16, 391–397, doi:10.3762/bjoc.16.37

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Synthesis of six-membered silacycles by borane-catalyzed double sila-Friedel–Crafts reaction

Yafang Dong,
Masahiko Sakai,
Kazuto Fuji,
Kohei Sekine and
Yoichiro Kuninobu

Letter
Published 17 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Synthetic methods of six-membered silacyclic compounds.
  
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3. Scheme 2: Scope of dihydrosilanes. Conditions: a: conditions B (Table 1, entry 5); b: conditions A (Table 1, entry 3).
  
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4. Scheme 3: Scope of diaryl ether and diaryl thioether derivatives. Conditions: a: conditions B (Table 1, entry 5); b:...
  
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5. Scheme 4: Gram-scale Synthesis of 3a.
  
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6. Scheme 5: Transformation of the amino groups in 3a.
  
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Beilstein J. Org. Chem. 2020, 16, 409–414, doi:10.3762/bjoc.16.39

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Synthesis of triphenylene-fused phosphole oxides via C–H functionalizations

Md. Shafiqur Rahman and
Naohiko Yoshikai

Letter
Published 27 Mar 2020

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1. Graphical Abstract
2. Figure 1: Examples of functional molecules based on π-extended phospholes.
  
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3. Scheme 1: Syntheses of PAH-fused phospholes featuring a 7-hydroxybenzo[b]phosphole as a key intermediate.
  
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4. Scheme 2: Synthesis of phosphole-fused ortho-teraryl compounds 7.
  
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5. Scheme 3: Oxidative cyclization of phosphole-fused ortho-teraryl compounds 7 into triphenylene-fused phosphol...
  
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6. Figure 2: ORTEP drawings of compound 8a (thermal ellipsoids set at 50% probability). a) top view; b) side vie...
  
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7. Figure 3: UV–vis absorption (solid lines) and fluorescence (dashed lines) spectra of compounds 8a–c.
  
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Beilstein J. Org. Chem. 2020, 16, 524–529, doi:10.3762/bjoc.16.48

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Copper-catalyzed remote C–H arylation of polycyclic aromatic hydrocarbons (PAHs)

Anping Luo,
Min Zhang,
Zhangyi Fu,
Jingbo Lan,
Di Wu and
Jingsong You

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Published 30 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Direct C–H arylation of PAHs.
  
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3. Scheme 2: Scope of aryliodonium salts. Reaction conditions: 1a (0.2 mmol), 2 (0.3 mmol) in DCE (1 mL) at 70 °...
  
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4. Scheme 3: Scope of PAHs. Reaction conditions: 1 (0.2 mmol), 2a (0.3 mmol) in DCE (1 mL) at 70 °C under N₂ for...
  
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5. Scheme 4: Proposed catalytic cycle.
  
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6. Figure 1: a) UV-visible absorption spectra of 4k, 4n and 4o in toluene (1 × 10⁻⁵ mol/L). b) Emission spectra ...
  
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Beilstein J. Org. Chem. 2020, 16, 530–536, doi:10.3762/bjoc.16.49

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Efficient synthesis of 3,6,13,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes by selective C–H/C–O arylations of anthraquinone derivatives

Seiya Terai,
Yuki Sato,
Takuya Kochi and
Fumitoshi Kakiuchi

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Published 31 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Projected synthetic routes for 3,6,13,16-tetrasubstituted tetrabenzo[a,d,j,m]coronenes.
  
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3. Scheme 2: Reported syntheses of 2,7,12,17-tetrasubstituted tetrabenzo[a,d,j,m]coronenes.
  
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4. Scheme 3: C–H tetraarylation of anthraquinone (1).
  
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5. Scheme 4: C–H diarylation of 1,4-diarylanthraquinones 5.
  
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6. Figure 1: Normalized UV–vis absorption spectra of 7aa, 7bb, and 7ba.
  
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7. Figure 2: Effects of the concentration and the temperature on the ¹H NMR spectra of 7aa.
  
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Beilstein J. Org. Chem. 2020, 16, 544–550, doi:10.3762/bjoc.16.51

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Regioselectively α- and β-alkynylated BODIPY dyes via gold(I)-catalyzed direct C–H functionalization and their photophysical properties

Takahide Shimada,
Shigeki Mori,
Masatoshi Ishida and
Hiroyuki Furuta

Full Research Paper
Published 01 Apr 2020

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1. Graphical Abstract
2. Figure 1: (a) Chemical structures of BODIPY (1) and dipyrromethane (2). (b) C–C bond forming alkynylations of...
  
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3. Scheme 1: Synthesis of α-ethynyl-substituted BODIPY derivatives 3a and 4a.
  
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4. Scheme 2: Synthesis of β-ethynyl-substituted BODIPY derivatives 5a and 5b and β,β'-diethynyl-substituted comp...
  
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5. Figure 2: Top and front views of the crystal structures of (a) 4a and (b) 6b with 50% thermal ellipsoid proba...
  
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6. Figure 3: Partial ¹H NMR spectra of (a) 1a, (b) 3a, (c) 4a, (d) 5a, and (e) 6a recorded in CDCl₃ at 298 K. As...
  
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7. Figure 4: UV–vis absorption spectra of the BODIPY derivatives, (a) 1a (green), 3a (blue), 4a (red), and (b) 1a...
  
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8. Figure 5: Fluorescence spectra of BODIPY derivatives. (a) 1a (green), 3a (blue), 4a (red) and (b) 1a (green), ...
  
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Beilstein J. Org. Chem. 2020, 16, 587–595, doi:10.3762/bjoc.16.53

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Direct borylation of terrylene and quaterrylene

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

Letter
Published 06 Apr 2020

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1. Graphical Abstract
2. Figure 1: Chemical structures of a) oligorylene-bisimides, b) oligorylenes, c) bay-bridging oligorylenes, d) ...
  
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3. Scheme 1: Synthesis of 2,5,10,13-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)terrylene (TB4): (a) (B...
  
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4. Figure 2: (Top) Single crystal X-ray structure of TB4. The thermal ellipsoids are scaled at 50% probability. ...
  
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5. Figure 3: UV–vis absorption and fluorescence spectra of terrylene (black) and TB4 (red) in toluene. λ_ex = 489...
  
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6. Figure 4: MO diagrams of terrylene and TB4 based on calculations at the B3LYP/6-31G(d).
  
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7. Scheme 2: Synthesis of 2,5,12,15-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quaterrylene (QB4): (a)...
  
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8. Figure 5: UV–vis absorption spectrum of QB4 in toluene.
  
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9. Figure 6: MO diagrams of terrylene and QB4 based on calculations at the B3LYP/6-31G(d).
  
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10. Scheme 3: Suzuki–Miyaura cross-coupling reaction of TB4 with 2-bromomesitylene. (a) 2-bromomesitylene (8 equi...
  
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Beilstein J. Org. Chem. 2020, 16, 621–627, doi:10.3762/bjoc.16.58

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Synthesis of C₇₀-fragment buckybowls bearing alkoxy substituents

Yumi Yakiyama,
Shota Hishikawa and
Hidehiro Sakurai

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Published 15 Apr 2020

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1. Graphical Abstract
2. Figure 1: Structure of the target buckybowls 5a–c.
  
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3. Scheme 1: Synthesis of dialkoxides 5a–c.
  
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4. Scheme 2: Proposed mechanism of the formation of 5b and 5c.
  
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5. Figure 2: Crystal structure of 5a. a) ORTEP drawing of the crystallographically independent unit with thermal...
  
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6. Figure 3: a) Definition of POAV angle (φ). b) Side and c) top view of the molecular skeleton of 1. The double...
  
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7. Figure 4: Crystal structure of 5b. a) ORTEP drawing of the crystallographically independent unit with thermal...
  
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8. Figure 5: Crystal structure of 5c. a) ORTEP drawing of the crystallographically independent unit with thermal...
  
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9. Figure 6: a) UV–vis spectra and b) emission spectra of 1 and dialkoxides 5a–c. For all the spectra, the conce...
  
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Beilstein J. Org. Chem. 2020, 16, 681–690, doi:10.3762/bjoc.16.66

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One-pot synthesis of dicyclopenta-fused peropyrene via a fourfold alkyne annulation

Ji Ma,
Yubin Fu,
Junzhi Liu and
Xinliang Feng

Letter
Published 20 Apr 2020

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1. Graphical Abstract
2. Scheme 1: Chemical structures of dicyclopenta-fused pyrene derivatives i–iii, peropyrene and the dicyclopenta...
  
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3. Scheme 2: Synthetic route towards compound 1. a) B₂pin₂, dtbpy, [Ir(OMe)cod]₂, cyclohexane, 70 °C, 20 h, 67%;...
  
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4. Figure 1: High-resolution MALDI-TOF mass spectrum of 1. Inset: isotopic distribution compared to mass spectru...
  
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5. Figure 2: Single-crystal X-ray structure of 1. (a) Top view and (b) side view of the (P,P) isomer. c) Crystal...
  
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6. Figure 3: (a) UV–vis absorption spectra of precursor 5 and 1 in CH₂Cl₂ solution (10⁻⁵ M). Inset: photograph o...
  
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7. Figure 4: Molecular orbitals of peropyrene derivative 6 and the dicyclopenta-fused peropyrene 1.
  
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Beilstein J. Org. Chem. 2020, 16, 791–797, doi:10.3762/bjoc.16.72

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Bipyrrole boomerangs via Pd-mediated tandem cyclization–oxygenation. Controlling reaction selectivity and electronic properties

Liliia Moshniaha,
Marika Żyła-Karwowska,
Joanna Cybińska,
Piotr J. Chmielewski,
Ludovic Favereau and
Marcin Stępień

Full Research Paper
Published 04 May 2020

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1. Graphical Abstract
2. Scheme 1: The previously reported family of the boomerang bipyrroles obtained by Pd-induced double C–H bond a...
  
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3. Scheme 2: Synthesis and structures of α-free and α-oxygenated bipyrrole boomerangs. Reagents and conditions: ...
  
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4. Figure 1: DFT-Optimized structures (B3LYP/6-31G(d,p)) of cNDA2^O and cNMI3^H.
  
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5. Figure 2: Absorption and emission spectra of cNMI2^H (top) and cNMI3^H (bottom) measured in toluene, dichlorome...
  
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Beilstein J. Org. Chem. 2020, 16, 895–903, doi:10.3762/bjoc.16.81

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Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes

Aya Yoshimura,
Hitoshi Kimura,
Kohei Kagawa,
Mayuka Yoshioka,
Toshiki Itou,
Dhananjayan Vasu,
Takashi Shirahata,
Hideki Yorimitsu and
Yohji Misaki

Full Research Paper
Published 12 May 2020

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1. Graphical Abstract
2. Figure 1: Target compounds.
  
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3. Scheme 1: Synthesis of compounds 3.
  
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4. Scheme 2: Synthesis of compound 4.
  
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5. Figure 2: An optimized structure of 1a. a) Top view, b) side view, and c) labeling of the 1,3-dithiole rings.
  
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6. Figure 3: Molecular orbitals of 1a.
  
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7. Figure 4: Cyclic voltammograms of 1a,b, 2a, and 4 in PhCN/CS₂ 1:1 (v/v) solution.
  
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8. Figure 5: Related compound 14.
  
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Beilstein J. Org. Chem. 2020, 16, 974–981, doi:10.3762/bjoc.16.86

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Clickable azide-functionalized bromoarylaldehydes – synthesis and photophysical characterization

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

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Published 14 Jul 2020

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1. Graphical Abstract
2. Scheme 1: a) Schematic depiction of the Jablonski diagram. b) Schematic representation of El-Sayed’s rule.
  
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3. Figure 1: Top: literature examples of organic compounds showing RTP in the crystalline state (a) and in solut...
  
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4. Scheme 2: Reaction conditions for para-bromobenzaldehyde 3: a) 1) 2-amino-2-methylpropan-1-ol, 4 Å MS, CH₂Cl₂...
  
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5. Scheme 3: Reaction conditions: a) Br₂, Fe powder, CHCl₃, 0 °C, 4 h, 99%; b) KOH, KI, MeI, DMSO, 25 °C, 18 h, ...
  
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6. Scheme 4: Reaction conditions: a) 1) NaH, THF, 0 °C, 30 min; 2) MeI, THF, 0 °C to 25 °C, 2 h, 99%; b) 1) MeOT...
  
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7. Scheme 5: a) CuAAC reactions of azide-functionalized bromocarbaldehydes 3, 4 and 5 with terminal alkynes to t...
  
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8. Figure 2: a) Normalized UV–vis absorption spectra of 3 (blue line), 34 (olive line), 4 (green line) and 38 (r...
  
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9. Figure 3: a) Normalized UV–vis absorption spectra of 5 (blue line), 16 (green line), 42 (olive line) and 45 (...
  
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Beilstein J. Org. Chem. 2020, 16, 1683–1692, doi:10.3762/bjoc.16.139

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C–H functionalization for materials science

Formal preparation of regioregular and alternating thiophene–thiophene copolymers bearing different substituents

Synthesis and circularly polarized luminescence properties of BINOL-derived bisbenzofuro[2,3-b:3’,2’-e]pyridines (BBZFPys)

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

Six-fold C–H borylation of hexa-peri-hexabenzocoronene

Synthesis of six-membered silacycles by borane-catalyzed double sila-Friedel–Crafts reaction

Synthesis of triphenylene-fused phosphole oxides via C–H functionalizations

Copper-catalyzed remote C–H arylation of polycyclic aromatic hydrocarbons (PAHs)

Efficient synthesis of 3,6,13,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes by selective C–H/C–O arylations of anthraquinone derivatives

Regioselectively α- and β-alkynylated BODIPY dyes via gold(I)-catalyzed direct C–H functionalization and their photophysical properties

Direct borylation of terrylene and quaterrylene

Synthesis of C₇₀-fragment buckybowls bearing alkoxy substituents

One-pot synthesis of dicyclopenta-fused peropyrene via a fourfold alkyne annulation

Bipyrrole boomerangs via Pd-mediated tandem cyclization–oxygenation. Controlling reaction selectivity and electronic properties

Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes

Clickable azide-functionalized bromoarylaldehydes – synthesis and photophysical characterization

Other Beilstein-Institut Open Science Activities

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