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1

Synthesis and Characterization of 10,10'-Dibromo-9,9'-bianthryl

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Unless otherwise
stated, all manipulations
of air- and/or moisture-sensitive compounds were carried out in oven-dried
glassware under an atmosphere of N2. All solvents and reagents
were purchased from Alfa Aesar, Spectrum Chemicals, Acros Organics,
TCI America, and Sigma-Aldrich and used as received unless otherwise
noted. Organic solvents were dried by passing through a column of
alumina and were degassed by vigorous bubbling of N2 through
the solvent for 20 min. Flash column chromatography was performed
on SiliCycle silica gel (particle size 40–63 μm). Thin-layer
chromatography was carried out using SiliCycle silica gel 60 Å
F-254 precoated plates (0.25 mm thick) and visualized by UV absorption.
All 1H and 13C NMR spectra were recorded on
a Bruker AV-600 spectrometer and are referenced to residual solvent
peaks (CDCl3, 1H NMR = 7.26 ppm, 13C NMR = 77.16 ppm; CD2Cl2, 1H NMR
= 5.32 ppm, 13C NMR = 53.84 ppm). EI mass spectrometry
was performed on an AutoSpec Premier (Waters) system in positive ionization
mode. MALDI mass spectrometry was performed on a Voyager-DE PRO (Applied
Biosystems Voyager System 6322) instrument in positive mode using
a matrix of dithranol. 10,10′-Dibromo-9,9′-bianthryl
was synthesized following a reported procedure.74 (link)
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2

Characterization of Organoboron Compounds

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Dried solvents and argon as protection gas were used. 11B, 13C, 19F, 29Si, and 77Se NMR spectra were recorded with a JEOL ECZ 400R or with a JEOL ECS 400 spectrometer (128.25, 100.51, 376.13, 79, and 76.24 MHz, respectively). Chemical shifts δ are reported in ppm relative to BF3OEt2 (11B), Me4Si (13C, 29Si), CFCl3 (19F), and Me2Se (77Se).
For ESI‐TOF mass spectra, the samples were measured from CH3CN, CH3CN/CH2Cl2, CH3OH, or CH3CN/CH3OH solutions with an Agilent 6210 ESI‐TOF, Agilent Technologies, Santa Clara, CA, USA. The solvent flow rate was adjusted to 4 μL min−1, spray voltage set to 4 kV, drying gas flow rate was set to 15 psi (1 bar; ESI‐TOF=electrospray ionization–time of flight). Non‐ionic compounds were analyzed with a HR‐EI‐MS (Autospec Premier, Waters Co., Milford, MA, USA) using 80 eV electron energy.
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3

Analytical Techniques for Natural Products

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Optical rotations were measured on an Anton Paar MCP 5100 polarimeter. IR spectra were obtained using a Nicolet 380 FT-IR instrument (Thermo, USA) using KBr pellets. HRESIMS were determined by a Waters Autospec Premier (Waters, USA) mass spectrometer. The NMR spectra were recorded on Bruker Avance 500 NMR spectrometers (Bruker, Germany) with TMS as an internal standard. The high performance liquid chromatography (HPLC) was performed with an analytic reversed-phased column (YMC–packed C18, 250 mm × 10 mm, 5 µm) (YMC, Japan) using a G1311C 1260 Quat Pump VL and detected with a G1315D 1260 DAD VL detector (190–500 nm) (Agilent Technologies 1260 infinity, USA). For column chromatography, silica gel (60–80, 200–300 mesh, Qingdao Haiyang Chemical Co., Ltd, China), ODS gel (20–45 µm, Fuji Silysia Chemical Co., Ltd, USA), and Sephadex LH-20 (Merck, Germany) were used. TLC analysis was performed on precoated silica gel GF254 plates (Qingdao Haiyang Chemical Co., Ltd, China), and spots were visualized by spraying with 5% H2SO4 in EtOH followed by heating. Thermo fisher scientific plate reader was used for enzyme inhibition assays.
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4

Organometallic Compound Synthesis Procedures

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Most manipulations of organometallic compounds were carried out using standard Schlenk techniques under an atmosphere of dry argon. CH2Cl2, hexane, toluene, and chloroform were dried by distillation over CaH2, pyridine over KOH. Melting points were determined on a Kofler apparatus of the Boetius type. 1H and 13C NMR spectra were recorded on a Bruker Avance II spectrometer (400 and 100 MHz, respectively). Spectra are referenced relative to the chemical shift (δ) of TMS. Mass spectra were obtained with Micromass LCT TOF and AutoSpec Premier (Waters) spectrometers. Infrared spectra were recorded on a FT-IR spectrometer as KBr pellets or as solid samples using the ATR technique. Flash chromatography (FC) was performed on silica gel 230–400 mesh. Yields refer to chromatographically purified products unless otherwise stated. Catalysts 3 and 5 were commercially available. Substrates for testing catalysts in RCM reactions were prepared by allylation of commercial diethyl malonate with allyl bromide and/or 3-chloro-2-methylpropene according to Hensle [24 (link)]. Their purity was estimated by 1H NMR spectroscopy and found to be at least 95 %. Other chemicals are commercially available and used as received. N-Mesityl-N’-(2-nitrophenyl)ethylenediamine (9) was prepared according to literature [14 (link)].
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5

NMR and Mass Spectra Analysis

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1 H and 13 C NMR spectra were acquired on a JEOL ECX 400 (400 MHz), JEOL ECP 500 (500 MHz) and a Bruker Avance 700 (700 MHZ) in CDCl3 as a solvent. The chemical shifts were reported relative to CDCl3 (δ = 1 H: 7.26 ppm, 13 C: 77.16 ppm). The multiplicities of the signals are described using the following abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, p = quintuplet, br = broad and combinations thereof.
The spectra were evaluated with the software MestRec.
Mass spectra were obtained on a ESI-FTICR-MS: Ionspec QFT-7 (Agilent/Varian), or a HR-EI-MS: Autospec Premier (Waters).
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