E
T. Sperger et al.
Paper
Synthesis
used in workup and purification were distilled prior to use. Pd(I)–
iodo dimer 2 was prepared from Pd2(dba)3, Pt-Bu3, and PdI2 according
to a literature procedure.11b All 1H, 13C, and 31P NMR spectra were re-
corded on Varian VNMRS 600, Varian VNMRS 400, or Varian Mercury
300 spectrometers at ambient temperature. Chemical shifts (δ) are
reported in ppm referenced either to the residual solvent peak (CDCl3
for 1H and 13C spectra) or PO(OMe)3 (δ = 3.05) added as an internal
standard for 31P NMR. GC-MS was performed on an Agilent Technolo-
gies 5975 series MSD mass spectrometer coupled with an Agilent
Technologies 7820A gas chromatograph. HRMS was performed by us-
ing a Thermo Scientific LTQ Orbitrap XL spectrometer. IR spectra were
recorded on a Spectrum 100 spectrometer with an UATR Dia-
mond/KRS-5 crystal with attenuated total reflectance (ATR). Kugel-
rohr distillation was performed by using a Büchi Glass Oven B-585
Kugelrohr apparatus.
Supporting Information
Supporting information for this article is available online at
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References
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Heck Cross-Coupling Reactions; General Procedure
Aryl iodide 3 (0.2 mmol, 1.0 equiv), acrylate/styrene 4 (0.202 mmol,
1.01 equiv), DIPEA (28.4 mg, 0.22 mmol, 1.1 equiv), and Pd(I)–iodo di-
mer 2 (1.3 mg, 0.0015 mmol, 0.75 mol%) were weighed into a 4 mL
screw cap vial, purged with argon, and dissolved in anhydrous tolu-
ene (1.5 mL). The vial was capped with a PTFE-lined screw cap and
sealed with PTFE tape prior to heating to 100 °C under stirring by us-
ing an aluminum heating block outside the glovebox. After 15 h, the
reaction mixture was allowed to cool to r.t. and diluted with EtOAc (to
20 mL); excess base was quenched by the addition of sat. aq NH4Cl (20
mL). The organic phase was separated and the aqueous layer was ex-
tracted with EtOAc (2 × 20 mL). The combined organic layer was dried
over MgSO4 and the solvent was removed under reduced pressure.
The obtained crude product was purified by flash column chromatog-
raphy.
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dimer 2 was first synthesized by: Vilar, R.; Mingos, D. M. P.;
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(Johnson Matthey) WO2011/12889A1, 2011.
tert-Butyl (E)-3-(4-{[(Trifluoromethyl)sulfonyl]oxy}phenyl)acry-
late (5mc)
The title compound was obtained according to the general procedure
from either 4-iodophenyl triflate or 4-bromophenyl triflate. The
crude mixture was purified by column chromatography (hexane–
EtOAc, 20:1); Rf = 0.41 (hexane–EtOAc, 10:1); this afforded the prod-
uct as a colorless oil.
Yield: 64.8 mg (0.184 mmol, 91%; from aryl iodide) or 65.2 mg (0.185
mmol, 92%; from aryl bromide).
IR (neat): 2969, 2325, 2095, 1711, 1409, 1165, 993, 866, 720 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.58–7.49 (m, 3 H, ArH, CH), 7.29–7.22
(m, 2 H, ArH), 6.34 (d, J = 16.0 Hz, 1 H, CH), 1.51 (s, 9 H, CH3).
13C NMR (101 MHz, CDCl3): δ = 165.8 (C), 150.2 (C), 141.2 (CH), 135.2
(C), 129.7 (CH), 122.5 (CH), 122.0 (CH), 118.85 (q, J = 320.9 Hz, CF3),
81.1 (C), 28.3 (CH3).
19F NMR (CDCl3, 376 MHz): δ = –72.87 (s, 3 F, SO2CF3).
MS (EI): m/z (%) = 352.1 (100) [M]+, 353.1 (16), 354.0 (6), 354.9 (1).
HRMS: m/z [M]+ calcd for C14H15F3O5S: 352.0587; found: 352.0588.
(10) (a) Bonney, K. J.; Proutière, F.; Schoenebeck, F. Chem. Sci. 2013,
4, 4434. (b) Kalvet, I.; Bonney, K. J.; Schoenebeck, F. J. Org. Chem.
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(11) (a) Yin, G.; Kalvet, I.; Schoenebeck, F. Angew. Chem. Int. Ed. 2015,
54, 6809. (b) Aufiero, M.; Sperger, T.; Tsang, A. S.; Schoenebeck,
F. Angew. Chem. Int. Ed. 2015, 54, 10322.
(12) Aufiero, M.; Scattolin, T.; Proutière, F.; Schoenebeck, F. Organo-
metallics 2015, 34, 5191.
Acknowledgment
We thank the RWTH Aachen University, the MIWF NRW, as well as
the Evonik Foundation (doctoral scholarship to T.S.) for financial sup-
port.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–F