10.1002/ejoc.201800651
European Journal of Organic Chemistry
FULL PAPER
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Experimental Section
General Information: All manipulations were conducted under argon
with exclusion of moisture and oxygen by using standard techniques for
the manipulation of air sensitive compounds. Reaction temperatures refer
to silicon oil in an additional pressure tube within the heated aluminium
block. NMR data were recorded on Bruker ARX 300, Bruker ARX 400
and Bruker Fourier 300 spectrometers. 13C and 1H NMR spectra are
given in ppm and referenced to signals of deuterated solvents and
residual protonated solvents, respectively (Acetone-d6: 1H: 2.050 ppm,
13C: 29.840 ppm; CD2Cl2: 1H: 5.320 ppm, 13C: 54.000 ppm). The
assignment of the carbon atoms was accomplished by aid of DEPT
spectra. Gas chromatography analysis was performed on an Agilent HP-
5890 instrument with a FID detector and HP-5 capillary column using
argon as carrier gas. Gas chromatography-mass analysis was carried out
on an Agilent HP-5890 instrument with an Agilent HP-5973 Mass
Selective Detector (EI) and HP-5 capillary column using helium carrier
gas. TOF HR-MS measurements were performed on an Agilent
1200/6210 Time-of-Flight LC-MS. Flash chromatography was performed
on a Teledyne Isco CombiFlash Rf 200 system. Chemicals were
purchased from Sigma Aldrich, Alfar Aesar, TCI or Strem and were used
as received. DMF was dried by a SPS from Innovative Technology while
H2O was flushed with argon for one hour. Solvents were stored in Aldrich
Sure/store flasks under argon.
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General Procedure for the Sonogashira-Semihydrogenation towards
Z-Alkenes: In general, all steps are conducted subsequently without any
intermediate work-up. Additives or solvents are only added after each
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step when indicated. In
a glass pressure tube under argon, 4-
bromotoluene (0.5 mmol, 63.5 µL), phenylacetylene (1 mmol, 110 µL)
and DMF (2 mL) were added to the already present solids PdCl2 (1 mol%,
0.9 mg), BuPAd2 (1 mol%, 1.8 mg) and K2CO3 (1 mmol, 138 mg). The
pressure tube was closed and the mixture was stirred in an aluminium
block at 60 °C for 16 hours. Afterwards, 0.2 mL H2O was added to
reaction mixture under argon counter flow. The tube was closed again
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temperature (25 °C) for
a specific time without further additives.
Afterwards, argon was passed through the solution for 10 minutes to
remove dissolved hydrogen gas. For work-up, the product was purified
by flash chromatography after initial extraction to give 73 mg (75%) of 4a.
Detailed information can be obtained from the provided Supporting
Information.
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Acknowledgements
We thank Patrick Piehl, Jacob Schneidewind, Max Hertrich,
Sandra Leiminger and the analytical department for fruitful
discussions and technical support. The research was conducted
as a part of the CHEM21 project funded by the EU and EFPIA.
This work was supported by the state of Mecklenburg-
Vorpommern, the BMBF and the EU.
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Keywords: Catalysis • Palladium • Z-Alkenes • Sonogashira
Coupling • Hydrogenation
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