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Letter
Synlett
Acknowledgment
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(13) AgF is shown to sever as an oxidant for homocoupling reaction
in the absence of aryl halide. See ref. 4b.
This work was supported financially by Special Coordination Funds
for Promoting Science and Technology, Creation of Innovation Centers
for Advanced Interdisciplinary Research Areas (Innovative Bioproduc-
tion Kobe) and Kakenhi (Challenging Exploratory Research
26620146, 2014-2016) by MEXT, Japan. ST thanks JSPS for the Re-
search Fellowship for Young Scientists.
#
Supporting Information
Supporting information for this article is available online at
tal details, spectroscopic characteristics, and copies of NMR spectra.
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References and Notes
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(14) Preparation of 2-Furylthiazole-4-carboxylic Acid Methyl
Ester (3)
To a solution of 2-cyanofuran (4) in MeOH–H2O (2:1, 43 mL)
were added L-cysteine (1.82 g, 15 mmol) and K2CO3 (2.07 g, 15
mmol). The solution warmed to 60 °C and stirred for 21.5 h
under nitrogen atmosphere. After cooling to r.t., the reaction
mixture was diluted with MeOH, and the solution was concen-
trated under reduced pressure to leave a crude solid, which was
purified by short column chromatography on silica gel (MeOAc)
to afford furylthiazoline carboxylic acid (5) as orange crude
solid.
To a solution of the crude solid of 5 in DMF (100 mL) were
added K2CO3 (4.14 g, 30 mmol) at r.t. under an nitrogen atmo-
sphere. After cooling to 0 °C, MeI (1.87 mL, 30 mmol) was added
dropwise. After stirring for 1.5 h at 0 °C, the mixture was
quenched by H2O, and the solution was poured into the mixture
of Et2O–H2O to result in separation into two phases. The
aqueous phase was extracted with Et2O repeatedly, and the
combined organic layer was dried over anhydrous Na2SO4 and
concentrated under reduced pressure to leave a crude oil, which
was purified by column chromatography on silica gel (hexane–
MeOAc, 3:1) to afford 1.33 g of furylthiazoline carboxylic acid
methyl ester (5′, 63%).
To a 20 mL Schlenk tube equipped with a magnetic stirring bar
were added 5′ (105.6 mg, 0.5 mmol) and toluene (1.5 mL). To
the solution was added activated carbon (105.6 mg, 100 wt%),
and stirring was continued at 100 °C for 22.5 h under oxygen
atmosphere. After cooling to r.t., the mixture was diluted with
CHCl3 and passed through a Celite pad, which was washed with
CHCl3 repeatedly. The filtrate was concentrated under reduced
pressure to leave the crude solid, which was purified by column
chromatography on silica gel to afford 98.3 mg of 3 as a yellow
solid (94%). The reaction was also performed in a larger scale
under similar conditions with 5′ (2.58 g, 12.2 mmol) and acti-
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 1496–1500