10.1002/chem.201701671
Chemistry - A European Journal
General procedure for Table 1
Lowe, Polym. Chem. 2010, 1, 17; d) J. Liu, J. Yang, Q. Yang, G. Wang, Y. Li,
Adv. Funct. Mater. 2005, 15, 1297.
A 5 mL sealable tube equipped with a Teflon-coated magnetic stir bar was
charged with catalyst (5 mol%), ligand (10 mol%) and base (1.7 equiv). The
tube was then evacuated and backfilled with argon (this sequence was repeated
three times), and 4-bromotoluene (0.160 mL, 1.3 mmol), thiophenol (0.102
mL, 1.0 mmol) and solvent (1.5 mL ) were then added into the tube via syringe.
The reaction mixture was stirred at 110 °C in an oil bath for 24 h. After cooling
to room temperature, the crude product was diluted with ethyl acetate (~40
mL), and filtered through silica gel pad. Then the filtrate was concentrated in
vacuum. The residue was purified by flash chromatography (SiO2, hexane) to
yield 3a.
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The representative example of Table 1
Phenyl(p-tolyl)sulfane (3a):[25] Following the condition A, using 4-
bromotoluene (0.160 mL, 1.3 mmol), CuI (9.5 mg), L5 (25.4 mg), KOtBu
(0.186g, 1.7 mmol), thiophenol (0.102 mL, 1.0 mmol) and dioxane (1.5 mL),
then purified by column chromatography (SiO2, hexane) to provide 3a as a
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1
yellow liquid (196 mg, 98% yield). H NMR (400 MHz, CDCl3): δ 2.28 (s,
3H), 7.06-7.13 (m, 3H), 7.17-7.28 (m, 6H); 13C NMR (100 MHz, CDCl3): δ
21.0, 126.2, 128.9, 129.6, 129.9, 131.2, 132.2, 137.0, 137.4.
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General procedure for Table 2-4 and Table 6:
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Condition A: A 5 mL sealable tube equipped with a Teflon-coated magnetic
stir bar was charged with CuI (9.5 mg), L5 (25.4 mg), (hetero)aryl halide (if
solid) (1.3 mmol), thiolphenol (if solid) (1.0 mmol) and KOtBu (1.7 mmol for
condition A, 2.5 mmol for condition B). The tube was then evacuated and
backfilled with argon (this sequence was repeated three times), and
(hetero)aryl halide (if liquid) (1.3 mmol), thiolphenol (if liquid) (1.0 mmol)
and solvent (1.5 mL dioxane ) were then added into the tube via syringe. The
reaction mixture was stirred at 110 °C (condition A) or 135 °C (condition B)
in an oil bath for 24 h. After cooling to room temperature, the crude product
was diluted with ethyl acetate (~40 mL), and filtered through silica gel pad.
Then the filtrate was concentrated in vacuum. The residue was purified by
flash chromatography (eluting with ethyl acetate/hexane) to afford the
corresponding thioethers.
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Condition C (for all aryl chlorides): A 5 mL sealable tube equipped with a
teflon-coated magnetic stir bar was charged with CuI (9.5 mg), L5 (25.4 mg),
(hetero)aryl halide (if solid) (1.3 mmol), thiolphenol (if solid) (1.0 mmol) and
KOtBu (2.5 mmol). The tube was then evacuated and backfilled with argon
(this sequence was repeated three times), and (hetero) aryl halide (if liquid)
(1.3 mmol), thiolphenol (if liquid) (1.0 mmol) and toluene (1.5 mL) were then
added into the tube via syringe. The reaction mixture was stirred at 135 °C in
an oil bath for 24 h. After cooling to room temperature, the crude product was
diluted with ethyl acetate (~40 mL), and filtered through silica gel pad. Then
the filtrate was concentrated in vacuum. The resulting residue was purified by
flash chromatography (eluting with ethyl acetate/hexane) to afford the
corresponding thioethers.
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Acknowledgements
The Ministry of Science and Technology, Taiwan (MOST 105-2113-M-005-001-) and
the National Chung Hsing University are gratefully acknowledged for financial support.
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