A. Byeun et al. / Tetrahedron Letters 54 (2013) 6712–6715
15. Typical experimental procedure: Pd(OAc)
6715
provided the highest yield. In addition, ligand 2 showed good activ-
2
(6.7 mg, 0.03 mmol), ligand 1 or 2
0.036 mmol), aryl halides (3.0 mmol), thiol (3.0 mmol) and NaHMDS
825 mg, 4.5 mmol) or KOtBu (505 mg, 4.5 mmol) were combined with
DMSO (10 mL) in a small round-bottomed flask. The resulting mixture was
stirred at 80 °C for 12 h. The reaction mixture was poured into water and
extracted with EtOAc. The solvent was removed under vacuum, and the
resulting crude product was purified by flash chromatography on silica gel to
give the desired product.
(
(
ity for the synthesis of unsymmetrical diaryl sulfide from the cou-
pling reaction of potassium thioacetate and aryl halides. We found
that the sterically bulky ligands do not always show good results,
and that the most important thing is the appropriate size of the
ligand toward the targeting coupling reaction.
Diphenylsulfane (7a): 1H NMR (300 MHz, CDCl
.07 (m, 3H); 13C NMR (75 MHz, CDCl
75 MHz, CDCl ) d 135.7, 131.0, 129.1, 127.0.
Phenyl(p-tolyl)sulfane (7b): H NMR (300 MHz, CDCl
2.28 (s, 3H); 13C NMR (75 MHz, CDCl
) d 137.4, 137.0, 132.2, 131.2, 129.9,
29.6, 128.9, 126.2, 21.0.
Phenyl(m-tolyl)sulfane (7c): H NMR (300 MHz, CDCl
) d 7.23–7.17 (m, 2H), 7.16–
13
3
7
(
3
) d 135.7, 131.0, 129.0, 127.0. C NMR
Acknowledgment
3
1
3
) d 7.28–7.06 (m, 9H),
This research was supported by the Nano Material Technology
Development Program through the National Research Foundation
of Korea (NRF) funded by the Ministry of Education, Science and
Technology (grant number 2012M3A7B4049655).
3
1
1
3
) d 7.32–7.13 (m, 17H),
.01 (d, J = 6.1 Hz, 2H), 2.26 (s, 6H); C NMR (75 MHz, CDCl ) d 138.9, 136.0,
135.2, 131.8, 130.6, 129.0, 129.0, 128.3, 127.9, 126.7, 21.2.
Phenyl(2,4,5-trimethylphenyl)sulfane (7d): 1H NMR (300 MHz, CDCl
.95 (m, 5H), 2.27 (s, 2H), 2.18 (s, 2H), 2.13 (s, 2H); 13C NMR (75 MHz, CDCl
d 138.4, 137.7, 137.2, 135.8, 134.9, 132.0, 128.8, 127.6, 125.3, 20.0, 19.3, 19.0.
4-Methoxyphenyl)(phenyl)sulfane (7e): 1H NMR (300 MHz, CDCl
) d 7.40 (dd,
13
7
3
3
) d 7.24–
6
3
)
Supplementary data
(
3
J = 8.7, 2.1 Hz, 2H), 7.24–7.01 (m, 5H), 6.88 (dd, J = 8.7, 2.1 Hz, 2H), 3.79 (s,
3
1
H); 13C NMR (75 MHz, CDCl
24.2, 114.9, 55.3.
3
) d 159.7, 138.5, 135.3, 128.9, 128.1, 125.7,
4-(Phenylthio)benzonitrile (7f): 1H NMR (300 MHz, CDCl
3
) d 7.52–7.47 (m,
1
3
3
H), 7.45–7.41 (m, 4H), 7.17–7.13 (d, J = 8.7 Hz, 2H); C NMR (75 MHz,
CDCl ) d 145.6, 134.4, 132.2, 130.7, 129.8, 129.3, 127.2, 118.7, 108.5.
4-Nitrophenyl)(phenyl)sulfane (7g): H NMR (300 MHz, CDCl
3
References and notes
1
(
3
) d 8.00 (d,
J = 9.0 Hz, 2H), 7.53–7.41 (m, 5H), 7.13 (d, J = 9.0 Hz, 2H); C NMR (75 MHz,
CDCl ) d 148.2, 145.0, 134.4, 130.1, 129.8, 129.4, 126.3, 123.7.
(4-(Phenylthio)phenyl)ethanone (7h): H NMR (300 MHz, CDCl
1
3
1
.
3
1
3
) d 7.81 (d,
J = 8.4 Hz, 2H), 7.51–7.46 (m, 2H), 7.45–7.35 (m, 3H), 7.20 (d, J = 8.4 Hz, 2H),
2.54 (s, 3H); 13C NMR (75 MHz, CDCl
129.6, 128.7, 127.4, 26.4.
) d 197.0, 144.8, 134.4, 133.8, 132.0,
3
Methyl 4-(phenylthio)benzoate (7i): 1H NMR (300 MHz, CDCl
) d 7.89 (d,
3
J = 8.7 Hz, 2H), 7.50–7.46 (m, 2H), 7.39–7.37 (m, 3H), 7.19 (d, J = 8.7 Hz, 2H),
3.88 (s, 3H); 13C NMR (75 MHz, CDCl
129.6, 128.6, 127.5, 127.4,52.0.
) d 166.6, 144.3, 133.6, 132.3, 130.0,
2
3
.
.
3
2-(Phenylthio)benzaldehyde (7j): 1H NMR (300 MHz, CDCl
) d 9.88 (S, 1H), 7.69
3
(dd, J = 8.7, 1.8 Hz, 2H), 7.52–7.49 (m, 2H), 7.41–7.38 (m, 3H), 7.21 (dd, J = 8.7,
1.8 Hz, 2H); 13C NMR (75 MHz, CDCl
129.9, 129.6, 129.0, 127.0.
) d 190.9, 147.0, 134.2, 133.5, 131.1,
Naphthalene-1-(phenyl)sulfane (7k): 1H NMR (300 MHz, CDCl
) d 8.39–8.26
3
3
4
5
.
.
(m, 1H), 7.82 (t, J = 9.3 Hz, 2H), 7.64 (dd, J = 7.2, 1.2 Hz, 1H), 7.50–7.40 (m,
2H), 7.37 (dd, J = 8.1, 7.2 Hz, 1H), 7.20–7.10 (m, 5H); 13C NMR (75 MHz,
3
CDCl ) d 136.9, 134.2, 133.5, 132.5, 131.1 129.1, 129.0, 128.9, 128.5, 126.9,
126.4, 126.1, 125.8, 125.6.
Biphenyl-4-(phenyl)sulfane (7l): 1H NMR (300 MHz, CDCl
) d 7.54–7.46 (m,
3
4H), 7.41–7.20 (m, 10H); 13C NMR (75 MHz, CDCl
) d 140.2, 139.8, 135.6,
134.8, 131.2, 131.0, 129.2, 128.8, 127.8, 127.4, 127.0, 126.8.
2-(Phenylthio)pyridine (7m): 1H NMR (300 MHz, CDCl
) 8.41 (ddd, J = 4.8, 1.8,
3
3
0.8 Hz, 1H), 7.60–7.57 (m, 2H), 7.45–7.39 (m, 4H), 6.99–6.94 (m, 1H), 6.86 (d,
J = 8.0 Hz, 1H); 13C NMR (75 MHz, CDCl
129.5, 128.9, 121.2, 119.7.
) d 161.3, 149.4, 136.6, 134.8, 130.9,
3-(Phenylthio)pyridine (7n): 1
H NMR (300 MHz, CDCl ) d 8.55 (d, J = 2.4,
3
3
6
7
.
.
0.6 Hz, 1H), 8.43 (dd, J = 4.2, 1.5 Hz, 1H), 7.54 (ddd, J = 8.0, 2.3, 1.6 Hz,
1H).), 7.37–7.24 (m, 5H), 7.14 (ddd, J = 7.2, 4.8, 0.6 Hz, 1H); 3C NMR
1
(75 MHz, CDCl
123.5.
3
) d 150.7, 147.5, 137.5, 133.6, 133.2, 131.4, 129.2, 127.5,
2-(Phenylthio)thiophene (7o): 1H NMR (300 MHz, CDCl
) d
7.47 (d,
8
9
.
.
3
1
3
J = 5.4 Hz, 1H), 7.30–7.14 (m, 6H), 7.07 (dd, J = 5.4, 3.6 Hz, 1H);
C
NMR (75 MHz, CDCl
126.0.
3
) d 138.6, 136.1, 131.3, 131.1, 128.9, 127.9, 127.1,
(4-tert-Butylphenyl)(4-methoxyphenyl)sulfane (7p): 1H NMR (300 MHz,
CDCl
J = 8.8 Hz, 2H), 6.83 (d, J = 8.9 Hz, 2H), 3.72 (s, 3H), 1.26 (s, 9H);
NMR (75 MHz, CDCl d 159.4, 148.9, 134.7, 134.6, 128.4, 125.9, 124.9,
114.8, 55.1, 34.3, 31.2.
(4-Chlorophenyl)(4-methoxyphenyl)sulfane (7q): 1H NMR (300 MHz, CDCl
3
) d 7.36 (d, J = 8.9 Hz, 2H), 7.23 (d, J = 8.7 Hz, 2H), 7.12 (d,
13
C
1
1
1
3
)
3
)
d 7.40 (d, J = 8.9 Hz, 2H), 7.19 (d, J = 8.8 Hz, 2H), 7.07 (d, J = 8.8 Hz, 2H),
6.90 (d, J = 8.9 Hz, 2H), 3.82 (s, 3H); 13C NMR (75 MHz, CDCl
) d 160.0,
3
1
1