5
1
1520 mg (89%). H NMR (400 MHz, CDCl3): δ 7.84 (d, J = 8.5
5.55; N, 10.06; S, 7.68. Found: C, 69.07; H, 5.58; N, 9.89, S,
7.72.
Hz, 2H), 7.51 (d, J = 8.5 Hz, 2H), 7.24 (t, J = 3.2 Hz, 6H), 7.07-
7.05 (m, 4H), 4.33 (s, 4H). 13C NMR (100 MHz, CDCl3): δ
140.6, 138.3, 135.3, 128.5, 128.4, 128.3, 127.8, 99.6, 50.6.
HRMS Calcd for C20H18INO2S [M+]: 463.0103. Found:
462.6567.
N,N-dibenzyl-4-(1H-imidazol-1-yl)benzenesulfonamide (2d).
Following the general procedure imidazole (0.054 g, 0.80 mmol)
and N,N-dibenzyl-4-iodobenzenesulfonamide ( 0.556 g, 1.20
mmol) provided 261 mg (81% yield) of the coupling product as
yellow powder after purification by flash chromatography (80: 20
General Procedure for the Cross Coupling Reaction. The N-
nucleophile (0.4-0.8 mmol), CuI (0.004-0.04 mmol), Cs2CO3
(0.8-1.6 mmol), N,N-dibenzyl-4-iodobenzenesulfonamide (0.6-
1.2 mmol) and dimethylformami-de (DMF) (0.2-0.4 mL) were
added to a reaction vial and a screw cap was fitted to it. The
reaction mixture was stirred under air in a closed system at 130˚C
for 24 h. After cooling to room temperature, the mixture was
diluted with dichloromethane and filtered through a pad of Celite.
The combined organic extracts were dried with anhydrous
Na2SO4 and the solvent was removed under reduced pressure.
The crude product was purified by silica-gel column
chromatography to afford the N-arylated product. The identity
and purity of the products was confirmed by 1H, 13C NMR
spectroscopic analysis and elemental analysis or mass
spectroscopy.
1
hexane/ethyl acetate). H NMR (400 MHz, CDCl3): δ 7.94-7.90
(m, 3H), 7.51-7.48 (m, 2H), 7.35 (s, 1H), 7.27-7.23 (m, 7H),
7.11-7.09 (m, 4H), 4.38 (s, 4H). 13C NMR (100 MHz, CDCl3): δ
140.2, 139.5, 135.3, 135.2, 131.3, 129.1, 128.6, 128.5, 127.8,
121.1, 117.7, 50.6. Anal. Calcd for C23H21N3O2S: C, 68.46; H,
5.25; N, 10.41; S, 7.95. Found: C, 68.25; H, 5.24; N, 10.44; S,
7.78.
N,N-dibenzyl-4-(1H-1,2,4-triazol-1-yl)benzenesulfonamide
(2e). Following the general procedure triazole (0.055 g, 0.80
mmol) and N,N-dibenzyl-4-iodobenzenesulfonamide ( 0.556 g,
1.20 mmol) provided 249 mg (77% yield) of the coupling
product as yellow powder after purification by flash
chromatography (70: 30 hexane/ethyl acetate). 1H NMR (400
MHz, CDCl3): δ 8.67 (s, 1H), 8.16 (s, 1H), 7.94 (d, J = 8.7 Hz,
2H), 7.83 (d, J = 8.8 Hz, 2H), 7.25-7.23 (m, 6H), 7.11-7.08 (m,
4H), 4.37 (s, 4H). 13C NMR (100 MHz, CDCl3): δ 153.8, 153.2,
141.1, 140.3, 139.6, 135.2, 129.8, 128.7, 127.9, 119.9, 50.6.
Anal. Calcd for C22H20N4O2S: C, 65.33; H, 4.98; N, 13.85; S,
7.93. Found: C, 65.17; H, 4.98; N, 13.41; S, 7.86.
N,N-dibenzyl-4-(3-(trifluoromethyl)-1H-pyrazol-1-
yl)benzenesulfonami -de (2a).11 Following the general
procedure
using
N,N-dibenzyl-4-iodobenzenesulfonamide
(0.556g, 1.20 mmol) and 3-trifluoromethylpyrazole (0.109 g,
0.80 mmol) provided 372 mg (99%) of the coupling product as
yellow powder after purification by flash chromatography (87: 13
N,N-dibenzyl-4-(1H-pyrrol-1-yl)benzenesulfonamide
(2f).
1
hexane/ethyl acetate). H NMR (400 MHz, CDCl3): δ 8.05 (s,
Following the general procedure pyrrole (0.056 mL, 0.80 mmol)
and N,N-dibenzyl-4-iodobenzenesulfonamide (0.556 g, 1.20
mmol) provided 224 mg (70% yield) of the coupling product as
yellow powder after purification by flash chromatography (95: 5
1H), 7.92 (d, J = 8.8 Hz, 2H), 7.85 (d, J = 8.9 Hz, 2H), 7.26-7.20
(m, 7H), 7.10-7.08 (m, 4H), 6.80 (d, J = 2.5 Hz, 1H), 4.33 (s,
4H). 13C NMR (100 MHz, CDCl3): δ 145.1, 144.8, 141.9, 139.6,
135.3, 128.8, 128.6, 128.5, 127.8, 119.6, 106.9, 106.8, 50.6.
Anal. Calcd for C24H20F3N3O2S: C, 61.14; H, 4.28; N, 8.91; S,
6.80. Found: C, 60.28; H, 4.48; N, 8.29; S, 6.40. HRMS Calcd
for C24H20F3N3O2S [M+]: 471.1228. Found: 471.0885.
1
hexane/ethyl acetate). H NMR (400 MHz, CDCl3): δ 7.86-7.84
(m, 2H), 7.47-7.45 (m, 2H), 7.22 (t, J = 3.1 Hz, 6H), 7.15 (t, J =
2.2 Hz, 2H), 7.09-7.06 (m, 4H), 6.41 (t, J = 2.2 Hz, 2H), 4.35 (s,
4H). 13C NMR (100 MHz, CDCl3): δ 143.9, 137.1, 135.4, 128.9,
128.5, 128.4, 127.7, 119.8, 119.0, 111.9, 50.5. Anal. Calcd for
C24H22N2O2S: C, 71.62; H, 5.51; N, 6.96; S, 7.97. Found: C,
71.08; H, 5.36; N, 6.80; S, 7.40.
N,N-dibenzyl-4-(1H-pyrazol-1-yl)benzenesulfonamide (2b).
Following the general procedure pyrazole (0.054 g, 0.80 mmol)
and N,N-dibenzyl-4-iodobenzenesulfonamide ( 0.556 g, 1.20
mmol) provided 298 mg (92% yield) of the coupling product as
yellow powder after purification by flash chromatography (75: 25
hexane/ethyl acetate). 1H NMR (400 MHz, CDCl3): δ 8.01 (d, J =
2.5 Hz, 1H), 7.92-7.85 (m, 2H), 7.84-7.82 (m, 2H), 7.79 (d, J =
1.6 Hz, 1H), 7.24-7.19 (m, 6H), 7.11-7.08 (m, 4H), 6.55 (t, J =
2.2 Hz, 1H), 4.35 (s, 4H). 13C NMR (100MHz, CDCl3): δ 142.9,
142.3, 138.1, 135.4, 128.8, 128.6, 128.6, 127.8, 126.9, 118.8,
108.8, 50.6. Anal. Calcd for C23H21N3O2S: C, 68.46; H, 5.25; N,
N,N-dibenzyl-4-(1H-indol-1-yl)benzenesulfonamide
(2g).
Following the general procedure indole (0.094 g, 0.80 mmol) and
N,N-dibenzyl-4-iodobenzenesulfonamide ( 0.556 g, 1.20 mmol)
provided 320 mg (88% yield) of the coupling product as yellow
powder after purification by flash chromatography (96: 4
hexane/ethyl acetate). 1H NMR (400 MHz, CDCl3): δ 7.92 (d, J =
8.6 Hz, 2H), 7.70 (d, J = 7.7 Hz, 1H), 7.59 (t, J = 7.7 Hz, 3H),
7.34 (d, J = 3.4 Hz, 1H), 7.28-7.21 (m, 8H), 7.11-7.09 (m, 4H),
6.74 (d, J = 3.3 Hz, 1H), 4.40 (s, 4H). 13C NMR (100 MHz,
CDCl3): δ 143.2, 138.0, 135.4, 135.3, 129.8, 128.8, 128.6, 128.5,
127.8, 127.2, 123.7, 123.1, 121.5, 121.2, 110.3, 105.3, 50.6.
Anal. Calcd for C28H24N2O2S: C, 74.31; H, 5.35; N, 6.19; S, 7.09.
Found: C, 74.26; H, 5.38; N, 6.04; S, 6.98.
1
10.41; S, 7.95. Found: C, 68.50; H, 5.26; N, 10.28; S, 8.08. H
NMR (400 MHz, CDCl3): δ 7.89-7.86 (m, 3H), 7.79-7.77 (m,
2H), 7.25-7.21 (m, 6H), 7.09-7.07 (m, 4H), 6.32 (s, 1H), 4.34 (s,
4H), 2.39 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 151.9, 142.7,
137.4, 135.5, 128.8, 128.6, 128.5, 127.8, 127.4, 118.3, 109.0,
50.5, 13.8. Anal. Calcd for C24H23N3O2S: C, 69.04; H, 5.55; N,
10.06; S, 7.68. Found: C, 69.07; H, 5.58; N, 9.89, S, 7.72.
N,N-dibenzyl-4-(1H-indazol-1-yl)benzenesulfonamide
(2h).
Following the general procedure indazole (0.095 g, 0.80 mmol)
and N,N-dibenzyl-4-iodobenzenesulfonamide ( 0.556 g, 1.20
mmol) provided 211 mg (58% yield) of the coupling product as
yellow powder after purification by flash chromatography (60: 40
N,N-dibenzyl-4-(3-methyl-1H-pyrazol-1-
yl)benzenesulfonamide (2c). Following the general procedure 3-
methylpyrazole (0.064 mL, 0.80 mmol) and N,N-dibenzyl-4-
iodobenzenesulfonamide ( 0.556 g, 1.20 mmol) provided 200 mg
(55% yield) of the coupling product as yellow powder after
purification by flash chromatography (84: 16 hexane/ethyl
acetate). 1H NMR (400 MHz, CDCl3): δ 7.89-7.86 (m, 3H), 7.79-
7.77 (m, 2H), 7.25-7.21 (m, 6H), 7.09-7.07 (m, 4H), 6.32 (s, 1H),
4.34 (s, 4H), 2.39 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 151.9,
142.7, 137.4, 135.5, 128.8, 128.6, 128.5, 127.8, 127.4, 118.3,
109.0, 50.5, 13.8. Anal. Calcd for C24H23N3O2S: C, 69.04; H,
1
hexane/ethyl acetate). H NMR (400 MHz, CDCl3): δ 8.26 (s,
1H), 7.98 (d, J = 8.7 Hz, 2H), 7.91 (d, J = 8.7 Hz, 2H), 7.83 (t, J
= 9.0 Hz, 2H), 7.51 (t, J = 7.7 Hz, 1H), 7.30 (t, J = 7.5 Hz, 1H),
7.25-7.22 (m, 6H), 7.12-7.10 (m, 4H). 13C NMR (100 MHz,
CDCl3): δ 143.6, 138.6, 137.9, 136.2, 134.6, 128.6, 128.5, 128.3,
128.0, 127.8, 126.0, 123.1, 121.9, 121.8, 110.4, 50.7. Anal. Calcd