The Journal of Organic Chemistry
Article
MHz, CDCl3): δ 7.83 (d, J = 7.2 Hz, 2H), 7.67 (t, J = 7.6 Hz, 1H),
7.57 (dd, J1 = J2 = 7.6 Hz, 2H), 7.13 (d, J = 8.8 Hz, 2H), 6.88 (d, J =
8.8 Hz, 2H), 2.44 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ
146.9, 137.8, 135.2, 134.2, 129.1, 128.5, 127.2, 122.8, 15.8. HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C13H13O3S2 281.0301; Found
281.0308.
Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 148.5, 135.0, 134.4,
132.7, 129.2, 128.4, 124.1, 120.7. This compound is known.
2,4,6-Tribromophenyl Benzenesulfonate (3n). The title com-
pound was prepared according to the general procedure using 2,4,6-
tribromophenol 1n (66.1 mg, 0.2 mmol) and sodium benzenesulfinate
2a (49.2 mg, 0.3 mmol, 1.5 equiv), purified by column
chromatography on silica gel, and eluted with petroleum ether to
4-(Trifluoromethoxy)phenyl Benzenesulfonate (3h). The title
compound was prepared according to the general procedure using 4-
(trifluoromethoxy)phenol 1h (35.6 mg, 0.2 mmol) and sodium
benzenesulfinate 2a (49.2 mg, 0.3 mmol, 1.5 equiv), purified by
column chromatography on silica gel, and eluted with petroleum ether
to afford 3h (63.0 mg, 99% yield) as a pale-yellow oil. 1H NMR (400
MHz, CDCl3): δ 7.86−7.83 (m, 2H), 7.72−7.67 (m, 1H), 7.57−7.52
(m, 2H), 7.15−7.12 (m, 2H), 7.03−6.99 (m, 1H); 13C{1H} NMR
(100 MHz, CDCl3) δ 147.6 (q, J = 2.0 Hz), 147.5, 135.0, 134.5,
129.3, 128.5, 123.8, 122.1, 120.2 (q, J = 256.4 Hz).
1
afford 3n (71.4 mg, 76% yield) as a pale-yellow oil. H NMR (400
MHz, CDCl3): δ 8.02 (d, J = 8.0 Hz, 2H), 7.73−7.68 (m, 3H), 7.58
(t, J = 8.0 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 145.3,
137.4, 135.6, 134.6, 129.2, 128.6, 120.8, 119.4. HRMS (ESI-TOF) m/
z: [M + Na]+ Calcd for C12H7Br3O3SNa 494.7517; Found 494.7522.
3-(Trifluoromethyl)phenyl Benzenesulfonate (3o).24 The title
compound was prepared according to the general procedure using 3-
(trifluoromethyl) phenol 1o (32.4 mg, 0.2 mmol) and sodium
benzenesulfinate 2a (49.2 mg, 0.3 mmol, 1.5 equiv), purified by
column chromatography on silica gel, and eluted with petroleum ether
to afford 3o (59.8 mg, 99% yield) as yellow oil. 1H NMR (400 MHz,
CDCl3): δ 7.84−7.82 (m, 2H), 7.70 (t, J = 7.6 Hz, 1H), 7.57−7.52
(m, 3H), 7.45 (dd, J1 = J2 = 8.0 Hz, 1H), 7.23 (d, J = 8.4 Hz, 2H),
7.17 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 149.5, 134.8,
134.6, 132.2 (q, J = 33.2 Hz), 130.4, 129.3, 128.5, 126.0, 124.0 (J =
3.6 Hz), 123.1 (q, J = 270.9 Hz), 119.7(q, J = 3.7 Hz). This
compound is known.
4-Fluorophenyl Benzenesulfonate (3i).23 The title compound was
prepared according to the general procedure using 4-fluorophenol 1i
(22.4 mg, 0.2 mmol) and sodium benzenesulfinate 2a (49.2 mg, 0.3
mmol, 1.5 equiv), purified by column chromatography on silica gel,
and eluted with petroleum ether to afford 3i (49.4 mg, 98% yield) as a
1
pale-yellow oil. H NMR (400 MHz, CDCl3): δ 7.82 (d, J = 7.2 Hz,
2H), 7.68 (t, J = 7.6 Hz, 1H), 7.54 (dd, J1 = J2 = 7.6 Hz, 2H), 6.99−
6.92 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3) δ 161.0 (C−F,
1JC−F = 245.3 Hz), 145.3, 135.0, 134.4, 129.2, 128.5, 124.0 (C−F,
3-Acetylphenyl Benzenesulfonate (3p).20 The title compound was
prepared according to the general procedure 3-acetylphenol 1p (27.2
mg, 0.2 mmol) and sodium benzenesulfinate 2a (49.2 mg, 0.3 mmol,
1.5 equiv), purified by column chromatography on silica gel, and
eluted with petroleum ether to afford 3p (36.4 mg, 66% yield) as a
2
3JC−F = 8.7 Hz), 116.4 (C−F, JC−F = 23.6 Hz). This compound is
known.
3-Fluorophenyl Benzenesulfonate (3j). The title compound was
prepared according to the general procedure using 3-fluorophenol 1j
(22.4 mg, 0.2 mmol) and sodium benzenesulfinate 2a (49.2 mg, 0.3
mmol, 1.5 equiv), purified by column chromatography on silica gel,
and eluted with petroleum ether to afford 3j (48.9 mg, 97% yield) as a
pale-yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.89 (d, J = 7.2, 2H),
7.74 (t, J = 7.6 Hz, 1H), 7.59 (dd, J1 = J2 = 8.0 Hz, 2H), 7.33−7.27
(m, 1H), 7.02 (ddd, J1 = J2 = 8.4 Hz, J3 = 2.4 Hz, 1H), 6.86−6.78 (m,
2H); 13C{1H} NMR (100 MHz, CDCl3) δ 162.6 (C−F, 1JC−F = 247.8
1
colorless oil. H NMR (400 MHz, CDCl3): δ 7.85−7.83 (m, 3H),
7.69 (t, J = 7.6 Hz, 3H), 7.54 (dd, J1 = J2 = 8.0 Hz, 2H), 7.49 (dd, J1 =
J2 = 8.0 Hz, 1H), 7.41 (dd, J1 = J2 = 8.0 Hz, 1H), 7.23 (ddd, J1 = 8.0
Hz, J2 = 2.4 Hz, J3 = 0.8 Hz, 1H), 2.51(s, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 196.3, 149.7, 138.6, 135.1, 134.5, 130.0, 129.3, 128.5,
127.0, 126.9, 122.1, 26.6. This compound is known.
Ethyl 4-((Phenylsulfonyl)oxy)benzoate (3q).25 The title com-
pound was prepared according to the general procedure using ethyl 4-
hydroxybenzoate 1q (33.2 mg, 0.2 mmol) and sodium benzenesulfi-
nate 2a (49.2 mg, 0.3 mmol, 1.5 equiv), purified by column
chromatography on silica gel, and eluted with petroleum ether to
4
5
Hz), 150.1 (C−F, JC−F = 10.6 Hz), 135.0, 134.5, 130.4 (C−F, JC−F
6
= 9.2 Hz), 129.2, 128.4, 118.1 (C−F, JC−F = 3.4 Hz), 114.4 (C−F,
3JC−F = 20.9 Hz), 110.4 (C−F, JC−F = 24.5 Hz). HRMS (ESI-TOF)
2
m/z: [M − H]− Calcd for C12H8FO3S 251.0184; Found 251.0185.
2,3,5,6-Tetrafluorophenyl Benzenesulfonate (3k). The title
compound was prepared according to the general procedure using
2,3,5,6-tetrafluorophenol 1k (33.2 mg, 0.2 mmol) and sodium
benzenesulfinate 2a (49.2 mg, 0.3 mmol, 1.5 equiv), purified by
column chromatography on silica gel, and eluted with petroleum ether
to afford 3k (54.5 mg, 89% yield) as a pale-yellow solid. mp: 64−66
1
afford 3q (56.9 mg, 93% yield) as a pale-yellow oil. H NMR (400
MHz, CDCl3): δ 7.97 (d, J = 8.8 Hz, 2H), 7.83−7.81 (m, 2H), 7.67
(t, J = 7.6 Hz, 1H), 7.52 (dd, J1 = J2 = 7.6 Hz, 2H), 7.04 (d, J = 8.8
Hz, 2H), 4.35 (q, J = 7.2 Hz, 2H), 1.36 (t, J = 7.2 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ 165.4, 152.7, 135.0, 134.4, 131.2, 129.3,
129.2, 128.4, 122.2, 61.3, 14.2. This compound is known.
4-Cyanophenyl Benzenesulfonate (3r).26 The title compound was
prepared according to the general procedure using 4-hydroxybenzoni-
trile 1r (23.8 mg, 0.2 mmol) and sodium benzenesulfinate 2a (49.2
mg, 0.3 mmol, 1.5 equiv), purified by column chromatography on
silica gel, and eluted with petroleum ether to afford 3r (50.8 mg, 98%
1
°C. H NMR (400 MHz, CDCl3): δ 7.99 (m, 2H), 7.77 (m, 1H),
7.64−7.59 (m, 2H), 7.04 (m, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ 146.0 (m), 141.6 (m), 135.2, 135.0, 129.5, 128.5, 104.6
(m). HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C12H6F4O3SNa
328.9866; Found 328.9863.
1
yield) as a colorless oil. H NMR (400 MHz, CDCl3): δ 7.84 (d, J =
4-Chlorophenyl Benzenesulfonate (3l).20 The title compound was
prepared according to the general procedure using 4-chlorophenol 1l
(25.7 mg, 0.2 mmol) and sodium benzenesulfinate 2a (49.2 mg, 0.3
mmol, 1.5 equiv), purified by column chromatography on silica gel,
and eluted with petroleum ether to afford 3l (50.9 mg, 95% yield) as a
7.2 Hz, 2H), 7.71 (t, J = 7.6 Hz, 1H), 7.61 (d, J = 8.8 Hz, 2H), 7.56
(dd, J1 = J2 = 7.6 Hz, 2H), 7.13 (ddd, J1 = 8.8 Hz, J2 = J3 = 2.0 Hz,
2H); 13C{1H} NMR (100 MHz, CDCl3) δ 152.4, 134.8, 133.9, 129.4,
128.4, 123.4, 117.6, 111.3. This compound is known.
4-Nitrophenyl Benzenesulfonate (3s).20 The title compound was
prepared according to the general procedure using 4-nitrophenol 1s
(27.8 mg, 0.2 mmol) and sodium benzenesulfinate 2a (49.2 mg, 0.3
mmol, 1.5 equiv), purified by column chromatography on silica gel,
and eluted with petroleum ether to afford 3s (35.2 mg, 63% yield) as a
yellow oil. 1H NMR (400 MHz, CDCl3): δ 8.20−8.16 (m, 2H), 7.85
(d, J = 7.2 Hz, 2H), 7.72 (t, J = 7.6 Hz, 1H), 7.57 (dd, J1 = J2 = 8.0
Hz, 2H), 7.26−7.17 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ
153.8, 146.2, 134.9, 134.8, 129.5, 128.4, 125.4, 123.2. This compound
is known.
1
colorless oil. H NMR (400 MHz, CDCl3): δ 7.88−7.85 (m, 2H),
7.73 (t, J = 7.6 Hz, 1H), 7.58 (dd, J1 = J2 = 7.6 Hz, 2H), 7.29 (d, J =
8.8 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ 147.9, 135.0, 134.4, 132.8, 129.7, 129.2, 128.4, 123.7. This
compound is known.
4-Bromophenyl Benzenesulfonate (3m).20 The title compound
was prepared according to the general procedure using 4-
bromophenol 1m (34.6 mg, 0.2 mmol) and sodium benzenesulfinate
2a (49.2 mg, 0.3 mmol, 1.5 equiv), purified by column
chromatography on silica gel, and eluted with petroleum ether to
4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl Benzene-
sulfonate (3t). The title compound was prepared according to the
general procedure using 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)phenol 1t (44.0 mg, 0.2 mmol) and sodium benzenesulfinate 2a
1
afford 3m (61.3 mg, 98% yield) as a colorless oil. H NMR (400
MHz, CDCl3): δ 7.83−7.81 (m, 2H), 7.68 (t, J = 7.6 Hz, 1H), 7.54
(dd, J1 = J2 = 8.0 Hz, 2H), 7.40 (d, J = 8.8 Hz, 2H), 6.86 (d, J = 8.8
H
J. Org. Chem. XXXX, XXX, XXX−XXX