D. C. Meadows et al. / Bioorg. Med. Chem. 15 (2007) 1127–1137
1135
white solid precipitated, this was filtered off and rinsed
with cold ethyl acetate to give 93 mg (53%) of the title
compound (mp = 238 ꢂC). 1H NMR (DMSO-d6,
400 MHz) d 3.78 (s, 6H), 3.81 (s, 6H), 5.47 (s, 2H),
7.33 (s, 2H), 7.40 (d, 2H, J = 16.0 Hz), 7.46 (d, 2H,
J = 16.0 Hz), 7.49 (s, 2H). 13C NMR (DMSO-d6,
100 MHz) d 56.20, 60.23, 71.36, 112.46, 116.96, 125.36,
126.47, 129.40, 143.65, 147.90, 153.33. FT-IR (KBr): m
3064, 1616, 1491 (C@C str), 1468 (–CH2– str), 1315,
1124 (SO2 str), 1282, 1047 (Ph–O–C str), 1228 (C–O
str), 970 (trans C@C str). Anal. (C21H22Br2O8S2) C, H.
4.2.15. Bis(trans-1,4-dihloro-2-(2-methanesulfonyl-vinyl)-
benzene) (17). The disulfone reagent10 (224 mg,
0.45 mmol) and 2,5-dichlorobenzaldehyde (258 mg,
1.47 mmol) were reacted according to general proce-
dure A. After removal of solvent, 142 mg (65%) of
the title compound was precipitated out of 4 mL of
acetone and filtered (mp = 246–247 ꢂC). 1H NMR
(DMSO-d6, 400 MHz) 5.68 (s, 2H), 7.50–7.56 (m,
4H), 7.64 (d, 2H, J = 15.6 Hz), 7.69 (d, 2H,
J = 15.6 Hz) d 7.93 (d, 2H, J = 2 Hz). 13C NMR
(DMSO-d6, 100 MHz)
d
71.05, 128.41, 130.47,
131.31, 131.71, 132.50, 132.64, 132.85, 138.74. FT-IR
(KBr): m 3068, 1608, 1462 (C@C str), 1340, 1149
(SO2 str), 1099 (Ph–Cl str), 970 (trans C@C str). Anal.
(C17H12Cl4O4S2) C, H.
4.2.12. Bis(trans-(2-methanesulfonyl-ethyl)-benzene) (14).
Compound 11 (64 mg, 0.18 mmol) was dissolved in
3 mL of ethyl acetate. To this was added 6 mg of palla-
dium (10 wt %) on carbon powder (wet) and allowed to
react on the Parr shaker overnight at 60 psi. This mix-
ture was filtered over a pad of Celiteꢁ 503 and subjected
to column chromatography (ethyl acetate/hexanes 1:2,
Rf = 0.40) to yield 6 mg (10%) after spilling of some title
4.2.16.
Bis(1,2,3-benzyloxy-trans-(2-ethanesulfonyl-vi-
nyl)-benzene) (18). The disulfone reagent10 (130 mg,
0.26 mmol) and 3,4,5-tribenzyloxybenzaldehyde were
used according to general method A. After removal of
the solvent, 4 mL of acetone was added to the pale yel-
low oil and a white solid precipitated. This solid was fil-
tered and washed with cold acetone to give 159 mg
1
product. H NMR (CDCl3, 400 MHz) d 3.14 (t, 4H,
J = 8 Hz), 3.66 (t, 4H, J = 8 Hz), 3.98 (s, 2H), 7.22–
7.35 (m, 10H). 13C NMR (CDCl3, 100 MHz) d 28.43,
55.24, 68.33, 127.62, 128.84, 129.24, 136.47. FT-IR
(film): m 3012 (C@C str), 1456 (–CH2– str), 1311, 1128
(SO2 str). Anal. (C17H20O4S2) C, H.
1
(62%) of the title compound (mp = 216 ꢂC). H NMR
(acetone-d6, 300 MHz) d 4.94 (s, 4H), 5.09 (s, 8H),
5.50 (s, 2H), 7.18–7.47 (m, 38H). 13C NMR (DMSO-
d6, 125 MHz) d 70.48, 70.78, 74.54, 108.22, 127.72–
128.76 (m), 136.82, 136.98, 137.61, 140.01, 145.93,
152.07, 152.53. FT-IR (KBr): m 3064, 1614, 1504 (C@C
str), 1454 (–CH2– str), 1329, 1122 (SO2 str), 1248
(Ph–O–C str), 972 (trans C@C str). Anal. (C59H52O10
S2) C, H.
4.2.13.
Bis(1-benzyloxy-trans-2-(2-methanesulfonyl-vi-
nyl)-benzene) (15). The disulfone reagent10 (201 mg,
0.40 mmol) and 2-benzyloxybenzaldehyde (282 mg,
1.33 mmol) were used according to general method A.
Following removal of solvent, the crude solid was purified
by column chromatography (30% ethyl acetate/70% hex-
anes, Rf = 0.36) to yield 108 mg (48%) of the title com-
4.2.17.
Bis(6-(2-methanesulfonyl-vinyl)-2,3-dihydro-
1
pound as a foamy solid. H NMR (CDCl3, 300 MHz) d
benzo[1,4]dioxine) (19). The disulfone reagent10
(221 mg, 0.44 mmol) and 1,4-benzodioxan-6-carboxal-
dehyde (240 mg, 1.45 mmol) were reacted according
to general method A. Following solvent removal,
the crude mixture was subjected to column chroma-
tography (8% acetone/92% toluene, Rf = 0.26) to yield
86 mg (42%) of the title compound. 1H NMR
(CDCl3, 500 MHz) d 4.29 (dapp, 8H, J = 13 Hz),
4.64 (s, 2H), 6.88 (d, 2H, J = 8.5 Hz), 7.00 (d, 2H,
J = 15.5 Hz), 7.05 (m, 4H), 7.53 (d, 2H,
4.56 (s, 2H), 5.17 (s, 4H), 6.98 (d, 2H, J = 8.1 Hz), 7.32–
7.49 (m, 18H), 7.93 (d, 2H, J = 15.6 Hz). 13C NMR
(CDCl3, 100 MHz) d 70.66, 74.18, 112.98, 121.13,
121.28, 125.21, 127.41, 128.32, 128.87, 131.34, 133.28,
136.12, 142.61, 158.25. FT-IR (film): m 3064, 1599, 1486
(C@C str), 1452 (–CH2– str), 1317, 1124 (SO2 str), 1250,
1051 (Ph–O–C str), 1223 (C–O str), 984 (trans C@C str).
Anal. (C31H28O6S2) C, H.
4.2.14.
Bis(1,2-benzyloxy-trans-5-(2-ethanesulfonyl-vi-
J = 15.5 Hz). 13C NMR (DMSO-d6, 75 MHz)
d
nyl)-benzene) (16). The disulfone reagent10 (219 mg,
0.44 mmol) and 3,4-benzyloxybenzaldehyde (419 mg,
1.44 mmol) were reacted according to general method
A. After removal of solvent, 4 mL of acetone was added
from which a white solid precipitated. This solid was fil-
tered and washed with cold acetone to give 134 mg
(40%) of the title compound (mp = 194–195 ꢂC). 1H
NMR (DMSO-d6, 400 MHz) d 5.07 (s, 4H), 5.14 (s,
4H), 5.42 (s, 2H), 7.05 (d, 2H, J = 6.3 Hz), 7.18 (d,
2H, J = 11.4 Hz), 7.22 (d, 2H, J = 11.7 Hz), 7.32–7.43
(m, 24H). 13C NMR (DMSO-d6, 100 MHz) d 70.49,
70.65, 72.45, 113.86, 114.23, 124.06, 124.82, 125.65,
127.68–128.60 m, 136.83, 145.30, 148.41, 151.23. FT-
IR (KBr): m 3064, 1597, (C@C str), 1456 (–CH2– str),
1323, 1140 (SO2 str), 1271, 1022 (Ph–O–C str), 1211
(C–O str), 979 (trans C@C str). Anal. Calcd for
C45H40O8S2: C, 69.93; H, 5.22. Found: C, 69.44; H,
5.19.
63.88, 64.40, 71.74, 117.39, 117.43, 122.81, 123.69,
125.25, 143.37, 144.40, 146.21. FT-IR (film): m 3060,
1600, 1510 (C@C str), 1325, 1122 (SO2 str), 1292,
1066 (Ph–O–C str), 976 (trans C@C str). Anal.
(C21H20O8S2) C, H.
4.2.18. Bis(4-bromo-2-(2-methanesulfonyl-vinyl)-1-meth-
oxy-benzene) (20). The disulfone reagent10 (175 mg,
0.35 mmol)
and
5-bromo-2-methoxybenzaldehyde
(248 mg, 1.15 mmol) were reacted according to general
procedure A. After removal of the solvent, 188 mg
(95%) of the title compound was precipitated from
5 mL of dichloromethane (mp = 282 ꢂC). 1H NMR
(DMSO-d6, 300 MHz) d 3.82 (s, 6H), 5.50 (s, 2H),
7.02 (d, 2H, J = 8.7 Hz), 7.43 (d, 2H, J = 15.6 Hz),
7.54 (d, 2H, J = 15.6 Hz), 7.57 (dd, 4H, J = 8.7 Hz,
J = 2.4 Hz), 7.79 (d, 2H, J = 2.4 Hz). 13C NMR
(DMSO-d6, 100 MHz) d 56.15, 71.23, 112.27, 114.13,