1
4
Tetrahedron
MA4.
residue which was dissolved in THF and
A
fil
C
ter
C
ed
E
th
P
ro
T
u
E
gh
D
a
N
4.1
U
.
S
1
C
,2
R
-Bi
I
s(5-iodo-2-methylbenzo[b]thiophen-3-yl)cyclopent-
P
T
silica plug. After evaporation of the filtrate the residue was
subjected to silica gel flash column chromatography
1-ene (9) via halogen exchange. Dibenzothienylethene 6 (150
mg, 0.29 mmol), copper (I) iodide (55 mg, 0.29 mmol), sodium
iodide (348 mg, 2.32 mmol), and N,N’-dimethylethylenediamine
(102 mg, 1.16 mmol) were sequentially placed into a Schott tube
under argon atmosphere. Dioxane (4 mL) was then added
washing all the solids from the walls of the tube. The reaction
(hexanes/ethyl acetate) to give 200 mg (82%) of white solid.
High quality single crystals suitable for X-ray diffraction were
grown by slow diffusion of hexanes into the chloroform solution:
mp 170-171 С; H NMR (300 MHz, CDCl ) δ 2.22 (s, 6H),
о
1
3
о
2
7
.16-2.32 (m, 2H), 2.85-3.05 (m, 4H), 7.32 (d, 2H, J = 8.3 Hz),
.39 (d, 2H, J = 8.3 Hz), 7.78 (s, 2H); C NMR (75 MHz,
mixture was stirred at 115 С for 24 h, after this time TLC
13
analysis showed no starting material left in the reaction mixture.
THF was added, and the formed suspension was filtered through
a silica plug. After evaporation of the filtrate, the residue was
subjected to silica gel flash column chromatography
(hexanes/ethyl acetate) to give 165 mg (93%) of white solid.
CDCl ) δ 15.0, 23.9, 37.6, 89.0, 123.4, 129.4, 131.1, 131.8,
3
-
1
1
1
36.7, 137.4, 137.5, 141.0; IR (KBr, cm ) ν 2914, 2840, 1571,
548, 1428, 1405, 1250, 1150, 1067, 964, 869, 804, 732; anal.
calcd for C H I S : C, 45.12; H, 2.96; I, 41.45; S, 10.47; found:
C, 44.64; H, 2.88; I, 40.49; S, 10.23; HRMS (m/z) [M + H] calcd
for C H I S , 612.9012; found 612.8992.
23
18 2 2
+
4
.4.2.
3,3'-(Cyclopentene-1,2-diyl)bis(2-
(14).
23
18 2 2
methylbenzo[b]thiophene-5-carbonitrile)
4
.3.2.
1,2-Bis(2-methyl-5-(trimethylsilyl)benzo[b]thiophen-3-
Dibenzothienylethene 6 (150 mg, 0.29 mmol), copper (I) iodide
(55 mg, 0.29 mmol), potassium iodide (48 mg, 0.29 mmol),
sodium cyanide (57 mg, 1.16 mmol), and N,N’-
dimethylethylenediamine (102 mg, 1.16 mmol) were sequentially
placed into a Schott tube under argon atmosphere. Toluene (2
mL) was then added washing all the solids from the walls of the
yl)cyclopent-1-ene (10). 180 mg (90%) of colorless foam
1
(hexanes) were obtained; H NMR (300 MHz, CDCl ) δ 0.08 (s,
3
9
1
7
H), 0.33 (s, 9H), 1.92 (s, 3H), 2.19-2.32 (m, 5H), 2.67-2.82 (m,
H), 2.82-2.98 (m, 1H), 3.10-3.29 (m, 2H), 7.22-7.40 (m, 2H),
.56-7.73 (m, 3H), 7.78-7.89 (m, 1H); C NMR (75 MHz,
13
о
CDCl ) δ -0.9, 15.0, 24.6, 38.1, 121.4, 123.3, 127.4, 127.9, 130.2,
1
1
tube. The reaction mixture was stirred at 120 С for 20 h, after
3
-
1
35.0, 135.8, 137.4, 139.2; IR (KBr, cm ) ν 2954, 2846, 1433,
399, 1267, 1247, 1176, 1098, 1053, 838, 804, 755; HRMS (m/z)
this time TLC analysis showed some of monosubstituted
intermediate left in the reaction mixture. All reagents were added
at this point once again in the same quantities followed by 2 mL
+
[
M + H] calcd for C H S Si , 504.1791; found 504.1774.
29
36
2
2
of toluene, and the well-stirred reaction was additionally kept at
4
.3.3.
3,3'-(Cyclopentene-1,2-diyl)bis(2-
о
1
20 С for 20 h to complete the transformation. Hot reaction
methylbenzo[b]thiophene-5-carbaldehyde) (11). 138 mg (83%)
of white solid (hexanes/ethyl acetate) were obtained. High quality
single crystals suitable for X-ray diffraction were grown by slow
mixture was filtered through a silica plug followed by hot ethyl
acetate. After evaporation of the combined filtrate the residue
was subjected to silica gel flash column chromatography
о
1
evaporation of the chloroform solution: mp 195 С dec.; H NMR
300 MHz, CDCl ) δ 2.21 (s, 6H), 2.35 (quin, 2H, J = 7.4 Hz),
(hexanes/ethyl acetate) to give 105 mg (88%) of white solid.
(
2
3
High quality single crystals suitable for X-ray diffraction were
grown by slow diffusion of hexanes into the chloroform solution:
.93-3.17 (m, 4H), 7.65 (d, 2H, J = 8.2 Hz), 7.71 (d, 2H, J = 8.2
13
Hz), 8.02 (s, 2H), 9.77-10.03 (broad s, 2H); C NMR (75 MHz,
CDCl ) δ 15.2, 23.9, 37.9, 122.5, 123.5, 124.7, 130.8, 132.8,
1
1
HRMS (m/z) [M + H] calcd for C H O S , 417.0977; found
4
о
1
mp 272 С dec.; H NMR (300 MHz, CDCl ) δ 2.16 (s, 6H), 2.32
3
3
-
1
(quin, 2H, J = 7.4 Hz), 2.90-3.10 (m, 4H), 7.39 (d, 2H, J = 8.2
37.0, 138.2, 139.2, 144.4, 192.0; IR (KBr, cm ) ν 2914, 2720,
685, 1588, 1553, 1433, 1376, 1304, 1193, 1141, 1067, 806, 715;
13
Hz), 7.69 (d, 2H, J = 8.2 Hz), 7.80 (s, 2H); C NMR (75 MHz,
+
CDCl
3
) δ 15.1, 24.0, 37.8, 107.6, 119.3, 122.9, 125.5, 126.4,
25
20
2 2
-1
1
2
29.9, 137.0, 138.9, 139.2, 142.5; IR (KBr, cm ) ν 2914, 2840,
223, 1594, 1445, 1385, 1227, 1141, 1064, 895, 809, 741;
17.0966.
+
4
.3.4.
1,1'-(3,3'-(Cyclopentene-1,2-diyl)bis(2-
HRMS (m/z) [M + H] calcd for C25H N S , 411.0984; found
18 2 2
methylbenzo[b]thiophene-5,3-diyl))diethanone (12). 92 mg
52%) of white solid (hexanes/ethyl acetate) were obtained. High
411.0975.
(
4
.4.3.
N,N'-(3,3'-(cyclopentene-1,2-diyl)bis(2-
(15).
quality single crystals suitable for X-ray diffraction were grown
о
methylbenzo[b]thiophene-5,3-diyl))dibenzamide
by slow evaporation of the chloroform solution: mp 185-186 С;
1
Dibenzothienylethene 6 (150 mg, 0.29 mmol), benzamide (140
mg, 1.16 mmol), copper (I) iodide (55 mg, 0.29 mmol),
potassium carbonate (320 mg, 2.32 mmol), and N,N’-
dimethylethylenediamine (102 mg, 1.16 mmol) were sequentially
placed into a Schott tube under argon atmosphere. Dioxane (4
mL) was then added washing all the solids from the walls of the
H NMR (300 MHz, CDCl ) δ 2.08-2.20 (m, 3H), 2.23-2.41 (m,
3
8
7
8
2
1
1
H), 2.60-2.71 (m, 3H), 2.83-3.01 (m, 2H), 3.09-3.24 (m, 2H),
.66 (d, 2H, J = 8.2 Hz), 7.71-7.79 (m, 2H), 8.01-8.10 (m, 1H),
13
.11-8.23 (m, 1H); C NMR (75 MHz, CDCl ) δ 15.2, 23.9,
3
6.3, 38.0, 121.9, 122.6, 122.9, 130.8, 133.4, 136.8, 137.8, 138.9,
-
1
43.0, 197.8; IR (KBr, cm ) ν 2926, 2846, 1677, 1585, 1428,
о
tube. The reaction mixture was stirred at 115 С for 24 h, after
362, 1307, 1267, 1230, 1050, 907, 821, 809; HRMS (m/z) [M +
+
this time TLC analysis showed no starting material left in the
reaction mixture. THF was added, and the formed suspension
was filtered through a silica plug. After evaporation of the filtrate
the residue was subjected to silica gel flash column
chromatography (hexanes/ethyl acetate) to give 104 mg (60%) of
white solid. High quality single crystals suitable for X-ray
diffraction were grown by slow diffusion of MeOH into the
DMSO solution: mp 279 С dec.; H NMR (300 MHz, CDCl ) δ
2.22-2.39 (m, 8H), 2.83-3.01 (m, 4H), 7.21-7.29 (m, 4H), 7.32-
7.37 (m, 2H), 7.38 (d, 2H, J = 8.4 Hz), 7.53 (d, 2H, J = 8.4 Hz),
7.53-7.61 (m, 4H), 7.79 (s, 2H), 8.10 (s, 2H); C NMR (75 MHz,
H] calcd for C H O S , 445.1290; found 445.1296.
27
24
2 2
4
.3.5.
1,1'-(3,3'-(Cyclopentene-1,2-diyl)bis(2-
methylbenzo[b]thiophene-5,3-diyl))diethanol (13). 145 mg (81%)
of white solid (hexanes/ethyl acetate) were obtained: mp 111-112
о
1
С; H NMR (300 MHz, CDCl ) δ 0.96-1.04 (m, 1H), 1.08-1.19
3
(
(
(
m, 1H), 1.39-1.51 (m, 4H), 2.10-2.43 (broad m, 10H), 2.82-3.18
о
1
broad m, 4H), 4.73-4.90 (m, 2H), 6.96-7.13 (m, 2H), 7.48-7.59
3
13
m, 2H), 7.66-7.78 (m, 2H); C NMR (75 MHz, CDCl ) δ 15.0,
3
2
1
1
3.8, 25.4, 37.9, 70.6, 118.6, 121.0, 121.6, 130.6, 136.4, 136.9,
37.2, 139.4, 142.0; IR (KBr, cm ) ν 3411, 2971, 2926, 2846,
-
1
13
545, 1442, 1370, 1293, 1199, 1150, 1075, 895, 802; HRMS
DMSO-d
6
) δ 14.7, 23.7, 37.1, 113.5, 117.3, 121.9, 127.5, 128.3,
+
(m/z) [M + H] calcd for C H O S , 448.1525; found 448.1503.
129.8, 131.4, 132.4, 135.0, 136.1, 136.3, 136.5, 139.3, 165.5; IR
27
28
2 2
-
1
(
KBr, cm ) ν 3349, 3297, 2920, 2846, 1651, 1599, 1574, 1511,
4
.4. Copper (I) iodide catalyzed coupling of dibromide 6