S.E. Denmark, W. Pan / Journal of Organometallic Chemistry 653 (2002) 98ꢂ
/
104
103
7
7
.37ꢂ
/
7.33 (m, 2H, HC(3?); 7.29ꢂ
7.21 (m, 2H, HC(2?)); 5.73 (m, 1 H, HC(8)); 4.58
3.8, 1H, HC(2)); 4.22 (ddd, Jꢃ1.3, 6.5, 11.5,
H, HC(7)); 3.90 (ddd, Jꢃ10.9, 6.5, 11.5, 1H, HC(7));
.82 (m, 1H, H C(6)); 3.47 (m, 1H, H C(6)); 2.12 (br s,
/
7.26 (m, 1H, HC(4?));
1610 (w), 1530 (s), 1454 (w), 1441 (m), 1352 (s), 1323 (w),
1261 (w), 1157 (w), 1118 (m), 1074 (m), 1051 (m), 1022
(s), 980 (m), 904 (m), 868 (w), 856 (w) 1051 (m), 856
.23ꢂ
/
(
br t, Jꢃ
/
/
ꢀ
1
ꢁ
1
3
3
1
/
(w) cm ; MS (EI, 70 eV) m/z 233 [M ꢀ
(25), 146 (10), 130 (30), 85 (100), 67 (17); TLC R
0.37 (C H /Et O, 3/2, SiO ); GC t (Z)-7d 8.50 min
/44, 5], 176
e
a
f
H, H C(10)); 1.87ꢂ
H, H C(5)); 1.64ꢂ
/
1.82 (m, 1H, H C(3)); 1.75ꢂ
/1.69 (m,
3
e
5
12
2
2
R
/
1.51 (m, 4H, H C(3), H C(5),
a
e
a
(100%) (HP5, injector 225 8C, detector 300 8C, column
270 8C, 15 psi). Anal. Calc. for C H NO : C,
1
3
H C(4)); C-NMR (125.6 MHz) d 141.50, 140.83,
1
2
15
21
4
28.30, 128.05, 127.28, 124.00, 98.60 (C(2)), 65.22
C(7)), 62.38 (C(6)), 30.92, 25.65, 25.63, 19.76; IR
64.97; H, 6.91; N, 5.05. Found: C, 64.71; H, 6.79; N,
(
4.84%.
(
CHCl ) 3009 (s), 2946 (s), 2873 (m), 2855 (m), 1600
3
(
1
w), 1494 (m), 1442 (m), 1378 (m), 1263 (m), 1119 (s),
ꢀ
1
022 (s), 907 (s) cm ; MS (EI, 70 eV) m/z 232 [M , 1],
ꢁ
4
.5. Reaction of 2-iodoanisole with (E)-1. 2-[(E)-3-(2?-
2
R 0.50 (C H /Et O, 4/1); GC t (Z)-7a 6.04 min
17 (4), 199 (1), 148 (2), 131 (94), 117 (22), 85(100); TLC
methoxyphenyl)-2-butenyloxy]-tetrahydro-2H-pyran
((E)-7c)
f
5
12
2
R
(
psi) Anal. Calc. for C H O : C, 77.55; H, 8.68. Found:
100%) (HP-5, injector 225 8C, column 270 8C, 15
.
15 20
2
Silanol (E)-1 (254 mg, 1.10 mmol, 1.10 equivalents),
C, 77.63; H, 8.79%.
was dissolved in a 1.0 M solution of TBAF in THF (2.0
ml, 2.0 mmol, Two equivalents) and the mixture was
stirred for 10 min at r.t. 2-iodoanisole (232 mg, 1.0
4.4. Reaction of 2-iodonitrobenzene with (Z)-1. 2-[(Z)-
3-(2?-Nitrophenyl-2-butenyloxy]-tetrahydro-2H-pyran
((Z)-7d)
mmol) was added followed by Pd(dba) (29.0 mg, 0.05
2
mmol, 0.050 equivalents). The mixture was stirred at r.t.
for a total of 100 min and was loaded onto 2.0 g of SiO2.
Silanol (Z)-1 (269.7 mg, 1.17 mmol, 1.10 equivalents),
was dissolved in a 1.0 M solution of TBAF in THF (2.13
ml, 2.13 mmol, 2.0 equivalents) and the mixture was
stirred for 10 min at r.t. Iodonitrobenzene (110 mg) was
added followed by Pd(dba)2 (30.6 mg, 0.054 mmol,
Purification by column chromatography (SiO , 51 g,
2
C H /Et O, 24/1) afforded 240 mg yellow oil which
12
5
2
contained ca. 5% of dibenzylidene acetone. To this oil
was added 5.0 ml C H and the solution was cooled in
5
12
0
.050 equivalents) and triphenylarsine (31.0 mg, 0.11
refrigerator overnight. Yellow needles of crystalline
dibenzylidene acetone (8.5 mg) were filtered off. Kugel-
rohr distillation of the residual oil afforded 202 mg
mmol, 0.10 equivalents). Two portions of iodide (90 mg
and 65 mg, respectively, for a total, 265 mg, 1.06 mmol)
were added 20 min and 55 min later. The mixture was
stirred at 35 8C for another 610 min. The mixture was
poured into 100 ml C H . After being well shaken, it
was allowed to settle down, and the organic layer was
decanted. The residue was washed with 2ꢄ20 ml of
C H /Et O, 4/1. The combined organic layers were
concentrated to afford the crude product as a yellow oil.
Purification of the oil by column chromatography (SiO2,
9
Kugelrohr distillation of which afforded 226 mg (77%)
(
77%) of (E)-7c as a colorless oil; bp 140 8C (air bath,
1
0
.3 mmHg); H-NMR (500 MHz) d 7.26 (ddd, Jꢃ
.7, 8.7, 1 H, HC(5?/4?)); 7.19 (dd, Jꢃ 1.7, 7.7, 1H,
7.7, 8.7, 1H, HC(4?/5?)); 6.88
8.7, 1H, HC(6?/3?)); 5.67 (qt, Jꢃ 1.1, 6.6, 1H,
HC(8)); 4.74 (t Jꢃ 3.4, 1 H, HC(2)); 4.33 (dd, Jꢃ6.0
2.5, 1H, HC(7)), 4.27 (dd, Jꢃ7.1, 12.5, 1H, HC(7));
.96 (ddd, Jꢃ 2.8, 7.7, 11.2, 1H, H C(6)), 3.83 (s, 3H,
/
1.7,
5
12
7
/
HC(3?/6?)); 6.93 (br dd, Jꢃ
/
/
(
br d, Jꢃ
/
/
5
12
2
/
/
1
3
/
/
e
g, C H /Et O, 9/1) afforded 261 mg of yellow oil,
5 12 2
H C(7?)), 3.58 (m, 1H, H C(6)); 2.05 (br s, 3H,
3
a
H C(10)); 1.96ꢂ
/
1.86 (m, 1H, H C(3)); 1.80ꢂ
/
1.74 (m,
C(5),
H C(4)); C-NMR (125.6 MHz) d 156.83 (C(2?)),
3
e
of (Z)-7d as a yellow oil; bp 165 8C (air bath, 0.2
1
1H,
H
e
C(5)); 1.67ꢂ1.53(m, 4H, H C(3), H
/
a a
mmHg); H-NMR (500 MHz) d 8.00 (dd, Jꢃ
/
1.3, 8.1, 1
1.3, 7.5, 1H, HC(5?)); 7.45
1.5, 7.5, 8.1, 1H, HC(4?)); 7.28 (dd, Jꢃ 1.5,
.5, 1H, HC(6?)); 5.76 (m, 1H, HC(8)); 4.48 (br t, Jꢃ
.8, 1H, HC(2)); 3.90 (ddd, Jꢃ 1.3, 6.4, 10.9, 1H,
3.2, 8.8, 11.1, 1H, H C(6)); 3.62
1
3
2
H, HC(3?)); 7.60 (dt, Jꢃ
/
138.93(C(9/1?)), 134.30 (C(1?/9)), 129.79 (C(3?/6?)),
128.46 (C(4?/5?)), 126.13 (C(8)), 120.74 (C(5?/4?)),
110.91 (C(6?/3?)), 98.05 (C(2)), 64.03 (C(7)), 62.50
(
ddd, Jꢃ
/
/
7
2
/
/
(
(
(
C(6)), 55.58 (C(7?)), 30.95 (C(3)), 25.75 (C(4)), 19.79
C(5)), 17.61 (C(10)); IR (neat) 2943 (m), 1597 (m), 1490
HC(7)); 3.67 (ddd, Jꢃ
ddd, Jꢃ 1.1, 7.5, 10.9, 1H, HC(7)); 3.40ꢂ
HC(6)); 2.11 (br s, 3H, H C(10)); 1.80ꢂ1.74 (m, 1H,
1.61 (m, 1H, H C(5)), 1.56ꢂ1.46 (m, 4H,
H C(3), H C(5), H C(4)); C-NMR (125.6 MHz) d
/
e
(
/
/
3.36(m, 1H,
ꢀ
1
m), 1249 (m), 1118 (m), 1043 (m) cm ; MS (EI, 70 eV)
/
3
ꢁ
m/z 262 [M , 2], 178 (13), 161 (42), 147 (13), 132 (16),
91 (11), 85 (97), 67 (11), 57 (14); TLC R 0.42 (C H /
H C(3)), 1.68ꢂ
/
/
e
e
1
3
a
a
2
f 5 12
1
1
2
48.33, 137.95, 137.01, 133.37, 130.98, 128.35, 125.09,
24.62, 98.25 (C(2)), 64.60 (C(7)), 62.15 (C(6)), 30.70,
5.56, 25.15, 15.54; IR (CHCl ) 3028 (w), 3026 (w), 3024
Et O 4/1, SiO ); GC t (E)-7c 7.68 min (100%) (HP5,
2 2 R
injector 225 8C, detector 300 8C, column 270 8C, 15
psi) Anal. Calc. for C16 : C, 73.25; H, 8.45. Found:
C, 73.09; H, 8.48%.
H O
22 3
3
.
(
w), 3008 (m), 2947 (s), 2873 (m), 2854 (m), 2854 (m),