PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
room temperature. The reaction mixture was concentrated m, H10a, H10s, CH ); 1.59 (1H, m, CH); 1.63 (2H, t, J = 7.50,
2
under reduced pressure, the crude product was subsequently CH ); 1.82-1.90 (7H, m, 7xCH); 2.97 (1H, t, J = 5.90, H );
2
1
purified through combiflash chromatography to yield the 3.18-3.36 (5H, m, N-CH , H , H , H ); 4.77 (1H, q, J = 7.3;
2
9n
8n
7
[
42]
desired products.
14.0, CH); 5.75 (1H, dt, J = 5.67; 28.37, NH); 7.57 (4H, m,
ArH). C NMR (125 MHz, CDCl ), d, ppm: 9.3 (CH ); 14.4
13
3
2
(
2
CH ); 14.6 (CH); 22.4 (CH ); 22.5 (7xCH ); 22.8 (CH );
3.8 (7xCH ); 23.9 (7xCH ); 25.6 (7xCH); 36.4 (CH ); 41.9
3 3 2
3 2 2 2
General procedure for heck reaction of POSS derivatives
5a–c, 6a–c and 7a–c)
(
(CH); 42.3 (CH ); 43.9 (CH); 45.7 (CH); 46.9 (CH); 49.2
2
(
1
CH); 127.4 (Cq); 128.3 (CAr); 128.4 (CAr); 131.0 (Car);
A solution of Pd(OAc)2 (5.6 mg, 0.025 mmol) and Ph As
3
32.1 (CAr); 155.9 (Cq); 167.8 (C ¼ O); 175.8 (C ¼ O); 176.2
(33.7 mg, 0.11 mmol) in dry DMF (5 mL) was stirred in a
þ
(
C ¼ O). HRMS:
-
Found, m/z: 1205.3800 [M þH].
flame-dried Schlenk tube under nitrogen atmosphere at
þ
ꢀ
C H ClN O Si Calculated, m/z: 1204.3920 [M] .
8
0 C for 15 min to form the catalyst complex. Then, aryl
49 87
2
15 8
iodide (1.5 mmol), alkene (4a, 4b or, Norbornenylethyl iso-
butyl POSS respectively; 1 mmol), Et N (354 mg, 3.5 mmol),
3
N-[3-(isobutylpolyhedral oligomeric
and formic acid (138 mg, 3 mmol) were added. The reaction
silsesquioxanyl)propyl]-2-(4-Azabicyclo[2.2.1]hept-8-(4-
methoxyphenyl)-3-endo,5-endo-dicarboximide-4-yl)
propanamide (5c)
ꢀ
mixture was stirred at 80 C for 24 h. The progress of the
reaction was monitored using TLC. After completion of the
reaction, brine (50 mL) was added, and the mixture was
ꢁ
1
extracted with ethyl acetate, dried over Na SO and concen- Colorless oil; Yield 55%. IR ꢀ cm 3301 (NH) 2952, 2926,
2
4
trated. The crude product purified by column 2906 and 2869 (Aliphatic C–H), 1699 (C ¼ O), 1551
1
chromatography.
(Si–O–Si), 1498, 1383, 1084 (Si–O–R), 740. H NMR
(
500 MHz, CDCl ), d, ppm (J, Hz): 0.63 (14H, dd, J = 3.4;
3
7
.3, 7xCH -Si); 0.83–0.90 (2H, m, CH ); 0.97 (42H, d,
2 2
N-[3-(isobutylpolyhedral oligomeric
J = 6.62, 14xCH ); 1.02 (3H, d, J = 6.62, CH ); 1.28-1.32 (2H,
m, H10a, H10s,); 1.56 (1H, d, J = 10.4, CH); 1.65 (4H, m,
3
3
silsesquioxanyl)propyl]-2-(4-Azabicyclo[2.2.1]hept-8-(4-
chlorophenyl)-3-endo,5-endo-dicarboximide-4-yl)
propanamide (5a)
2
3
xCH ); 1.82-1.92 (7 H, m, 7xCH); 2.97 (1 H, m, H ); 3.17-
2 1
.40 (5H, m, N-CH , H , H , H ); 3.78 (3H, s, OCH );
2
9n
8n
7
3
ꢀ
ꢁ1
White solid. mp 122–124 C; Yield 65%. IR ꢀ cm 3340 4.75 (1H, q, J = 7.2; 14.5, CH); 5.76 (1H, dt, J = 5.7; 25.0,
13
(
amide NH), 2953 and 2870 (Aliphatic C–H), 1704 (C ¼ O), NH); 7.52 (4H, dd, J = 2.4; 5.4, ArH). C NMR (125 MHz,
1
1
537 (Si–O–Si), 1463, 1381 and 1085 (Si–O–R), 740.
H
CDCl ), d, ppm: 9.3 (CH ); 14.4 (CH ); 14.6 (CH); 22.5
3 2 3
NMR (500 MHz, CDCl ), d, ppm (J, Hz): 0.61 (14H, dd, (7xCH
); 22.8 (CH
); 23.8 (7xCH
); 41.9 (CH); 42.3 (CH
d, J = 6.62, 14xCH ); 0.99 (3H, d, J = 6.62, CH ); 1.25–1.30 45.7 (CH); 46.9 (CH); 49.2 (CH); 54.9 (OCH
); 23.9 (7xCH
); 43.9 (CH);
); 124.3 (Cq);
4H, m, H10a, H10s, CH ); 1.58 (1H, m, CH); 1.62 (2H, t, 128.3 (CAr); 128.4 (CAr); 132.0 (2xCAr); 155.9 (Cq); 167.7
); 25.7
3
2
2
3
3
J = 3.40; 7.25, 7xCH -Si); 0.82-0.86 (2H, m, CH ); 0.96 (42H, (7xCH); 36.4 (2xCH
2
2
2
2
3
3
3
(
2
J = 7.25, CH ); 1.81–1.90 (7 H, m, 7xCH); 2.96 (1H, t, (C ¼ O); 175.6 (C ¼ O); 175.8 (C ¼ O). HRMS: - Found, m/
2
þ
J = 6.00, H ); 3.17–3.36 (5H, m, N-CH , H , H , H ); 4.76 z: 1200.4508 [M þH]. C50
H N O16Si Calculated, m/z:
90 2 8
1
2
9n
8n
7
þ
(
1H, q, J = 7.25; 14.50, CH); 5.73 (1H, dt, J = 5.65; 25.37, 1199.4478 [M] .
NH); 7.52 (2H, d, J = 2.50, ArH); 7.54 (2H, d, J = 1.91, ArH).
1
3
C NMR (125 MHz, CDCl ), d, ppm: 9.4 (CH ); 14.4
3
2
N-[3-(isobutylpolyhedral oligomeric
(
2
(
(
CH ); 14.7 (CH); 22.4 (CH ); 22.5 (7xCH ); 22.8 (CH );
3.8 (7xCH ); 23.9 (7xCH ); 25.6 (7xCH); 36.4 (CH ); 42.0
3 3 2
3 2 2 2
silsesquioxanyl)propyl]-2-(4-Azabicyclo[2.2.1]hept-8-(4-
chlorophenyl)-3-endo,5-endo-dicarboximide-4-yl)-3-
phenyl propanamide (6a)
CH); 42.3 (CH ); 43.9 (CH); 44.4 (CH); 45.7 (CH); 46.4
2
CH); 124.3 (Cq); 128.3 (CAr); 128.4 (CAr); 132.0 (2xCAr);
ꢀ
ꢁ1
1
55.6 (Cq); 167.7 (C ¼ O); 175.6 (C ¼ O); 176.3 (C ¼ O). White solid; mp 131–133.5 C; Yield: 45%. IR ꢀ cm 3307
þ
HRMS:
-
Found,
m/z:
1205.3805
[M þH]. (N–H), 2953 and 2869 (Aliphatic C–H), 1705 (C ¼ O), 1541
þ
1
C H ClN O Si Calculated, m/z: 1204.3920 [M] .
4
9
87
2
15
8
(Si–O–Si), 1463, 1399, 1228, 1086 (Si–O–R), 836, 740. H
NMR (500 MHz, CDCl ), d, ppm (J, Hz): 0.56–0.58 (2H, m,
3
CH ); 0.61 (14H, t, J = 6.93, 7xCH -Si); 0.82–0.90 (2H, m,
2
2
N-[3-(isobutylpolyhedral oligomeric
CH ); 0.95 (42H, dd, J = 3.2; 6.6, 14xCH ); 1.43 (2H, m,
2
3
silsesquioxanyl)propyl]-2-(4-Azabicyclo[2.2.1]hept-8-(2-
chlorophenyl)-3-endo,5-endo-dicarboximide-4-yl)
propanamide (5b)
CH ); 1.57–1.65 (3H, m, H10a, H10s, CH); 1.86 (7H, pent,
2
J = 6.6, 7xCH); 2.73 (1H, dd, J = 4.7; 19.9, H ); 3.02–3.11
1
(
3H, m, CH , H ); 3.21–3.31 (2H, m, N-CH ); 3.37–3.42
2 7 2
ꢀ
ꢁ1
White solid. mp 108–110 C; Yield 50%. IR ꢀ cm 2953, (1H, m, CH); 3.54 (1H, dd, J = 12.0; 14.2, H8n), 4.05 (1H, m,
2
930, 2906 and 2870 (Aliphatic C–H), 1690 (C ¼ O), 1524 CH); 5.94 (1H, m, NH), 6.92 (1H, t, J = 7.3, ArH); 7.15 (3H,
1
(
Si–O–Si), 1463, 1398, 1382, 1083 (Si–O–R), 808. H NMR dd, J = 7.9; 15.4, ArH); 7.26 (1 H, d, J = 6.0, ArH); 7.36 (1H,
(
500 MHz, CDCl ), d, ppm (J, Hz): 0.62 (14H, dd, J = 3.46; d, J = 8.51, ArH); 7.43 (1H, d, J = 8.51, ArH); 7.52 (2H, dd,
3
13
7
.25, 7xCH -Si); 0.83–0.88 (2H, m, CH ); 0.97 (42H, d, J = 5.04; 8.27, ArH). C NMR (125 MHz, CDCl ), d, ppm:
2
2
3
J = 6.61, 14xCH ); 1.00 (3H, d, J = 6.61, CH ); 1.26–1.33 (4H, 9.4 (CH ); 22.5 (7xCH ); 22.8 (2xCH ); 23.9 (7xCH); 23.9
3
3
2
2
2