7144 J . Org. Chem., Vol. 61, No. 20, 1996
Alvisi et al.
) 18.7 Hz, 4.6 Hz, 1H); 13C NMR δ -1.40, 28.3, 45.0, 79.2,
130.2, 142.3, 155.1; MS m/ z (relative intensity) 173 (6), 158
(54), 140 (32), 114 (30), 100 (53), 73 (100), 59 (70), 57 (60).
Anal. Calcd for C11H23NO2Si: C, 57.60; H, 10.12; N, 6.11,
found: C, 57.62; H, 10.13; N, 6.13.
The crude mixture was purified by column chromatography
with petroleum ether/diethyl ether (100/3) to give 300 mg (32%)
of the (Z)-isomer 1g and 280 mg (30%) of the (E)-isomer as
light yellow oils.
1g, (Z)-isomer:
1H NMR δ 0.45 (s, 6H), 3.75 (s, 3H), 6.58
(E)-3-(1-Eth oxyeth oxy)-1-(tr im eth ylsilyl)p r op en e (1b).
The silylcupration was performed according to procedure I,
starting from 666 mg (5.2 mmol) of 3-(1-ethoxyethoxy)propyne,
and after 1 h was subjected to the usual workup. The crude
mixture was purified by column chromatography with petro-
leum ether/ether (95:5) to give 735 mg (70%) of 1b as a light
yellow oil.
(d, J ) 14.7 Hz, 1H), 6.93 (d, J ) 14.7 Hz, 1H), 7.30-7.60 (m,
5H); 13C NMR δ -2.0, 51.4, 128.0, 129.2, 133.3, 135.5, 136.4,
150.3, 162.0; MS m/ z (relative intensity) 220 (1), 205 (100),
175 (30), 143 (75), 135 (15). Anal. Calcd for C12H16O2Si: C,
65.41; H, 7.32, found: C, 66.51; H, 7.35.
1g, (E)-isomer: 1H NMR δ 0.43 (s, 6H), 3.75 (s, 3H), 6.24
(d, J ) 18.9 Hz, 1H), 7.26-7.56 (m, 6H); 13C NMR δ -3.7, 51.3,
127.6, 127.9, 128.8, 129.5,133.7, 134.9, 166.0; MS m/ z (relative
intensity) 220 (20), 219 (65), 205 (60), 189 (25), 135 (50), 121
(65), 89 (100). Anal. Calcd for C12H16O2Si: C, 65.41; H, 7.32,
found: C, 66.48; H, 7.34.
1b: 1H NMR δ 0.30 (s, 9H), 1.17 (t, J ) 7.1 Hz, 3H), 1.29 (d,
J ) 5.3 Hz, 3H), 3.35-3.75 (m, 2H), 3.92-4.17 (m, 2H), 4.70
(q, J ) 5.3 Hz, 1H), 5.87 (dt, J ) 18.7 Hz, 1.3 Hz, 1H), 6.07
(dt, J ) 18.7 Hz, 4.6 Hz, 1H); 13C NMR δ -1.42, 15.2, 19.8,
60.6, 67.9, 99.1, 131.5, 142.3; MS m/ z (relative intensity) 187
(5), 157 (5), 129 (23), 75 (45), 73 (100). Anal. Calcd for
C10H22O2Si: C, 59.35; H, 10.96, found: C, 59.39; H, 10.95.
(E) 3-Meth oxy-1-(tr im eth ylsilyl)p r op en e (1c). The si-
lylcupration was performed according to procedure I, starting
from 1.05 g (15.0 mmol) of 3-methoxypropyne, and after 2 h
was subjected to the usual workup. The crude mixture was
distilled at atmospheric pressure to give 890 mg (41%) of 1c
as a light yellow oil.
(Z)-4-(Dim eth ylph en ylsilyl)-3-h exylbu t-3-en -2-on e (1h ).
The silylated vinyl-copper intermediate prepared according to
procedure II, starting from 0.620 mL (4.2 mmol) of oct-1-yne,
was treated, after 2 h, at -23 °C with 0.90 mL (12.6 mmol) of
acetyl chloride. After stirring for 2 h at -23 °C, the resulting
mixture was quenched and worked up as usual. The crude
mixture was purified by column chromatography with petro-
leum ether/ether (90:5) to give 900 mg (75%) of 1h as a
colorless oil.
1c: 1H NMR δ 0.05 (s, 9H), 3.35 (s, 3H), 3.90-3.98 (m, 2H),
5.90 (dt, J ) 18.9 Hz, 1.2 Hz, 1H), 6.07 (dt, J ) 18.9 Hz, 4.4
Hz, 1H); 13C NMR δ -0.91, 58.6, 75.9, 132.6, 142.6; MS m/ z
(relative intensity) 129 (73), 99 (10), 89 (58), 75 (70), 73 (100),
59 (52), 45 (26). Anal. Calcd for C7H16OSi: C, 58.27; H, 11.18,
found: C, 58.29; H, 11.19.
(E)-N-(ter t-Bu t oxyca r b on yl)-4-(t r im et h ylsilyl)b u t -3-
en yla m in e (1d ). The silylcupration was performed according
to procedure I, starting from 330 mg (1.95 mmol) of N-(tert-
butoxycarbonyl)butynylamine, and after 1 h was quenched and
treated as usual. The crude mixture was purified by column
chromatography with petroleum ether/ether (10:1) to give 370
mg (78%) of 1d as a colorless oil.
1h : IR (neat) 1692, 1420, 1245 cm-1; 1H NMR δ 0.38 (s, 6H),
0.90 (br s, 3H), 1.20-1.50 (m, 8H), 2.15 (s, 3H), 2.38 (m, 2H),
5.90 (br s, 1H), 7.25-7.60 (m, 5H); 13C NMR δ -2.0, 13.8, 22.4,
27.9, 28.4, 28.7,31.4, 36.3, 127.7, 128.8, 133.8, 136.5, 140.2,
157.5, 203.1; MS m/ z (relative intensity) 288 (1), 273 (100),
203 (63), 135 (33), 75 (15). Anal. Calcd for C18H28OSi: C,
74.94; H, 9.78, found: C, 75.01; H, 9.79.
(Z)-4-(Dim eth ylph en ylsilyl)-3-ph en ylbu t-3-en -2-on e (1i).
Following exactly the same procedure as for 1h , but starting
from 0.925 mL (8.4 mmol) of phenylacetylene, 2.15 g (91%) of
1i were obtained as a colorless oil.
1
1i: IR (neat) 1700, 1688, 1427, 1246 cm-1; H NMR δ 0.35
(s, 6H), 1.90 (s, 3H), 6.15 (s, 1H), 7.05-7.55 (m, 10 H); 13C
NMR δ -2.0, 29.5, 127.1, 127.8, 128.4, 128.7, 129.0, 134.0,
136.0, 139.0, 139.2, 158.6, 204.0; MS m/ z (relative intensity)
280 (5), 265 (100), 203 (54), 135 (32); HRMS (EI) calcd for
C18H20OSi 280.128 34, found 280.128 96.
1d : 1H NMR δ 0.02 (s, 9H), 1.41 (s, 9H), 2.20-2.36 (m,
2H),3.10-3.26 (m, 2H), 4.57 (br s, 1H), 5.68 (dt, J ) 18.7 Hz,
1 Hz, 1H), 5.92 (dt, J ) 18.7 Hz, 6.1 Hz, 1H); 13C NMR δ -0.81,
28.9, 37.5, 40.0, 79.5, 133.4, 142.5, 155.4; MS m/ z (relative
intensity) 187 (5), 172 (8), 99 (12), 73 (40), 59 (45), 57 (100).
Anal. Calcd for C12H25NO2Si: C, 59.21; H, 10.35; N, 5.75,
found: C, 59.28; H, 10.37; N, 5.78.
(E)-4-(1-Eth oxyeth oxy)-1-(tr im eth ylsilyl)bu t-1-en e (1e).
The silylcupration was performed according to procedure I,
starting from 1.28 g (8.45 mmol) of 4-(1-ethoxyethoxy)but-1-
yne, and after 2 h was subjected to the usual workup. The
crude mixture was purified by column chromatography with
petroleum ether/ethyl acetate (20:1) to give 1.08 g (59%) of 1e
as a light yellow oil.
(E)-2-Meth yl-3-(tr im eth ylsilyl)a cr ylic Acid Eth yl Ester
(1l). The silylated vinylcopper intermediate prepared accord-
ing to procedure I, starting from 1.21 mL (12.0 mmol) of ethyl
propiolate, was treated, after 2 h, at -23 °C with 2.24 mL (36.0
mmol) of iodomethane. The reaction mixture was stirred
under argon overnight at rt. After the usual quench and
workup, the crude mixture was purified by column chroma-
tography with petroleum ether/ether (95:5) to give 470 mg
(21%) of 1l as a colorless oil.
1l: 1H NMR δ 0.13 (s, 9H), 1.25 (t, J ) 7.5 Hz, 3H), 1.95 (s,
3H), 4.15 (q, J ) 7.5 Hz, 2H), 6.80 (s, 1H); 13C NMR δ -0.73,
14.2, 17.4, 60.7, 140.7, 142.8, 167.4; MS m/ z (relative intensity)
171 (42), 143 (66), 103 (17), 75 (100), 73 (60). Anal. Calcd for
C9H18O2Si: C, 58.02; H, 9.74, found: C, 58.00; H, 9.74.
Deu ter ia ted Vin ylsila n es 1a D a n d 1bD. 1a D was pre-
pared by silylcupration of N,N′-bis(trimethylsilyl)propargyl-
amine according to procedure I, followed by quench with
deuteriated water. Subsequent deprotection of nitrogen and
conversion to the NHBoc-protected derivative led to the target
compound in 51% isolated yield.
1e: 1H NMR δ 0.05 (s, 9H), 1.20 (t, J ) 7.5 Hz, 3H), 1.30 (d,
J ) 5.0 Hz, 3H), 2.30-2.45 (m, 2H), 3.40-3.75 (m, 4H), 4.70
(q, J ) 5.0 Hz, 1H), 5.70 (dt, J ) 19.0 Hz, 2.0 Hz, 1H), 6.03
(dt, J ) 19.0 Hz, 6.6 Hz, 1H); 13C NMR δ -1.30, 15.3, 19.7,
37.0, 60.7, 64.1, 99.4, 132.2, 143.2; MS m/ z (relative intensity)
170 (3), 155 (5), 103 (25), 89 (10), 73 (100). Anal. Calcd for
C11H24O2Si: C, 61.06; H, 11.18, found: C, 61.08; H, 11.18.
(E)-1-(Dim eth ylp h en ylsilyl)oct-1-en e (1f). The silylcu-
pration was performed according to procedure II, starting from
0.620 mL (4.2 mmol) of oct-1-yne, and after 1 h was subjected
to the usual workup. The crude reaction mixture was purified
by column chromatography (petroleum ether) to give 1.04 g
(100%) of 1f as a colorless oil.
1bD was obtained in 74% yield following the same procedure
as for 1b and quenching with deuteriated water.
Gen er a l P r oced u r e for th e Gen er a tion of th e Ca ta -
lytic System . In a Pyrex tube with magnetic stirrer and
rubber cap, THF (0.8 mL), Pd(OAc)2 (10 mg, 0.045 mmol), and
ligand (DPPE or DPPB) (0.090 mmol) were sequentially added
and thoroughly degassed (argon) at rt. The stirred mixture
became yellow-orange and was generally used immediately.
P a lla d iu m -Ca ta lyzed Rea ction s. Typ ica l P r oced u r e.
P r ep a r a t ion of N-(ter t-Bu t oxyca r b on yl)-2-(4-m et h oxy-
p h en yl)a llyla m in e (2a ) a n d (Z)-N-(ter t-Bu toxyca r bon yl)-
1
1f: H NMR δ 0.35 (s, 6H), 0.80-1.00 (m, 3H), 1.25-1.60
(m, 8H), 2.10-2.24 (m, 2H), 5.77 (dt, J ) 18.7 Hz, 1.4 Hz, 1H),
6.16 (dt, J ) 18.6 Hz, 6.2 Hz, 1H), 7.30-7.60 (m, 5H); 13C NMR
δ -2.60, 13.9, 22.5, 28.5, 28.7, 31.6, 36.7, 127.4, 127.8, 128.9,
134.0, 139.5, 149.7; MS m/ z (relative intensity) 246 (5%), 231
(10), 161 (25), 135 (100), 121 (40). Anal. Calcd for C16H26Si:
C, 77.97; H, 10.63, found: C, 77.89; H, 10.60.
(Z)- a n d (E)-3-(Dim eth ylp h en ylsilyl)a cr ilic Acid Meth -
yl Ester s (1g). The silylcupration was carried out according
to procedure II, starting from 0.374 mL (4.2 mmol) of methyl
propiolate, and after 1 h was quenched and treated as usual.
3-(4-m eth oxyp h en yl)a llyla m in e (3a ). In
a Pyrex tube
under an atmosphere of argon, vinylsilane 1a (250 mg, 1.1
mmol), p-iodoanisole (515 mg, 2.2 mmol), triethylamine (0.38