1104
M. Hoshi, K. Shirakawa
LETTER
mixture was neutralized with sat. NH4Cl, the resultant
References
mixture was treated with NaBO3·4H2O (1.846 g, 12 mmol)
and H2O (4 mL) at room temperature with vigorous stirring
for 2 h to decompose the residual organoboron compound.
Workup is the same as described in ref. 9. The crude product
was purified by column chromatography on silica gel, with
n-pentane as eluent, to give product 3a (0.401 g, 72% yield)
as a colorless liquid. Compound 3a: 1H NMR (CDCl3) :
0.17 (s, 9 H), 0.88 (t, 3 H), 1.1–1.5 (m, 8 H), 2.0–2.2 (m, 2
H), 5.52 (dt, J = 15.8, 1.5 Hz, 1 H), 6.20 (dt, J = 15.8, 6.8 Hz,
1 H); 13C NMR (CDCl3) 0.00 (Me 3), 14.00, 22.55,
28.58, 28.78, 31.63, 33.06, 92.43 ( C–), 104.28 ( C–),
109.61 (=CH–), 146.26 (=CH–); IR(neat) 2958, 2927, 2856,
2175, 2133, 1249, 1085, 952, 842, 759 cm–1; HRMS (EI)
C13H24Si: requires 208.1647, found 208.1664.
(1) Saito, S.; Yamamoto, Y. Chem. Rev. 2000, 100, 2901.
(2) For example, see: (a) Stille, J. K.; Simpson, H. J. Am. Chem.
Soc. 1987, 109, 2138. (b) Cabezas, J. A.; Oehlschlager, A.
C. Synthesis 1999, 107.
(3) For example, see: Tsushima, K.; Murai, A. Tetrahedron Lett.
1992, 33, 4345; and references therein.
(4) For example, see: Kobayashi, S.; Reddy, R.; Sugiura, Y.;
Sasaki, D.; Miyagawa, N.; Hirama, M. J. Am. Chem. Soc.
2001, 123, 2887; and references therein.
(5) For the cross-coupling reaction of organocopper, see:
(a) Normant, J. F.; Commercon, A.; Villieras, J. Tetrahedron
Lett. 1975, 16, 1465. (b) Commercon, A.; Normant, J. F.;
Villieras, J. Tetrahedron 1980, 36, 1215.
(6) For the cross-coupling reaction of organostannane, see:
(a) Palmisano, G.; Santagostino, M. Synlett 1993, 771.
(b) Palmisano, G.; Santagostino, M. Tetrahedron 1993, 49,
2533. (c) Palmisano, G.; Santagostino, M. Helv. Chim. Acta
1993, 76, 2356. (d) Untiedt, S.; de Meijere, A. Chem. Ber.
1994, 127, 1511. (e) Suzenet, F.; Parrain, J.-L.; Quintard, J.-
P. Eur. J. Org. Chem. 1999, 2957. (f) Siegel, K.; Brückner,
R. Synlett 1999, 1227.
(7) For the cross-coupling reaction of organozirconium, see:
(a) Kasai, K.; Liu, Y.; Hara, R.; Takahashi, T. Chem.
Commun. 1998, 1989. (b) Liu, Y.; Xi, C.; Hara, R.;
Nakajima, K.; Yamazaki, A.; Kotora, M.; Takahashi, T. J.
Org. Chem. 2000, 65, 6951. (c) For Heck reaction, see:
Jeffery, T. Synthesis 1987, 70.
(11) Negishi, E.; Williams, R. M.; Lew, G.; Yoshida, T. J.
Organomet. Chem. 1975, 92, C4.
(12) (Z)-3-Decen-1-yne(5a): 1H NMR (CDCl3) : 0.88 (t, 3 H),
1.1–1.55 (m, 8 H), 2.2–2.45 (m, 2 H), 3.05 (d, J = 2.2 Hz, 1
H), 5.45 (ddt, J = 11.0, 1.3, 0.9 Hz, 1 H), 5.98 (dtd, J = 11.0,
7.3, 0.9 Hz, 1 H); 13C NMR (CDCl3) : 14.04, 22.60, 28.74,
28.87, 30.29, 31.68, 80.62 ( C–), 81.11 ( CH), 108.03
( CH–), 146.22 (=CH–); IR(neat) 3313, 3024, 2956, 2927,
2856, 2358, 1465, 738 cm–1; HRMS (EI) C10H16: requires
136.1252, found 136.1253.
(13) (Z)-1-Trimethylsilyl-3-decen-1-yne(6a): 1H NMR (CDCl3)
: 0.19 (s, 9 H), 0.88 (t, 3 H), 1.1–1.55 (m, 8 H), 2.2–2.45 (m,
2 H), 5.48 (dt, J = 11.0, 1.3 Hz, 1 H), 5.94 (dt, J = 11.0, 7.3
Hz, 1 H); 13C NMR (CDCl3) : 0.00 (Me 3), 14.00, 22.59,
28.66, 28.78, 30.25, 31.59, 98.41 ( C–), 102.24 ( C–),
109.16 (=CH–), 145.57 (=CH–); IR(neat) 3020, 2958, 2927,
2856, 2148, 1249, 842, 759 cm–1; HRMS (EI) C13H24Si:
requires 208.1647, found 208.1671.
(14) (a) Allred, G. D.; Liebeskind, L. S. J. Am. Chem. Soc. 1996,
118, 2748. (b) Zhang, S.; Zhang, D.; Liebeskind, L. S. J.
Org. Chem. 1997, 62, 2312.
(15) Evans, D. A.; Katz, J. L.; West, T. R. Tetrahedron Lett.
1998, 39, 2937.
(8) For example, see: (a) Miyaura, N.; Suzuki, A. Chem. Rev.
1995, 95, 2457. (b) Suzuki, A. In Metal-Catalyzed Cross-
coupling Reactions; Diederich, F.; Stang, P. J., Eds.; Wiley-
VCH: Weinheim, 1998. (c) Suzuki, A. J. Organomet. Chem.
1999, 576, 147.
(9) To a stirred solution of (E)-1-octenylbis(1,2-dimethyl-
propyl)borane (4 mmol) in THF (12 mL) at –15 °C,
Cu(acac)2 (0.052 g, 0.2 mmol) was added under an argon
flow. (Trimethylsilyl)ethynyl bromide (0.474 g, 2.68 mmol)
and 1 M NaOMe (4 mL, 4 mmol) were then added dropwise
to the solution, and the resulting mixture was allowed to
warm gradually to room temperature and to stir overnight.
The reaction mixture was treated with 3 M NaOH (4 mL)
and 30% H2O2 (2 mL) at 0 °C and stirred for 1 h at the same
temperature to decompose the residual organoboron
compound. The resultant mixture was extracted with ether,
washed with brine, and dried over anhydrous Na2SO4. The
solvent was removed on a rotary evaporator under reduced
pressure, and the crude product was purified by column
chromatography on silica gel, with n-pentane as eluent, to
give product 2a (0.255 g, 70% yield) as a colorless liquid.
Compound 2a: 1H NMR (CDCl3) : 0.88 (t, 3 H), 1.1–1.5
(m, 8 H), 2.0–2.2 (m, 2 H), 2.76 (dd, J = 2.2, 0.4 Hz, 1 H),
5.47 (ddt, J = 16.0, 2.2, 1.5 Hz, 1 H), 6.22 (dtd, J = 16.0, 6.8,
0.4 Hz, 1 H); 13C NMR (CDCl3) : 14.04, 22.60, 28.58,
28.79, 31.68, 33.02, 75.49 (CH), 82.66 ( C–), 108.52
( CH–), 146.96 (=CH–); IR(neat) 3315, 3024, 2956, 2927,
2856, 2104, 1629, 1465, 1436, 954, cm–1; HRMS (EI)
C10H16: requires 136.1252; found 136.1254.
(16) For example, see: Sonogashira, K. In Metal-Catalyzed
Cross-coupling Reactions; Diederich, F.; Stang, P. J., Eds.;
Wiley-VCH: Weinheim, 1998.
(17) Mori, A.; Shimada, T.; Kondo, T.; Sekiguchi, A. Synlett
2001, 649.
(18) (E)-1-Phenyl-3-decen-1-yne: 1H NMR (CDCl3) : 0.88 (t, 3
H), 1.1–1.5 (m, 8 H), 2.05–2.3 (m, 2 H), 5.70 (dt, J = 15.8,
1.4 Hz, 1 H), 6.22 (dt, J = 15.8, 7.0 Hz, 1 H), 7.2–7.5 (m, 5
H); 13C NMR (CDCl3) : 14.04, 22.60, 28.79(–CH2– 2),
31.68, 33.22, 87.91 (C–), 88.44 (C–), 109.57 (=CH–),
123.79 (=C<), 127.82 (=CH–), 128.22 (=CH– 2), 131.44
(=CH– 2), 145.16 (=CH–); IR (neat) 3080, 3055, 3020,
2954, 2927, 2854, 2202, 1596, 1571, 1488, 1463, 1454,
1442, 1379, 1303, 1068, 952, 912, 754, 690 cm–1; MS (EI)
m/z 212 (M+, 51%), 183(3), 169(6), 155(24), 141(78),
128(100), 115(41), 102(6), 91(13), 77(7), 63(4). (Z)-1-
Phenyl-3-decen-1-yne: 1H NMR (CDCl3) : 0.88 (t, 3 H),
1.1–1.5 (m, 8 H), 2.25–2.55 (m, 2 H), 5.67 (dt, J = 10.8, 1.1
Hz, 1 H), 5.96 (dt, J = 10.8, 7.0 Hz, 1 H), 7.2–7.5 (m, 5 H);
13C NMR (CDCl3) : 14.08, 22.64, 28.87(–CH2– 2), 30.41,
31.72, 86.57 ( C–), 93.45 ( C–), 109.05 (=CH–), 123.87
(=C<), 127.94 (=CH–), 128.27 (=CH– 2), 131.40 (=CH–
2), 144.31 (=CH–); IR (neat) 3080, 3058, 3020, 2956, 2927,
2856, 1595, 1571, 1488, 1467, 1456, 1440, 1398, 1377,
1068, 1028, 1014, 912, 754, 732, 690 cm–1; HRMS (EI)
C16H20: requires 212.1565, found 212.1559.
(10) To a stirred solution of (E)-1-octenyldicyclohexylborane (4
mmol) in THF (12 mL) at –15 °C, Cu(acac)2 (0.052 g, 0.2
mmol) was added under an argon flow. (Trimethyl-
silyl)ethynyl bromide (0.474 g, 2.68 mmol) was added
dropwise to the solution, and then LiOH·H2O (0.168 g, 4
mmol) was introduced into the solution under an argon flow.
The resulting mixture was allowed to warm gradually to
room temperature and to stir overnight. After the reaction
Synlett 2002, No. 7, 1101–1104 ISSN 0936-5214 © Thieme Stuttgart · New York