PAPER
Regio- and Stereoselective Dimerization of Terminal Alkynes
1065
Dimerization of Alkynes Catalyzed by Y[N(SiMe ) ] with
(Z)-1,4-Di(p-anisyl)but-1-en-3-yne (4d)
3
2 3
Amine Additives; (Z)-1,4-Diphenylbut-1-en-3-yne (4c); Typical
Procedure
Yellow liquid; R 0.20 (hexane–EtOAc, 25:1, SiO ).
IR (neat) = 3005, 2957, 2930, 2835, 2185 cm–1.
f
2
Y[N(SiMe ) ] (1) (39 mg, 0.07 mmol) and 4-chloroaniline (8.9 mg,
3
2 3
1
H NMR (CDCl ): d = 3.80 (3 H, s), 3.81 (3 H, s), 5.77 (1 H, d,
0
.07 mmol) were placed in a 20-mL Schlenk tube and dissolved in
3
J = 11.8 Hz), 6.58 (1 H, d, J = 11.8 Hz), 6.87 (2 H, d, J = 8.9 Hz),
toluene (0.7 mL). The mixture was stirred for 1 h at r.t. Then, phe-
nylacetylene (2c; 146 mg, 1.4 mmol) was added to the mixture. The
Schlenk tube was closed and stirring was continued for 17 h at 100
6
.89 (2 H, d, J = 8.9 Hz), 7.42 (2 H, d, J = 8.9 Hz), 7.88 (2 H, d,
J = 8.7 Hz).
°
C. The reaction mixture was quenched with H O (2 mL) and aq sat.
13
2
C NMR (CDCl ): d = 55.22, 55.23, 87.4, 95.4, 105.1, 113.6, 114.0,
3
NH Cl solution (1 mL), and diluted with Et O (2 mL). GC yield was
4
2
115.7, 129.7, 130.1, 132.8, 137.3, 159.5, 159.6.
determined by using methyl benzoate as an internal standard. The
+
MS: m/z (%) = 264 (M , 100), 249 (38).
organic layer was extracted with Et O (30 mL), washed with brine
2
(
30 mL), dried (MgSO ), and concentrated in vacuo. The crude
4
(
Z)-1,4-Di(p-tolyl)but-1-en-3-yne (4e)
product was purified by flash column chromatography on silica gel
with hexane as eluent to give 129 mg (90%) of the dimer 4c; yellow
liquid; R 0.27 (hexane, SiO ).
Yellow solid; mp 61–63 °C; R 0.26 (hexane, SiO ).
f
2
–
1
IR (KBr): 3026, 2920, 2856, 2361 cm .
1H NMR (CDCl
): d = 2.37 (6 H, s), 5.85 (1 H, d, J = 11.8 Hz), 6.65
f
2
–
1
IR (neat): 3061, 3020, 2189 cm .
3
1
(1 H, d, J = 11.8 Hz), 7.16 (2 H, d, J = 8.2 Hz), 7.19 (2 H, d, J = 8.2
Hz), 7.38 (2 H, d, J = 8.0 Hz), 7.83 (2 H, d, J = 8.2 Hz).
H NMR (CDCl ): d = 5.93 (1 H, d, J = 11.8 Hz), 6.71 (1 H, d,
3
J = 12.1 Hz), 7.29–7.41 (6 H, m), 7.48–7.50 (2 H, m), 7.93 (2 H, d,
J = 7.5 Hz).
13C NMR (CDCl
129.0, 129.2, 131.3, 133.9, 138.2, 138.4.
): d = 21.4, 21.5, 87.9, 95.9, 106.5, 120.5, 128.7,
3
1
3
C NMR (CDCl ): d = 88.2, 95.8, 107.4, 123.4, 128.27, 128.34,
3
+
1
28.4, 128.5, 128.7, 131.4, 136.5, 138.6.
MS: m/z (%) = 232 (M , 100), 215 (58), 202 (67).
+
MS: m/z (%) = 204 (M , 59), 202 (100), 101 (50).
(
Z)-1,4-Di(4-bromophenyl)but-1-en-3-yne (4f)
Yellow liquid; R 0.36 (hexane, SiO ).
f
2
2
-Hexyldec-1-en-3-yne (3a)
1H NMR (CDCl
J = 11.8 Hz), 7.32 (2 H, d, J = 8.4 Hz), 7.49 (2 H, d, J = 7.6 Hz),
): d = 5.92 (1 H, d, J = 11.9 Hz), 6.66 (1 H, d,
Yellow liquid; R 0.73 (hexane, SiO ) .
3
f
2
–
1
IR (neat) = 3427, 2928, 2858, 2212 cm .
7
.51 (2 H, d, J = 7.6 Hz), 7.76 (2 H, d, J = 8.5 Hz).
1
H NMR (CDCl ): d = 0.89 (3 H, t, J = 6.8 Hz), 0.90 (3 H, t, J = 6.9
3
13
C NMR (CDCl ): d = 88.9, 95.4, 107.9, 122.1, 122.5, 122.9, 130.1,
3
Hz), 1.20–1.57 (16 H, m), 2.11 (2 H, t, J = 7.5 Hz), 2.30 (2 H, t,
J = 7.0 Hz), 5.12 (1 H, d, J = 1.2 Hz), 5.20 (1 H, d, J = 1.4 Hz).
1
31.5, 131.8, 132.8, 135.3, 137.8.
1
3
C NMR (CDCl ): d = 14.0, 14.1, 19.3, 22.57, 22.62, 28.1, 28.5,
3
(Z)-1,4-Di(4-fluorophenyl)but-1-en-3-yne (4g)
2
8.6, 28.8, 31.4, 31.7, 37.6, 81.0, 90.0, 119.2, 132.4.
Yellow liquid; R 0.32 (hexane, SiO ).
f
2
+
MS: m/z (%) = 220 (M , 10), 29 (100).
–1
IR (CCl ): 3024, 2925, 2855, 2186 cm .
4
1
H NMR (CDCl ): d = 5.87 (1 H, d, J = 11.8 Hz), 6.66 (1 H, d,
3
2
-Butyloct-1-en-3-yne (3b)
J = 11.8 Hz), 7.03–7.09 (4 H, m), 7.43–7.47 (2 H, m), 7.87–7.91 (2
Yellow liquid; R 0.77 (hexane, SiO ).
f
2
H, m).
–
1
IR (neat): 3094, 2957, 2930, 2224 cm .
1
3
C NMR (CDCl ): d = 87.6, 94.8, 106.8 (d, J = 2.5 Hz), 115.2 (d,
3
1
H NMR (CDCl ): d = 0.91 (3 H, t, J = 7.3 Hz), 0.92 (3 H, t, J = 7.3
3
J = 21.3 Hz), 115.7 (d, J = 23.0 Hz), 119.4 (d, J = 3.3 Hz), 130.4
Hz), 1.25–1.55 (8 H, m), 2.12 (2 H, t, J = 7.4 Hz), 2.31 (2 H, t,
J = 6.9 Hz), 5.12 (1 H, s), 5.20 (1 H, s).
(
(
d, J = 8.2 Hz), 132.7 (d, J = 4.1 Hz), 133.3 (d, J = 8.2 Hz), 137.4
d, J = 8.2 Hz), 162.5 (d, J = 249.4 Hz), 162.6 (d, J = 250.2 Hz).
1
3
C NMR (CDCl ): d = 10.8, 11.1, 16.2, 19.1, 19.2, 27.5, 28.1, 34.5,
+
3
MS: m/z = 240 (M , 76), 239 (60), 238 (100).
7
8.2, 87.2, 116.5, 129.6.
1
1
+
(Z)-1,4-Di(o-tolyl)but-1-en-3-yne (4h)
MS: m/z (%) = 164 (M , 1), 149 (4), 122 (60), 107 (91), 93 (86), 79
(
1
H NMR (CDCl ) : d = 2.33 (3 H, s), 2.43 (3 H, s), 5.99 (1 H, d,
100).
3
J = 11.8 Hz), 6.86 (1 H, d, J = 11.8 Hz), 7.12–7.22 (6 H, m), 7.38
(1 H, d, J = 7.3 Hz), 8.25–8.27 (1 H, m).
,4-Diphenylbut-1-en-3-yne (3c)11
2
1
H NMR (CDCl ): d = 5.82 (1 H, d, J = 0.8 Hz), 6.03 (1 H, d, J = 0.8
+
3
MS: m/z = 232 (M , 92), 215 (100), 202 (75), 115 (79).
Hz), 6.69–6.98 (2 H, m), 7.40–7.60 (4 H, m), 7.69–7.74 (4 H, m).
(
Z)-Hexadec-7-en-9-yne (4a)
Acknowledgment
Yellow liquid; R 0.63 (hexane, SiO ).
f
2
This work was partially supported by a Grant-in-Aid for Scientific
Research from the Ministry of Education, Science, Sport and Cul-
ture, Japan.
–
1
IR (neat): 3020, 2925, 2856 cm .
1
H NMR (CDCl ): d = 0.86–0.90 (6 H, m), 1.27–1.44 (14 H, m),
.48–1.57 (2 H, m), 2.26 (2 H, q, J = 7.2 Hz), 2.32 (2 H, dt, J = 1.8,
.0 Hz), 5.42 (1 H, dt, J = 10.6, 1.8 Hz), 5.80 (1 H, dt, J = 10.6, 7.2
3
1
7
Hz).
References
1
3
C NMR (CDCl ): d = 14.04, 14.08, 19.5, 22.58, 22.61, 28.6, 28.85,
(1) (a) Trost, B. M. Science 1991, 254, 1471. (b) Trost, B. M.
Angew. Chem. Int. Ed. 1995, 34, 259. (c) Nicolaou, K. C.;
Dai, M. W.; Tsay, S. C.; Estevez, V. A.; Wrasidlo, W.
Science 1992, 256, 1172.
3
2
8.86, 28.89, 30.0, 31.4, 31.7, 77.4, 94.3, 109.3, 142.6.
+
MS: m/z (%) = 220 (M , 5), 29 (100).
Synthesis 2004, No. 7, 1062–1066 © Thieme Stuttgart · New York