11696
E. Thomas et al. / Tetrahedron 63 (2007) 11686–11701
1
compound as a colourless oil (185 mg, 50%). H NMR
(400 MHz, CDCl3): d¼7.23 (2H, t, J¼7.4 Hz), 7.15–7.12
(3H, m), 5.83 (1H, dt, J¼10.5, 7.5 Hz), 5.47 (1H, d,
J¼10.5 Hz), 3.30 (3H, s), 3.26 (3H, s), 3.17–3.09 (4H, m),
3.00 (1H, dd, J¼13.3, 3.6 Hz), 2.60 (1H, m), 2.33 (2H, m),
2.28 (1H, dd, J¼13.3, 9.8 Hz), 2.20 (1H, dt, J¼14.8,
7.5 Hz), 1.77 (1H, m), 1.74 (1H, dd, J¼13.3, 7.3 Hz), 1.65
(1H, m), 1.57 (1H, dd, J¼13.3, 7.0 Hz), 1.55–1.48 (2H,
m), 1.45–1.38 (2H, m), 1.14 (1H, dd, J¼13.3, 10.6 Hz),
1.09 (1H, dd, J¼13.3, 10.8 Hz), 0.90 (3H, t, J¼7.2 Hz)
ppm. 13C NMR (100 MHz, CDCl3): d¼141.76 (s), 140.71
(d), 129.06 (d), 128.29 (d), 125.76 (d), 110.36 (d), 94.86
(s), 77.87 (2ꢂt), 77.69 (s), 59.37 (q), 59.31 (q), 46.58 (d),
45.27 (s), 44.69 (d), 40.43 (t), 39.08 (t), 38.81 (t), 33.93
(t), 31.12 (t), 22.14 (t), 19.39 (t), 13.75 (q) ppm. IR (film):
2824 (m), 1603 (w), 1494 (w), 1453 (m), 1198 (m), 1104
(s), 963 (m), 750 (m) cmꢀ1. LRMS (EI) m/z (%): 368 (M+,
4), 304 (M+ꢀC6H5, 6), 291 (M+ꢀC6H5CH2, 12), 91
(C6H5CH+2, 100), 77 (C6H5+, 45). HRMS (EI): C25H36O2
(M)+ requires m/z 368.2715. Found 368.2708.
13.60 (q), 13.10 (q) ppm. The following signals for 27
could be distinguished. 1H NMR (400 MHz, CDCl3):
d¼5.69 (1H, dt, J¼10.5, 7.3 Hz), 5.36 (1H, d, J¼10.6,
2.1, 1.4 Hz), 0.99 (3H, s) ppm. 13C NMR (100 MHz,
CDCl3): d¼141.17 (d), 139.36 (d), 128.40 (d), 128.05
(d), 111.33 (d), 110.11 (d), 95.00 (s), 94.67 (s), 77.66
(s), 77.20 (s), 65.54 (t), 60.73 (t), 59.38 (t), 49.08 (d),
43.19 (s), 36.14 (t), 29.53 (t), 25.83 (q), 21.99 (t), 13.52
(q) ppm. IR (film): 2209 (w), 1705 (m), 1119 (s) cmꢀ1
.
LRMS (CI) m/z (%): 310 (M+H+, 44), 252 (22), 186
(44), 91 (100). HRMS (ES+): C22H32N (M+H+) requires
m/z 310.2529. Found 310.2533. Also observed bis-inser-
tion product 27 at m/z 416.3315 requires m/z 416.3312
for M+H+ (C30H42N).
4.4.6. 1-(Octa-1,2,7-trienyl)benzene (30). A solution of
b-bromostyrene (1.54 mL, 12.04 mmol) in THF (10 mL)
was cooled to ꢀ90 ꢁC before addition of LDA (10 mL,
12.04 mmol) over 30 min. After stirring at ꢀ90 ꢁC for
30 min a solution of hex-5-enal (1.18 g, 12.04 mmol) in
THF (4 mL) was added to the reaction mixture over
30 min. The solution was allowed to warm to ꢀ30 ꢁC over
3.5 h before addition of NaHCO3 (aq) (30 mL). The prod-
ucts were extracted into diethyl ether (3ꢂ50 mL), the com-
bined organic phases washed with water (50 mL) and brine
(50 mL), dried over MgSO4 and concentrated in vacuo.
Purification by column chromatography (SiO2 eluted with
4:1 hexane/Et2O) gave (E)-2-bromo-1-phenyl-octa-1,7-
dien-3-ol 28 as a clear oil (1.445 g, 43%). 1H NMR
(400 MHz, CDCl3): d¼7.50–7.30 (6H, m), 5.89 (1H, ddt,
J¼17.0, 10.3, 6.7 Hz), 5.09 (1H, d+fs, J¼17.0 Hz), 5.07
(1H, d+fs, J¼10.3 Hz), 4.66 (1H, t, J¼6.9 Hz), 2.16 (2H, ap-
parent q, J¼6.9 Hz), 1.92–1.77 (3H, m), 1.56 (2H, apparent
pentet, J¼7.6 Hz) ppm. 13C NMR (100 MHz, CDCl3):
d¼138.39 (d), 135.82 (s), 134.19 (d), 134.03 (s), 128.75
(2ꢂd), 128.41 (2ꢂd), 128.00 (d), 115.03 (t), 69.95 (d),
36.09 (t), 33.46 (t), 24.56 (t) ppm. IR (film): 3571 (m, br),
4.4.5.3. rac-(3R,3aR,4S,7aS)-1,1-Bis(methoxymethyl)-
3-methyl-4-((Z)-oct-1-en-3-ynyl)octahydro-1H-indene
(18). The zirconacycle 6 was prepared from 3-(1-methoxy-
2-(methoxymethyl)pent-4-en-2-yl)cyclohex-1-ene accord-
ing to Method A and elaborated using Method F. Purification
by column chromatography (SiO2 eluted with 10:1 petrol/
EtOAc) gave the title compound as a colourless oil
(206 mg, 62%). 1H NMR (400 MHz, CDCl3): d¼5.70 (1H,
t, J¼10.5 Hz), 5.28 (1H, br d, J¼10.5 Hz), 3.23 (10H, m),
2.88 (1H, tt, J¼10.8, 4.3 Hz), 2.28 (2H, dt, J¼1.8, 7.0 Hz),
2.07 (1H, m), 1.95 (2H, m), 1.66 (3H, m), 1.05–1.45 (9H,
m), 0.92 (3H, d, J¼6.5 Hz), 0.87 (3H, t, J¼7.1 Hz) ppm.
13C NMR (100 MHz, CDCl3): d¼146.21 (d), 106.54 (d),
93.43 (s), 75.84 (s), 73.19 (t), 72.96 (t), 58.04 (q), 57.99
(q), 47.92 (d), 47.75 (s), 44.29 (d), 38.96 (d), 38.57 (t),
29.91 (t), 28.93 (d), 26.27 (t), 24.97 (t), 22.79 (q), 22.59
(t), 20.88 (t), 18.21 (t), 12.60 (q) ppm. IR (film): 2206 (w,
br), 750 (m) cmꢀ1. LRMS (CI) m/z (%): 333 (M+H+, 35),
255 (17), 192 (64), 147 (100). HRMS (EI): C22H36O2 (M+)
requires m/z 332.2715. Found 332.2723.
1639 (m), 1443 (s), 1261 (m), 805 (m), 756 (s) cmꢀ1
.
According to the method of Tanaka29 a solution of (E)-2-
bromo-1-phenyl-octa-1,7-dien-3-ol 28 (0.70 g, 2.50 mmol)
and triethylamine (3.48 mL, 25.00 mmol) in THF (20 mL)
was cooled to 0 ꢁC before the dropwise addition of trichlo-
roacetylchloride (1.40 mL, 15.00 mmol). After stirring for
30 min, NaHCO3 (aq) (30 mL) was added. The products
were extracted into diethyl ether (3ꢂ50 mL), the combined
organic phases washed with water (50 mL) and brine
(50 mL), dried over MgSO4 and concentrated in vacuo. Pu-
rification by column chromatography (SiO2 eluted with 9:1
hexane/Et2O) gave (E)-2-bromo-1-phenylocta-1,7-dien-3-
yl 2,2,2-trichloroacetate 29 as a clear oil (0.847 g, 79%).30
1H NMR (400 MHz, CDCl3): d¼7.42–7.22 (6H, m), 5.74
(1H, ddt, J¼18, 9.5, 6.5 Hz), 5.67 (1H, dd, J¼8.4, 6.0 Hz),
4.97 (1H, m), 4.92 (1H, m), 2.07–1.96 (3H, m), 1.85 (1H,
dddd, J¼14, 8.5, 7.5, 6.2 Hz), 1.43 (2H, apparent pentet,
J¼7.5 Hz) ppm. 13C NMR (100 MHz, CDCl3): d¼160.92
(s), 137.73 (d), 137.59 (d), 135.30 (s), 128.92 (2ꢂd),
128.43 (d), 128.21 (2ꢂd), 124.95 (s), 115.52 (t), 77.10 (d),
33.05 (t), 32.58 (t), 23.98 (t) ppm.
4.4.5.4.
rac-(3S,4R)-1-Benzyl-3,4-dimethyl-3-((Z)-
non-2-en-4-ynyl)pyrrolidine (19). The zirconacycle 7
was prepared from N-allyl-N-benzyl-2-methylprop-2-en-
1-amine according to Method A and elaborated using
Method F. Purification by column chromatography (SiO2
eluted with 10:1 petrol/Et3N) yielded a pale yellow oil
(255 mg) estimated to contain the title compound (19)
(204 mg, 66%) and the inseparable bis-addition product
rac-(3R,4S)-1-benzyl-3-methyl-3,4-di((Z)-non-2-en-4-ynyl)-
pyrrolidine 27 (40 mg, 10%). Data for 19: 1H NMR
(400 MHz, CDCl3): d¼7.27–7.17 (5H, m), 5.76 (1H, dt,
J¼10.8, 7.5 Hz), 5.45 (1H, dtt, J¼10.8, 2.2, 1.4 Hz),
3.59 (1H, d, J¼13.1 Hz), 3.51 (1H, d, J¼13.1 Hz), 2.85
(1H, dd, J¼9.1, 7.4 Hz), 2.41 (1H, d, J¼9.4 Hz), 2.37
(1H, d, J¼9.4 Hz), 2.33–2.11 (5H, m), 1.89 (1H, dq,
J¼8.8, 7.1 Hz), 1.51–1.34 (4H, m), 0.96 (3H, s), 0.86
(3H, d, J¼6.8 Hz), 0.84 (3H, t, J¼7.7 Hz) ppm. 13C
NMR (100 MHz, CDCl3): d¼139.89 (s), 139.66 (d),
128.50 (d), 128.09 (d), 126.63 (d), 111.16 (d), 94.63 (s),
77.71 (s), 65.45 (t), 61.45 (t), 60.82 (t), 43.54 (d), 42.94
(s), 36.00 (t), 30.96 (t), 25.68 (q), 21.95 (t), 19.23 (t),
To a stirred solution of (E)-2-bromo-1-phenylocta-1,7-dien-
3-yl 2,2,2-trichloroacetate 29 (0.840 g, 1.98 mmol) and tet-
rakispalladiumtriphenyl phosphine (0.229 g, 0.20 mmol) in