102
Y. Wang, F. G. West
PAPER
(E)-9,9-Dimethoxy-2-methylnona-1,3-diene
1H NMR (500 MHz, CDCl3): = 6.13 (d, 1 H, J = 15.7 Hz), 5.66
(dt, 1 H, J = 15.6, 7.0 Hz), 4.85 (s, 2 H), 2.09 (q, 2 H, J = 6.9 Hz),
1.83 (s, 3 H), 1.42–1.24 (m, 14 H), 0.88 (t, 3 H, J = 7.0 Hz).
13C NMR (125 MHz, CDCl3): = 142.47, 132.86, 131.38, 114.27,
33.00, 32.13, 29.79, 29.76, 29.67, 29.56, 29.49, 22.92, 18.94, 14.35.
The diene was prepared from lithiated 5b and 6,6-dimethoxyhexa-
nal according to the general procedure and was obtained as a color-
1
less oil in 65% yield (single isomer by H NMR); Rf 0.39 (1:9
EtOAc–hexanes).
IR (film): 3082, 2950, 1609, 1456, 1382, 1128, 1076, 964 cm–1.
(E)-1-Cyclohexyl-3-methylbuta-1,3-diene
1H NMR (300 MHz, CDCl3): = 6.14 (d, 1 H, J = 15.7 Hz), 5.64
(dt, 1 H, J = 15.6, 6.9 Hz), 4.86 (br s, 2 H), 4.36 (t, 1 H, J = 5.8 Hz),
3.31 (s, 6 H), 2.11 (q, 2 H, J = 6.7 Hz), 1.83 (br s, 3 H), 1.65–1.56
(m, 2 H), 1.49–1.30 (m, 4 H).
13C NMR (75 MHz, CDCl3): = 142.34, 133.14, 130.82, 114.47,
104.64, 52.80, 32.85, 32.54, 29.46, 24.41, 18.91.
The diene10,27 was prepared from lithiated 5b and cyclohexanecar-
baldehyde according to the general procedure and was obtained as
1
a colorless oil in 75% yield (single isomer by H NMR); Rf 0.90
(hexanes).
IR (film): 3081, 2926, 1607 cm–1.
1H NMR (500 MHz, CDCl3): = 6.10 (d, 1 H, J = 15.8 Hz), 5.60
(dd, 1 H, J = 15.9, 7.0 Hz), 4.87 (br s, 2 H), 2.06–1.98 (m, 1 H), 1.83
(s, 3 H), 1.77–1.62 (m, 5 H), 1.34–1.05 (m, 5 H).
Anal. Calcd for C12H22O2: C, 72.68; H, 11.18. Found: C, 72.55; H,
11.30.
(E)-11,11-Dimethoxy-2-methylundeca-1,3-diene
The diene was prepared from lithiated 5b and 8,8-dimethoxyoctanal
according to the general procedure and was obtained as a colorless
oil in 69% yield (single isomer by 1H NMR); Rf 0.42 (1:9 EtOAc–
hexanes).
13C NMR (125 MHz, CDCl3): = 142.61, 136.99, 130.38, 114.47,
41.08, 33.22, 26.39, 26.29, 18.90.
(E)-Nona-6,8-dienal (1); Typical Procedure
To a solution of 4a (1.0 g, 5.43 mmol) in THF (20 mL) was added
6% aq HCl (15 mL). After stirring for 8 h at r.t., the mixture was ex-
tracted with Et2O (3 30 mL). The organic phases were combined,
washed with sat. aq NaHCO3 (25 mL), and brine (2 25 mL), dried
(MgSO4) and concentrated to give 0.70 g (93%) of known aldehyde
12 as a clear, colorless oil; Rf 0.33 (1:9 EtOAc–hexanes).
1H NMR (500 MHz, CDCl3): = 9.71 (t, 1 H, J = 1.8 Hz), 6.25
(ddd, 1 H, J = 17.1, 10.2, 10.2 Hz), 6.00 (dd, 1 H, J = 15.1, 10.3
Hz), 5.62 (dt, 1 H, J = 15.1, 6.8 Hz), 5.05 (br d, 1 H, J = 17.0 Hz),
4.91 (br d, J = 10.1 Hz), 2.39 (td, 2 H, J = 7.2, 1.8 Hz), 2.07 (br q, 2
H, J = 6.4 Hz), 1.66–1.55 (m, 2 H), 1.46–1.34 (m, 2 H).
IR (film): 3081, 2987, 1608, cm–1.
1H NMR (500 MHz, CDCl3): = 6.12 (d, 1 H, J = 15.6 Hz), 5.64
(dt, 1 H, J = 15.6, 7.9 Hz), 4.85 (s, 2 H), 4.35 (t, 1 H, J = 5.9 Hz),
3.31 (s, 6 H), 2.09 (q, 2 H, J = 7.0 Hz), 1.83 (s, 3 H), 1.62–1.56 (m,
2 H), 1.44–1.28 (m, 8 H).
13C NMR (125 MHz, CDCl3): = 142.39, 132.95, 131.17, 114.34,
104.74, 52.81, 32.92, 32.68, 29.54, 29.52, 29.34, 24.76, 18.92.
(E)-8-(2-Tetrahydropyranyloxy)-2-methylocta-1,3-diene
The diene was prepared from lithiated 5b and the corresponding al-
dehyde according to the general procedure and was obtained as a
colorless oil in 63% yield (single isomer by 1H NMR); Rf 0.48 (1:9
EtOAc–hexanes).
13C NMR (125 MHz, CDCl3): = 202.48, 137.17, 134.46, 131.48,
115.06, 43.73, 32.25, 28.65, 21.60.
(E)-Deca-7,9-dienal (6)
IR (film): 3082, 2966, 1608 cm–1.
Aldehyde 6 was prepared from 4b by following the typical proce-
dure for the preparation of 1 and was obtained as a colorless oil in
88% yield; Rf 0.34 (1:9 EtOAc–hexanes).
1H NMR (500 MHz, CDCl3): = 6.13 (d, 1 H, J = 15.6 Hz), 5.64
(dt, 1 H, J = 15.6, 7.0 Hz), 4.85 (s, 2 H), 4.57 (dd, 1 H, J = 4.4, 3.0
Hz), 3.90–3.84 (m, 1 H), 3.78–3.71 (m, 1 H), 3.53–3.47 (m, 1 H),
3.42–3.36 (m, 1 H), 2.14 (q, 2 H, J = 6.3 Hz), 1.83 (s, 3 H), 1.74–
1.45 (m, 10 H).
13C NMR (125 MHz, CDCl3): = 142.28, 133.21, 130.76, 114.45,
99.01, 67.60, 62.49, 32.73, 30.95, 29.49, 26.26, 25.69, 19.86, 18.87.
IR (film): 3093, 2931, 2858, 1725, 1650, 1601 cm –1
.
1H NMR (500 MHz, CDCl3): = 9.76 (t, 1 H, J = 1.8 Hz), 6.30
(ddd, 1 H, J = 17.0, 10.2, 10.2 Hz), 6.45 (br dd, 1 H, J = 15.1, 10.4
Hz), 5.68 (dt, 1 H, J = 15.1, 6.9 Hz), 5.08 (br d, 1 H, J = 16.9 Hz),
4.96 (br d, 1 H, J = 10.1 Hz), 2.42 (td, 2 H, J = 7.3, 1.8 Hz), 2.09 (br
q, 2 H, J = 7.1 Hz), 1.64 (tt, 2 H, J = 7.5, 7.3 Hz), 1.46–1.30 (m, 4
H).
Anal. Calcd for C14H24O2: C, 74.95; H, 10.78. Found: C, 74.79; H,
10.63.
13C NMR (125 MHz, CDCl3): = 202.90, 137.37, 135.13, 131.34,
115.04, 44.01, 32.45, 29.06, 28.84, 22.08.
HRMS: m/z calcd for C10H16O (M+) 152.1201; found 152.1209.
(E)-1-Phenyl-3-methylbuta-1,3-diene
The diene10,26 was prepared from 5b and benzaldehyde according to
the general procedure and was obtained as a colorless oil in 57%
yield (single isomer by 1H NMR); Rf 0.84 (hexanes).
IR (film): 3081, 2949, 1603 cm–1.
References
1H NMR (500 MHz, CDCl3): = 7.41–7.37 (m, 2 H), 7.30–7.25 (m,
2 H), 7.20–7.16 (m, 1 H), 6.85 (d, 1 H, J = 16.1 Hz), 6.50 (d, 1 H,
J = 16.3 Hz), 5.09 (s, 1 H), 5.05 (s, 1 H), 1.94 (s, 3 H).
13C NMR (125 MHz, CDCl3): = 142.16, 137.53, 131.81, 128.85,
128.75, 127.56, 126.63, 117.52, 18.75.
(1) Wang, Y.; Arif, A. M.; West, F. G. J. Am. Chem. Soc. 1999,
121, 876.
(2) (a) Bull, J. R.; Gordon, R.; Hunter, R. J. Chem. Soc., Perkin
Trans. 1 2000, 3129. (b) Craig, D.; Geach, N. J.; Pearson, C.
J.; Slawin, A. M. Z.; White, A. J. P.; Williams, D. J.
Tetrahedron 1995, 51, 6071. (c) Wulff, W. D.; Powers, T. S.
J. Org. Chem. 1993, 58, 2381. (d) Smith, D. A.; Houk, K. N.
Tetrahedron Lett. 1991, 32, 1549. (e) Segi, M.; Takahashi,
M.; Nakajima, T.; Suga, S.; Sonoda, N. Synth. Commun.
1989, 19, 2431. (f) Oppolzer, W.; Dupuis, D. Tetrahedron
Lett. 1985, 26, 5437. (g) Roush, W. R.; Hall, S. E. J. Am.
Chem. Soc. 1981, 103, 5200.
(E)-2-Methyltrideca-1,3-diene
The diene was prepared from 5b and decanal according to the gen-
eral procedure and was obtained as a colorless oil in 71% yield (sin-
gle isomer by 1H NMR); Rf 0.85 (hexanes).
IR (film): 3082, 2958, 1609 cm–1.
Synthesis 2002, No. 1, 99–103 ISSN 0039-7881 © Thieme Stuttgart · New York