J. A. Marco et al. / Tetrahedron 59 (2003) 4085–4101
4091
chromatography on silica gel (hexanes–EtOAc mixtures)
furnished the expected ethers 8. Chemical yields: 65–90%.
(1H, ddt, J¼17, 10.5, 5.7 Hz), 5.27 (1H, br d, J¼17 Hz),
5.14 (1H, br d, J¼10.5 Hz), 4.79 (1H, br s), 4.74 (1H, br s),
4.00 (2H, m), 3.46 (1H, quint, J¼6 Hz), 2.30 (1H, br dd,
J¼14, 6 Hz), 2.13 (1H, br dd, J¼14, 6 Hz), 1.77 (3H, s),
1.55–1.20 (20H, br m), 0.89 (3H, t, J¼7 Hz); 13C NMR
(125 MHz) d 143.1 (C), 136.2, 77.6 (CH), 116.5, 112.5,
70.0, 42.7, 34.1, 32.0, 29.8, 29.6 (£4), 29.4, 25.4, 22.7
(CH2), 23.0, 14.1 (CH3). Anal. Calcd for C19H36O: C, 81.36;
H, 12.94. Found: C, 81.45; H, 13.00.
3.3.1. 3-(2-Propenyloxy)tetradec-1-ene, 8a (R35H,
1
R45H, n50). Oil; H NMR (500 MHz) d 5.93 (1H, ddt,
J¼17, 10.5, 5.2 Hz), 5.70 (1H, ddd, J¼17, 10.5, 7.5 Hz),
5.26 (1H, dq, J¼17, 1.5 Hz), 5.20–5.15 (3H, m), 4.07 (1H, br
dd, J¼13, 5.2 Hz), 3.85 (1H, br dd, J¼13, 5.2 Hz), 3.70 (1H,
q, J¼7.5 Hz), 1.65 (1H, m), 1.50 (1H, m), 1.40–1.20 (18H,
br m), 0.89 (3H, t, J¼7 Hz); 13C NMR (125 MHz) d 139.3,
135.3, 80.8 (CH), 116.7, 116.5, 69.2, 35.5, 32.0, 29.7, 29.6,
29.5 (£3), 29.4, 25.4, 22.7 (CH2), 14.1 (CH3). Anal. Calcd
for C17H32O: C, 80.88; H, 12.78. Found: C, 81.00; H, 12.67.
3.3.7. [1-(2-propenyloxy)-2-propenyl]benzene, 8b
1
(R35H, R45H, n50). H NMR (400 MHz) d 7.40–7.25
(5H, br m), 6.00–5.90 (2H, m), 5.35–5.15 (4H, br m),
4.82 (1H, d, J¼6.8 Hz), 4.05–3.95 (2H, m); 13C NMR
(100 MHz) d 141.0 (C), 138.9, 134.8, 128.3, 127.6, 126.8,
82.0 (CH), 116.8, 116.2, 69.2 (CH2).
3.3.2. 3-(2-Propenyloxy)-2-methyltetradec-1-ene, 8a
1
(R35Me, R45H, n50). Oil; H NMR (500 MHz) d 5.90
(1H, ddd, J¼17, 10.5, 1.5 Hz), 5.24 (1H, dq, J¼17, 1.5 Hz),
5.13 (1H, dq, J¼10.5, 1.5 Hz), 4.90 (1H, br s), 4.86 (1H, br
s), 3.95 (1H, ddt, J¼13, 5.3, 1.5 Hz), 3.74 (1H, ddt, J¼13, 6,
1.5 Hz), 3.65 (1H, t, J¼7 Hz), 1.64 (3H, s), 1.60 (1H, m),
1.48 (1H, m), 1.40–1.20 (18H, br m), 0.88 (3H, t, J¼7 Hz);
13C NMR (125 MHz) d 144.9 (C), 135.3, 83.5 (CH), 116.4,
113.3, 68.9, 33.6, 32.0, 29.7, 29.6, 29.5 (£2), 29.4, 29.3,
25.8, 22.7 (CH2), 16.5, 14.1 (CH3). Anal. Calcd for
C18H34O: C, 81.13; H, 12.86. Found: C, 81.07; H, 12.78.
3.3.8. [3-Methyl-1-(2-propenyloxy)-3-butenyl]benzene,
1
8b (R35Me, R45H, n51). Oil; H NMR (500 MHz) d
7.40–7.25 (5H, br m), 5.94 (1H, ddt, J¼17, 10.5, 5.5 Hz),
5.27 (1H, ddt, J¼17, 1.5, 1.5 Hz), 5.16 (1H, ddt, J¼10.5,
1.5, 1.5 Hz), 4.83 (1H, br s), 4.74 (1H, br s), 4.50 (1H, dd,
J¼8, 5.5 Hz), 3.96 (1H, br dd, J¼12, 5.5 Hz), 3.77 (1H, br
dd, J¼12, 6 Hz), 2.62 (1H, dd, J¼14, 8 Hz), 2.37 (1H, dd,
J¼14, 5.5 Hz), 1.78 (3H, s); 13C NMR (125 MHz) d 142.3,
142.2 (C), 135.0, 128.3, 127.6, 126.7, 80.2 (CH), 116.7,
112.7, 69.5, 46.6 (CH2), 22.9 (CH3). Anal. Calcd for
C14H18O: C, 83.12; H, 8.97. Found: C, 83.33; H, 8.86.
3.3.3. 3-(2-Methyl-2-propenyloxy)tetradec-1-ene, 8a
1
(R35H, R45Me, n50). Oil; H NMR (500 MHz) d 5.68
(1H, ddd, J¼18, 10, 7 Hz), 5.17 (1H, br d, J¼10 Hz), 5.15
(1H, br d, J¼18 Hz), 4.95 (1H, br s), 4.87 (1H, br s), 3.93
(1H, d, J¼12.5 Hz), 3.75 (1H, d, J¼12.5 Hz), 3.66 (1H, q,
J¼7 Hz), 1.75 (3H, s), 1.70–1.20 (20H, br m), 0.90 (3H, d,
J¼7 Hz); 13C NMR (125 MHz) d 142.6 (C), 139.3, 80.5
(CH), 116.6, 111.8, 72.0, 35.6, 32.0, 29.7, 29.6 (£2), 29.5
(£2), 29.4, 25.5, 22.7 (CH2), 19.7, 14.1 (CH3). Anal. Calcd
for C18H34O: C, 81.13; H, 12.86. Found: C, 81.30; H, 12.95.
3.3.9. [1-(2-Methyl-2-propenyloxy)-3-butenyl]benzene,
1
8b (R35H, R45Me, n51). Oil; H NMR (300 MHz) d
7.35–7.25 (5H, br m), 5.73 (1H, ddt, J¼17.3, 10.2, 7 Hz),
4.97 (1H, br d, J¼17.3 Hz), 4.92 (1H, br d, J¼10.2 Hz),
4.86 (1H, br s), 4.78 (1H, br s), 4.22 (1H, dd, J¼7.5, 6 Hz),
3.74 (1H, d, J¼12.5 Hz), 3.57 (1H, d, J¼12.5 Hz), 2.52 (1H,
dt, J¼14, 7.5 Hz), 2.33 (1H, dt, J¼14, 6 Hz), 1.64 (3H, s);
13C NMR (75 MHz) d 142.0, 141.7 (C), 134.6, 128.0, 127.3,
126.5, 80.7 (CH), 116.6, 111.8, 72.1, 42.7 (CH2), 19.6
(CH3). Anal. Calcd for C14H18O: C, 83.12; H, 8.97. Found:
C, 83.03; H, 9.08.
3.3.4. 4-(2-Propenyloxy)pentadec-1-ene, 8a (R35H,
1
R45H, n51). Oil; H NMR (500 MHz) d 5.95–5.80 (2H,
br m), 5.25 (1H, br d, J¼17 Hz), 5.13 (1H, br d, J¼10.3 Hz),
5.05 (1H, br d, J¼17 Hz), 5.03 (1H, br d, J¼10.5 Hz), 4.02
(1H, br dd, J¼12.5, 5.5 Hz), 3.96 (1H, br dd, J¼12.5,
5.5 Hz), 3.34 (1H, quint, J¼5.8 Hz), 2.25 (2H, m), 1.50–
1.20 (20H, br m), 0.88 (3H, t, J¼7 Hz); 13C NMR
(125 MHz) d 135.5, 135.2, 78.6 (CH), 116.6, 116.3, 70.0,
38.5, 33.9, 32.0, 29.8, 29.7 (£2), 29.6 (£2), 29.4, 25.4, 22.7
(CH2), 14.1 (CH3). Anal. Calcd for C18H34O: C, 81.13; H,
12.86. Found: C, 81.24; H, 12.99.
3.3.10. 2-[1-(2-Propenyloxy)but-3-enyl]furan, 8c (R35H,
R45H, n51). 1H NMR (500 MHz) d 7.37 (1H, d, J¼
1.7 Hz), 6.27 (1H, dd, J¼3.2, 1.7 Hz), 6.19 (1H, d, J¼
3.2 Hz), 5.80 (1H, ddt, J¼17.5, 10.5, 5.5 Hz), 5.70 (1H, ddt,
J¼17, 10, 7 Hz), 5.18 (1H, dq, J¼17.5, 11 Hz), 5.09 (1H,
dq, J¼17.5, 1.5 Hz), 5.02 (1H, dq, J¼17, 1.5 Hz), 4.96 (1H,
dq, J¼10, 1.5 Hz), 4.32 (1H, t, J¼7 Hz), 3.92 (1H, ddt,
J¼13, 5.5, 1.5 Hz), 3.80 (1H, ddt, J¼13, 5.5, 1.5 Hz), 2.60
(1H, dtt, J¼14, 7, 1.5 Hz), 2.53 (1H, dtt, J¼14, 7, 1.5 Hz);
13C NMR (125 MHz) d 154.2 (C), 142.2, 134.7, 134.2,
110.0, 108.1, 73.9 (CH), 117.2, 117.1, 69.5, 38.7 (CH2).
3.3.5. 4-(2-Methyl-2-propenyloxy)pentadec-1-ene, 8a
1
(R35H, R45Me, n51). Oil; H NMR (500 MHz) d 5.86
(1H, ddt, J¼17.5, 10.5, 7 Hz), 5.10 (1H, br d, J¼17.5 Hz),
5.06 (1H, br d, J¼10.5 Hz), 5.00 (1H, br s), 4.88 (1H, br s),
3.94 (1H, br d, J¼12.5 Hz), 3.89 (1H, br d, J¼12.5 Hz),
3.36 (1H, quint, J¼5.8 Hz), 2.30 (2H, m), 1.78 (3H, s),
1.55–1.20 (20H, br m), 0.90 (3H, t, J¼7 Hz); 13C NMR
(125 MHz) d 142.9 (C), 135.2, 78.6 (CH), 116.7, 111.9,
73.0, 38.3, 33.8, 32.0, 29.8, 29.7 (£4), 29.4, 25.4, 22.7
(CH2), 19.8, 14.1 (CH3). Anal. Calcd for C19H36O: C, 81.36;
H, 12.94. Found: C, 81.34; H, 12.82.
3.3.11. 2-[3-Methyl-1-(2-propenyloxy)but-3-enyl]furan,
1
8c (R35Me, R45H, n51). Oil; H NMR (500 MHz) d
7.36 (1H, s), 6.30 (1H, br s), 6.25 (1H, br d, J¼3 Hz), 5.85
(1H, ddt, J¼17.2, 10.5, 5.7 Hz), 5.22 (1H, br d, J¼17.2 Hz),
5.13 (1H, br d, J¼10.5 Hz), 4.75 (1H, br s), 4.71 (1H, br s),
4.49 (1H, t, J¼7 Hz), 3.95 (1H, br dd, J¼12.5, 5 Hz), 3.80
(1H, br dd, J¼12.5, 6 Hz), 2.65 (1H, br dd, J¼14, 7 Hz),
2.53 (1H, br dd, J¼14, 7 Hz), 1.70 (3H, s); 13C NMR
(125 MHz) d 154.3, 141.8 (C), 142.2, 134.7, 110.0, 108.0,
73.0 (CH), 117.1, 112.9, 69.5, 42.5 (CH2), 22.7 (CH3). Anal.
3.3.6. 2-Methyl-4-(2-propenyloxy)pentadec-1-ene, 8a
1
(R35Me, R45H, n51). Oil; H NMR (500 MHz) d 5.90