Y. Wang, J. Lugtenburg
FULL PAPER
1-H) ppm. 13C NMR (75.5 MHz, 1H-noise-decoupled, CD3Cl3):
δ ϭ 22.1 (C-2 of isopropyl), 23.2 (2Ј-CH3), 24.0 (C-4Ј), 27.4 (6Ј-
CH3), 28.2 (6Ј-CH3), 29.7 (C-1 of isopropyl), 32.6 (C-5Ј), 33.5 (C-
3
3J9-H,10-H ϭ 10.7 Hz, 1 H, H-9), 6.38 (dd, J11-H,10-H ϭ 11.9,
3
3J11-H,12-H ϭ 11.8 Hz, 1 H, 11-H), 6.45 (dd, J8-H,7-H ϭ 15.0,
3
3J8-H,9-H ϭ 11.0 Hz, 1 H, 8-H), 6.75 (dd, J10-H,11-H ϭ 11.2,
3
6Ј), 57.9 (C-1Ј), 123.1 (C-3Ј), 124.7 (C-2), 130.0 (C-5), 134.4 (C-2Ј), 3J10-H,9-H ϭ 14.8 Hz, 1 H, 10-H), 10.0 (d, J15-H,14-H ϭ 8.2 Hz,
141.3 (C-4), 169.7 (C-3), 192.3 (C-1) ppm.
1 H, 15-H) ppm. 13C NMR (75.5 MHz, 1H-noise-decoupled,
CD3OD): δ ϭ 12.8 (C-20), 18.2 (C-19), 23.3 (C-18), 24.1 (C-3), 27.4
(C-16), 28.2 (C-17), 32.7 (C-2), 33.5 (C-1), 56.2 (C-6), 122.2 (C-4),
126.7 (C-14), 130.5 (C-10), 131.5 (C-12), 132.7 (C-11), 135.0 (C-7),
134.9 (C-5), 142.3 (C-9), 158.9 (C-13), 193.5 (C-15) ppm.
(9Z)-30: 1H NMR (300 MHz, CDCl3): δ ϭ 0.83 (s, 3 H, 16-H),
3
0.91 (s, 3 H, 17-H), 1.21 (d, JCH3a,CHisopropyl ϭ 6.93 Hz, 3 H, iso-
3
propyl-Ha,), 1.23 (d, JCH3b,CHisopropyl ϭ 6.94 Hz, 3 H, isopropyl-
Hb), 1.26 (m, 1 H, 5Ј-H), 1.49 (m, 1 H, 5Ј-H), 1.63 (s, 3 H, 2Ј-
3
(all-E)-α-Retinal [(all-E)-6]: 1H NMR (300.1 MHz, CD3OD): δ ϭ
0.84 (s, 3 H, 16-H), 0.92 (s, 3 H, 17-H), 1.20 (m, 1 H, 2-H), 1.45
(m, 1 H, 2-H), 1.59 (s, 3 H, 18-H), 1.97 (s, 3 H, H-19), 2.02 (m, 2
H, 3-H), 2.29 (s, 3 H, 20-H), 2.31 (d, 3J6-H,7-H ϭ 9.50 Hz, 1 H, 6-H),
5.43 (m, 1 H, 4-H), 5.77 (dd, 3J7-H,8-H ϭ 15.2, 3J7-H,6-H ϭ 9.50 Hz, 1
CH3), 2.08 (2 H, 4Ј-H), 2.36 (d, J6Ј-H,7-H ϭ 9.50 Hz, 6Ј-H), 3.43
(m, 3JCH3a,CHisopropyl ϭ 6.93, 3JCH3b,CHisopropyl ϭ 6.94 Hz, 1 H, iso-
3
propyl-H), 5.47 (m, 2 H, 3Ј-H), 6.11 (d, J2-H,1-H ϭ 8.2 Hz, 1 H, 2-
H), 6.11 (dd, 3J5-H,4-H ϭ 15.2, 3J5-H,6Ј-H ϭ 9.67 Hz, 1 H, 5-H), 6.63
(d, 3J4-H,5-H ϭ 15.2 Hz, 1 H, 4-H), 10.3 (d, 3J1-H,2-H ϭ 8.2 Hz, 1 H,
1-H) ppm. 13C NMR (75.5 MHz, 1H-noise-decoupled, CD3Cl3):
δ ϭ 17.6 (C-2 of isopropyl), 18.3 (C-4Ј), 22.3 (2Ј-CH3), 27.2 (6Ј-
CH3), 28.3 (6Ј-CH3), 32.7 (C-1 of isopropyl), 33.4 (C-6Ј), 38.3 (C-
5Ј), 54.6 (C-1Ј), 123.1 (C-3Ј), 124.7 (C-2), 129.3 (C-5), 131.9 (C-2Ј),
136.8 (C-4), 165.5 (C-3), 192.6 (C-1) ppm.
3
H, 7-H), 5.93 (d, J14-H,15-H ϭ 8.1 Hz, 1 H, 14-H), 6.07 (d,
3
3J12-H,11-H ϭ 15.1 Hz, 1 H, 12-H), 6.28 (d, J10-H,11-H ϭ 11.5 Hz, 1
3
H, 10-H), 6.68 (d, J8-H,7-H ϭ 15.2 Hz, 1 H, 8-H), 7.21 (dd,
3
3J11-H,10-H ϭ 11.5, J11-H,12-H ϭ 15.0 Hz, 1 H, 11-H), 10.1 (d,
1
3J15-H,14-H ϭ 8.1 Hz, 1 H, 15-H) ppm. 13C NMR (75.5 MHz, H-
noise-decoupled, CD3OD): δ ϭ 13.3 (C-20), 13.6 (C-19), 23.6 (C-
18), 24.1 (C-3), 27.6 (C-16), 28.3 (C-17), 32.7 (C-2), 33.5 (C-1), 56.1
(C-6), 122.2 (C-4), 129.8 (C-14), 130.4 (C-10), 134.0 (C-11), 134.9
(C-5), 134.9 (C-7), 135.8 (C-12), 137.0 (C-8), 141.8 (C-9), 157.1 (C-
13), 192.7 (C-15) ppm.
Repeating the general procedures as described for the preparation
of (9Z)-1, (all-E)-1 and (9Z,11Z)-1, respectively, the following
products were synthesized.
(all-E)-9-Demethyl-α-retinal [(all-E)-5]: 1H NMR (300.1 MHz,
CD3OD): δ ϭ 0.83 (s, 3 H, 16-H), 0.91 (s, 3 H, 17-H), 1.19 (m, 1
H, 2-H), 1.48 (m, 1 H, 2-H), 1.57 (s, 3 H, 18-H), 2.02 (m, 2 H, 3-
1
(9Z)-α-Retinal [(9Z)-6]: H NMR (300.1 MHz, CD3OD): δ ϭ 0.84
3
(s, 3 H, 16-H), 0.92 (s, 3 H, 17-H), 1.20 (m, 1 H, 2-H), 1.45 (m, 1
H, 2-H), 1.59 (s, 3 H, 18-H), 1.93 (s, 3 H, H-19), 2.02 (m, 2 H, 3-
H), 2.30 (d, J6-H,7-H ϭ 9.57 Hz, 1 H, 6-H), 2.32 (s, 3 H, 20-H),
3
3
5.43 (m, 1 H, 4-H), 5.72 (dd, J7-H,8-H ϭ 15.0, J7-H,6-H ϭ 9.57 Hz,
3
3
H), 2.29 (s, 3 H, 20-H), 2.31 (d, J6-H,7-H ϭ 9.65 Hz, 1 H, 6-H),
1 H, 7-H), 5.93 (d, J14-H,15-H ϭ 8.22 Hz, 1 H, 14-H), 6.16 (dd,
3
3
3
5.42 (m, 1 H, 4-H), 5.70 (dd, J7-H,8-H ϭ 15.3, J7-H,6-H ϭ 9.65 Hz,
3J8-H,7-H ϭ 15.0, J8-H,9-H ϭ 10.7 Hz, 1 H, 8-H), 6.33 (dd,
3
3
1 H, 7-H), 5.91 (d, J14-H,15-H ϭ 8.2 Hz, 1 H, 14-H), 6.05 (d,
3J9-H,8-H ϭ 10.7, J9-H,10-H ϭ 14.8 Hz, 1 H, H-9), 6.41 (dd,
3
3
3J10-H,11-H ϭ 11.5 Hz, 1 H, 10-H), 6.32 (d, J12-H,11-H ϭ 15.1 Hz, 1
3J12-H,11-H ϭ 15.3 Hz, 1 H, 12-H), 6.54 (dd, J10-H,11-H ϭ 10.7,
3
3
H, 12-H), 6.74 (d, J8-H,7-H ϭ 15.3 Hz, 1 H, 8-H), 7.33 (dd,
3J10-H,9-H ϭ 14.8 Hz, 1 H, 10-H), 6.93 (dd, J11-H,10-H ϭ 10.8,
3
3
3J11-H,10-H ϭ 11.5, J11-H,12-H ϭ 15.0 Hz, 1 H, 11-H), 10.0 (d,
3J11-H,12-H ϭ 15.3 Hz, 1 H, 11-H), 10.0 (d, J15-H,14-H ϭ 8.0 Hz,
3J15-H,14-H ϭ 8.2 Hz, 1 H, 15-H) ppm. 13C NMR (75.5 MHz, H-
1
1 H, 15-H) ppm. 13C NMR (75.5 MHz, 1H-noise-decoupled,
CD3OD): δ ϭ 13.1 (C-20), 23.3 (C-18), 24.1 (C-3), 27.3 (C-16), 28.2
(C-17), 32.5 (C-2), 33.5 (C-1), 56.1 (C-6), 122.3 (C-4), 129.8 (C-14),
131.7 (C-9), 133.1 (C-8), 134.9 (C-5), 135.3 (C-12), 138.7 (C-11),
139.4 (C-10), 140.7 (C-7), 157.7 (C-13), 193.4 (C-15) ppm.
noise-decoupled, CD3OD): δ ϭ 13.3 (C-20), 21.4 (C-19), 23.5 (C-
18), 24.1 (C-3), 27.5 (C-16), 28.3 (C-17), 32.8 (C-2), 33.5 (C-1), 56.2
(C-6), 122.2 (C-4), 128.9 (C-10), 129.2 (C-8), 129.8 (C-14), 133.0
(C-11), 135.0 (C-5), 135.1 (C-12), 136.6 (C-7), 140.8 (C-9), 157.3
(C-13), 193.0 (C-15) ppm.
(9Z)-9-Demethyl-α-retinal [(9Z)-5]: 1H NMR (300.1 MHz,
CD3OD): δ ϭ 0.84 (s, 3 H, 16-H), 0.93 (s, 3 H, 17-H), 1.32 (m, 1
H, 2-H), 1.49 (m, 1 H, 2-H), 1.59 (s, 3 H, 18-H), 2.04 (m, 2 H, 3-
(11Z)-α-Retinal [(11Z)-6]: 1H NMR (300.1 MHz, CD3OD): δ ϭ
0.83 (s, 3 H, 16-H), 0.92 (s, 3 H, 17-H), 1.43 (m, 2 H, 2-H), 1.58
(s, 3 H, 18-H), 1.99 (s, 3 H, H-19), 2.02 (m, 2 H, 3-H), 2.28 (d,
3J6-H,7-H ϭ 9.42 Hz, 1 H, 6-H), 2.32 (s, 3 H, 20-H), 5.43 (m, 1 H,
3
H), 2.31 (d, J6-H,7-H ϭ 9.60 Hz, 1 H, 6-H), 2.34 (s, 3 H, 20-H),
3
3
5.42 (m, 1 H, 4-H), 5.70 (dd, J7-H,8-H ϭ 14.8, J7-H,6-H ϭ 9.60 Hz,
3
3
3
4-H), 5.76 (dd, J7-H,8-H ϭ 15.4, J7-H,6-H ϭ 9.42 Hz, 1 H, 7-H),
1 H, 7-H), 5.96 (d, J14-H,15-H ϭ 8.1 Hz, 1 H, 14-H), 6.07 (dd,
3
3
3J10-H,11-H ϭ 11.2, J10-H,9-H ϭ 10.8 Hz, 1 H, 10-H), 6.24 (dd,
3
5.98 (d, J14-H,15-H ϭ 8.2 Hz, 1 H, 14-H), 5.99 (d, J10-H,11-H
11.7 Hz, 1 H, 10-H), 6.06 (d, J8-H,7-H ϭ 15.4 Hz, 1 H, 8-H), 6.55
ϭ
3
3J9-H,8-H ϭ 10.8, J9-H,10-H ϭ 10.8 Hz, 1 H, H-9), 6.43 (dd,
3
3
3
3J12-H,11-H ϭ 15.2 Hz, 1 H, 12-H), 6.74 (dd, J8-H,7-H ϭ 14.8,
3
(d, J12-H,11-H ϭ 15.3 Hz, 1 H, 12-H), 6.73 (dd, J11-H,10-H ϭ 11.9,
3J11-H,12-H ϭ 12.1 Hz, 1 H, 11-H), 10.0 (d, J15-H,14-H ϭ 8.2 Hz, 1
3
3J8-H,9-H ϭ 11.3 Hz, 1 H, 8-H), 7.36 (dd, J11-H,10-H ϭ 11.5,
3
H, 15-H) ppm. 13C NMR (75.5 MHz, 1H-noise-decoupled,
CD3OD): δ ϭ 13.2 (C-20), 21.6 (C-19), 24.0 (C-3), 27.3 (C-18), 28.0
(C-16), 28.2 (C-17), 32.5 (C-2), 33.4 (C-1), 55.1 (C-6), 122.5 (C-4),
128.5 (C-14), 129.1 (C-8), 130.0 (C-10), 134.6 (C-5), 133.8 (C-11),
138.1 (C-9), 139.4 (C-7), 157.8 (C-13), 193.4 (C-15) ppm.
3J11-H,12-H ϭ 15.02 Hz, 1 H, 11-H), 10.1 (d, J15-H,14-H ϭ 8.0 Hz,
3
1 H, 15-H) ppm. 13C NMR (75.5 MHz, 1H-noise-decoupled,
CD3OD): δ ϭ 13.2 (C-20), 23.2 (C-18), 24.1 (C-3), 27.3 (C-16), 28.2
(C-17), 32.7 (C-2), 33.4 (C-1), 56.2 (C-6), 122.3 (C-4), 128.0 (C-10),
128.3 (C-8), 130.2 (C-14), 133.0 (C-11), 134.9 (C-5), 135.7 (C-9),
136.3 (C-12), 141.3 (C-7), 157.7 (C-13), 193.5 (C-15) ppm.
(all-E)-19,19-Ethano-α-retinal [(all-E)-7]: 1H NMR (300.1 MHz,
CD3OD): δ ϭ 0.45 (m, 2 H, cyclopropyl-Ha,aЈ), 0.85 (s, 3 H, 16-H),
0.93 (s, 3 H, 17-H), 0.94 (m, 2 H, cyclopropyl-Hb,bЈ), 1.10 (s, 3 H,
(11Z)-9-Demethyl-α-retinal [(11Z)-5]: 1H NMR (300.1 MHz,
CD3OD): δ ϭ 0.83 (s, 3 H, 16-H), 0.91 (s, 3 H, 17-H), 1.19 (m, 1
H, 2-H), 1.46 (m, 1 H, 2-H), 1.59 (s, 3 H, 18-H), 2.02 (m, 2 H, 3-
16-H), 1.12 (s, 3 H, 17-H), 1.46 (m, 2 H, 2-H), 1.57 (s, 3 H, 18-H),
3
3
H), 2.22 (d, J6-H,7-H ϭ 9.59 Hz, 1 H, 6-H), 2.38 (s, 3 H, 20-H), 2.04 (m, 2 H, 3-H), 2.22 (d, J6-H,7-H ϭ 6.52 Hz, 1 H, 6-H), 2.35
3
3
3
5.43 (m, 1 H, 4-H), 5.73 (dd, J7-H,8-H ϭ 15.0, J7-H,6-H ϭ 9.60 Hz, (s, 3 H, 20-H), 5.43 (m, 1 H, 4-H), 5.95 (d, J14-H,15-H ϭ 8.2 Hz, 1
3
3
1 H, 7-H), 5.91 (dd, J12-H,11-H ϭ 11.2 Hz, 1 H, 12-H), 5.95 (d,
H, 14-H), 5.99 (d, J8-H,7-H ϭ 15.4 Hz, 1 H, 8-H), 6.03 (dd,
3
3
3J14-H,15-H ϭ 8.2 Hz, 1 H, 14-H), 6.18 (dd, J9-H,8-H ϭ 15.0, 3J7-H,8-H
ϭ
15.4, J7-H,6-H
ϭ
6.6 Hz,
1
H, 7-H), 6.24 (d,
3508
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2004, 3497Ϫ3510