extracted with ethyl acetate. The organic layers were combined,
dried over MgSO4, filtered and concentrated in vacuo. Purification
by silica gel column chromatography afforded 23 (223 mg, 73%):
IR (neat, cm-1) 3327, 2957, 2920, 2852, 1460, 1417, 1375, 1340,
2-(((2¢E,4¢E,6¢E)-7¢-((1¢¢S,2¢¢R,4¢¢S)-4¢¢-Acetoxy-1¢¢,2¢¢-epoxy-
2¢¢,6¢¢,6¢¢-trimethylcyclohexylidene-1¢¢-yl)-5¢-methylhepta-2,4,6-
triene)sulfonyl)benzothiazole (7). To a solution of the thioether
25 (30 mg, 0.064 mmol) in ethanol (0.64 mL) was added dropwise
a solution of sodium tungstate(VI) dihydrate (42 mg, 0.128 mmol)
1
1292, 1089, 1005; H NMR (CDCl3, 400 MHz) d 6.64 (dd, J =
◦
15.1, 10.5 Hz, 1H), 6.19 (d, J = 10.5 Hz, 1H), 5.78 (dt, J = 14.8,
5.9 Hz, 1H), 4.22 (t, J = 5.8 Hz, 2H), 2.00 (s, 3H), 1.49 (m, 6H),
1.30 (m, 6H), 0.89 (m, 15H); 13C NMR (CDCl3, 100 MHz) d 145.2,
138.0, 130.9, 126.3, 63.7, 29.2, 27.5, 19.9, 13.8, 9.2.
in hydrogen peroxide (30 wt.% in water, 0.51 mL) at 0 C. After
being stirred for 50 min at room temperature, the reaction mixture
was poured into water and then extracted with diethyl ether.
The organic layers were combined, dried over MgSO4, filtered
and concentrated in vacuo. Purification by short silica gel column
chromatography afforded the sulfone 7 (18 mg, 56%) as a yellow
(2E,4E,6E)-7-[(1¢S,2¢R,4¢S)-4¢-Acetoxy-1¢,2¢-epoxy-2¢,6¢,6¢-
trimethylcyclohexa-1¢-yl]-5-methylhepta-2,4,6-trien-1-ol (24). To
a solution of iodide 21 (560 mg, 1.6 mmol) and (2E,4E)-5-
(tributylstannyl)hexa-2,4-dien-1-ol 23 (915 mg, 2.40 mmol) in
DMF (8 mL) was added bis(acetonitrile)dichloropalladium(II)
(21 mg, 0.05 mmol) and lithium chloride (136 mg, 3.20 mmol).
After being stirred for 10 min at 55 ◦C, the reaction mixture
was poured into water and then extracted with ethyl acetate.
The organic layers were combined, washed with brine, dried
over MgSO4, filtered and concentrated in vacuo. Purification by
silica gel column chromatography afforded coupling product 24
solid: [a]24.0 -22.5 (c 0.79, CHCl3); IR (neat, cm-1) 3471, 2930,
D
2865, 1736, 1637, 1473, 1381, 1334, 1240, 1147, 1116, 976, 763;
1H NMR (CDCl3, 400 MHz) d 8.22 (d, J = 7.8 Hz, 1H), 8.01 (d,
J = 8.7 Hz, 1H), 7.65 (m, 2H), 6.59 (dd, J = 14.7, 11.0 Hz, 1H),
6.20 (d, J = 15.6, 1H), 6.02 (d, J = 15.6 Hz, 1H), 5.90 (d, J =
15.6 Hz, 1H), 5.64 (dt, J = 15.1, 7.8 Hz, 1H), 4.91 (m, 1H), 4.31
(d, J = 7.8 Hz, 1H), 2.36 (dd, J = 15.1, 5.7, 1H), 2.00 (s, 3H),
1.78 (dd, J = 15.2, 6.5 Hz, 1H), 1.71 (s, 3H), 1.63 (m, 1H), 1.37
(dd, J = 13.7, 8.5 Hz, 1H), 1.13 (s, 3H), 1.12 (s, 3H), 0.95 (s, 3H);
13C NMR (CDCl3, 100 MHz) d 170.7, 165.9, 153.0, 137.5, 137.2,
129.5, 128.3, 128.0, 125.8, 125.7, 122.7, 116.5, 70.5, 67.9, 65.9,
59.3, 41.7, 37.1, 35.0, 28.9, 25.8, 21.7, 20.5, 13.1; ESI-HRMS m/z
calcd for 26H31NO5S2Na (M + Na)+ 524.1541, found 524.1524.
(482 mg, 94%) as a yellow oil: [a]23.0 -41.6 (c 1.02, CHCl3); IR
D
1
(neat, cm-1) 3443, 2964, 2928, 1736, 1450, 1365, 1244, 1030; H
NMR (CDCl3, 400 MHz) d 6.60 (dd, J = 14.2, 10.3 Hz, 1H),
6.27 (d, J = 15.8 Hz, 1H), 6.10 (d, J = 11.2 Hz, 1H), 5.88 (d,
J = 15.8 Hz, 1H), 5.86 (m, 1H), 4.93 (m, 1H), 4.24 (m, 2H), 2.40
(dd, J = 15.1, 5.8 Hz, 1H), 2.01 (s, 3H), 1.88 (s, 3H), 1.77 (dd,
J = 14.8, 6.8 Hz, 1H), 1.66 (dd, J = 13.2, 3.4 Hz, 1H), 1.34 (m,
1H), 1.18 (s, 3H), 1.15 (s, 3H), 0.96 (s, 3H); 13C NMR (CDCl3,
100 MHz) d 170.3, 137.4, 134.5, 132.8, 130.4, 127.5, 123.7, 70.3,
67.7, 65.5, 63.5, 41.4, 36.8, 34.7, 28.6, 25.5, 21.4, 20.2, 12.8; ESI-
HRMS m/z calcd for C19H28O4Na (M + Na)+ 343.1885, found
343.1883.
Peridinin derivative C (3). To a solution of olefin segment 7
(22 mg, 0.044 mmol) and ylidenbutenolide segment 5 (15 mg,
0.044 mmol) in THF (0.65 mL) was added dropwise sodium
bis(trimethylsilyl)amide (1.0M in THF, 0.13 mL, 0.13 mmol)
at -78 ◦C in the dark. After being stirred for 5 min at the
same temperature, the reaction mixture was poured into water
and then extracted with diethyl ether. The organic layers were
combined, washed with brine, dried over MgSO4, filtered and
concentrated in vacuo. Purification by short silica gel column
chromatography (from 30% to 50% ethyl acetate in hexane) in
the dark afforded peridinin derivative 3 (11 mg, 40%) as a mixture
of the isomers as a red film. A solution of a mixture of all-trans-
peridinin derivative 3 and its cis-isomer in benzene was left at room
temperature under the fluorescence light. After 2 days, partial
separation by preparative HPLC [column: Develosil CN-UG
(0.6 ¥ 25 cm); mobile phase: acetone/n-hexane = 1/10; flow
rate: 2.0 mL/min; UVdetect: 450 nm; retention time: (all-trans-
isomer) 49 min, (15-cis-isomer) 43 min] in the dark, and HPLC
[column: YMC Carotenoid C30 (10 ¥ 250 mm); reverse phase:
acetonitrile/methanol/water = 87/10/3; flow rate: 2.0 mL/min.;
UVdetect: 450 nm; retention time: (all-trans-isomer) 30 min, (15-
cis-isomer) 24 min] in the dark, afforded the desired optically
active peridinin derivative 3 as a red film: IR (neat, cm-1) 3327,
2924, 1741, 1712, 1462, 1377, 1259, 1153, 1028; 1H NMR (C6D6,
750 MHz) d 7.57 (d, J = 15.5 Hz, 1H), 6.68 (d, J = 15.4 Hz, 1H),
6.62 (dd, J = 14.0, 12.3 Hz, 1H), 6.56 (d, J = 15.5 Hz, 1H), 6.45
(dd, J = 14.1, 11.9 Hz, 1H), 6.38 (dd, J = 14.3, 11.2 Hz, 1H), 6.33
(d, J = 11.7 Hz, 1H), 6.26 (dd, J = 14.2, 11.3 Hz, 1H), 6.17 (d,
J = 11.7 Hz, 1H), 6.15 (s, 1H), 5.92 (d, J = 15.5 Hz, 1H), 5.20 (s,
1H), 5.19 (m, 1H), 3.86 (m, 1H), 2.35 (dd, J = 14.7, 5.3 Hz, 1H),
2.19 (ddd, J = 14.7, 5.1, 1.1 Hz, 1H), 2.13 (s, 3H), 1.79 (s, 3H),
1.72 (s, 3H), 1.71 (m, 1H), 1.62 (dd, J = 14.8, 7.2 Hz, 1H), 1.42
(m, 2H), 1.35 (m, 1H), 1.13 (s, 3H), 1.12 (s, 3H), 1.09 (s, 3H), 1.09
(s, 3H), 1.08 (s, 3H), 1.05 (s, 3H), 1.05 (m, 1H); 13C NMR (C6D6,
2-(((2¢E,4¢E,6¢E)-7¢-((1¢¢S,2¢¢R,4¢¢S)-4¢¢-Acetoxy-1¢¢,2¢¢-epoxy-
2¢¢,6¢¢,6¢¢-trimethylcyclohexylidene-1¢¢-yl)-5¢-methylhepta-2,4,6-
triene)sulfanyl)benzothiazole (25). To a solution of 24 (330 mg,
1.03 mmol), 2-mercaptobenzothiazole (241 mg, 1.44 mmol) and
triphenylphosphine (378 mg, 1.44 mmol) in THF (10 mL)
was added dropwise diisopropyl azodicarboxylate (0.32 mL,
1.65 mmol) at 0 ◦C. The reaction mixture was stirred for 10 min at
room temperature and the all solvents were removed in vacuo. To
a residue was added diethyl ether and the precipitate was removed
by filtration through a pad of Celite to give the crude products
as a solution, which was concentrated in vacuo. Purification by
short silica gel column chromatography afforded the thioether
25 (444 mg, 92%): [a]23.0 -25.6 (c 1.08, CHCl3); IR (neat, cm-1)
D
2964, 2926, 1734, 1460, 1427, 1365, 1242, 1028; 1H NMR (CDCl3,
400 MHz) d 7.87 (m, 1H), 7.75 (m, 1H), 7.40 (m, 1H), 7.28 (m,
1H), 6.71 (dd, J = 14.7, 11.3 Hz, 1H), 6.24 (d, J = 15.5 Hz, 1H),
6.07 (d, J = 11.4 Hz, 1H), 5.88 (d, J = 15.5 Hz, 1H), 5.86 (m,
1H), 4.93 (m, 1H), 4.11 (d, J = 7.5 Hz, 2H), 2.38 (dd, J = 15.8,
5.7 Hz, 1H), 2.01 (s, 3H), 1.87 (s, 3H), 1.76 (dd, J = 14.8, 6.8 Hz,
1H), 1.65 (dd, J = 13.2, 3.4 Hz, 1H), 1.33(m, 1H), 1.16 (s, 3H),
1.14 (s, 3H), 0.96 (s, 3H); 13C NMR (CDCl3, 100 MHz) d 170.3,
166.1, 153.2, 137.2, 135.3, 134.9, 130.9, 129.9, 127.4, 125.9, 124.2,
124.1, 121.5, 120.9, 70.3, 67.6, 65.5, 41.4, 36.7, 36.1, 34.7, 28.5,
25.5, 21.4, 20.2, 12.8; ESI-HRMS m/z calcd for C26H31NO3S2Na
(M + Na)+ 492.1643, found 492.1640.
3730 | Org. Biomol. Chem., 2009, 7, 3723–3733
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The Royal Society of Chemistry 2009
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