(Ϫ13.5), 316 (0), 340 (ϩ2.7), 380 (0) (Found: Mϩ, 714.4871.
C46H66O6 requires M, 714.4856).
(3H, s, 9-Me), 2.33 (2H, t, J 7.5, CH2CO), 2.47 (1H, dd, J 17
and 6, 4-Heq), 3.39 (2H, br t-like, J 9.5, 2Ј-H and 4Ј-H), 3.50
(1H, ddd, J 9.5, 6 and 2.5, 5Ј-H), 3.57 (1H, t, J 9, 3Ј-H), 4.02
(1H, m, 3-H), 4.32 (1H, dd, J 12 and 6, 6Ј-H), 4.39 (1H, dd, J 12
and 1.5, 6Ј-H), 4.43 (1H, d, J 7.5, 1Ј-H), 6.10 (1H, d, J 16, 8-H),
7.20 (1H, br d, J 16, 7-H) [Found: (M ϩ Na)ϩ, 617.4011.
C34H58O8Na requires M ϩ Na, 617.4026].
(9ЈZ)-Isomer. λmax(EtOH)/nm 473, 446, 420sh, 340, 265;
δH(500 MHz) 0.98 and 1.04 (each 6H, s, 1-gem-Me and 1Ј-gem-
Me), 1.42 (2H, m, 2Ј-H2), 1.52–1.60 (3H, m, 2-Hax and 3Ј-H2),
1.67 and 1.73 (each 3H, s, 5-Me and 5Ј-Me), 1.84 (1H, br d,
J 13, 2-Heq), 1.91, 1.92 and 1.93 (12H, each s, 9-Me, 9Ј-Me, 13-
Me and 13Ј-Me), 1.97 (2H, br t, J 6, 4Ј-H2), 2.08 (1H, br dd,
J 16.5 and 9, 4-Hax), 2.44 (1H, br dd, J 16.5 and 5, 4-Heq), 3.30
(2H, m, 2Љ-H and 5Љ-H), 3.49 (1H, br t, J 8.5, 4Љ-H), 3.52 (1H, br
t, J 8.5, 3Љ-H), 3.79 (1H, br dd, J 12 and 3.5, 6Љ-H), 3.84 (1H, br
d, J 12.5, 6Љ-H), 4.06 (1H, m, 3-H), 4.45 (1H, d, J 7.5, 1Љ-H),
6.02 (1H, br d, J 12, 10Ј-H), 6.08–6.12 (2H, m, 7Ј-H and 10-H),
6.09 (1H, d, J 16, 8-H), 6.13 (1H, br d, J 16, 7-H), 6.20 (2H, br
d-like, J 9.5, 14-H and 14Ј-H), 6.25 (1H, d, J 15, 12Ј-H), 6.30
(1H, d, J 15, 12-H), 6.59 (3H, m, 11-H, 15-H and 15Ј-H), 6.61
(1H, d, J 16.5, 8Ј-H), 6.68 (1H, dd, J 15 and 12, 11Ј-H).
Compound 27
λmax(EtOH)/nm 291, 218; νmax/cmϪ1 3602 and 3436 (OH), 1726
(OCO), 1668 (conj. CO), 1606 (C᎐C); δ (300 MHz) 0.86 (6H, d,
᎐
H
J 6.5, CHMe2), 1.10 and 1.12 (each 3H, s, gem-Me), 1.13–1.40
(18H, m, CH2 × 9), 1.51 (1H, nonet, J 6.5, CHMe2), 1.64 (1H,
br t, J 12, 2-Hax), 1.66 (2H, m, CH2CH2CO), 1.77 (3H, s, 5-Me),
1.89 (1H, br ddd, J 12.5, 3.5 and 2, 2-Heq), 2.14 (1H, br dd,
J 17.5 and 9.5, 4-Hax), 2.30 (3H, s, 9-Me), 2.42 (2H, t, J 7.5,
CH2CO), 2.49 (1H, br dd, J 17.5 and 5.5, 4-Heq), 2.56 (1H, br s,
OH), 3.44 (1H, m, 5Ј-H), 3.47 (1H, t-like, J 8, 2Ј-H), 3.68 (1H,
br t, J 9, 4Ј-H), 3.84 (1H, br dd, J 12 and 4.5, 6Ј-H), 3.93 (1H, br
dd, J 12 and 4, 6Ј-H), 4.07 (1H, m, 3-H), 4.54 (1H, d, J 8, 1Ј-H),
4.93 (1H, t, J 9, 3Ј-H), 6.10 (1H, d, J 16.5, 8-H), 7.19 (1H, br d,
J 16.5, 7-H) [Found: (M ϩ Na)ϩ, 617.4014. C34H58O8Na
requires M ϩ Na, 617.4026].
(3E )-4-[(4R)-4-(ꢀ-D-Glucopyranosyloxy)-2,6,6-trimethyl-
cyclohex-1-enyl]but-3-en-2-one 25
According to the procedure described in the preparation of the
compound 16, methanolysis of the tetrabenzoate 10 (1.83 g)
followed by purification by SCC (CH2Cl2–MeOH, 9 : 1) gave
the tetraol 25 (733 mg, 85%) as a pale yellow foam; λmax(EtOH)/
nm 291, 218; νmax/cmϪ1 3631 and 3406 (OH), 1670 (conj. CO),
Compound 28
λmax(EtOH)/nm 291, 218; νmax/cmϪ1 3598 and 3489 (OH), 1731
1606 (C᎐C); δH (CDCl3 ϩ D2O, 300 MHz) 1.06 and 1.09 (each
᎐
(OCO), 1668 (conj. CO), 1603 (C᎐C); δ (300 MHz) 0.86 (6H, d,
᎐
H
3H, s, gem-Me), 1.53 (1H, t, J 12, 2-Hax), 1.73 (3H, s, 5-Me),
1.86 (1H, br d, J 12, 2-Heq), 2.13 (1H, br dd, J 18 and 9, 4-Hax),
2.28 (3H, s, 9-Me), 2.48 (1H, br dd, J 18 and 4.5, 4-Heq), 3.32
(2H, m, 2Ј-H and 5Ј-H), 3.49 (1H, t, J 9, 4Ј-H), 3.57 (1H, t, J 9,
3Ј-H), 3.82 (2H, m, 6Ј-H2), 4.03 (1H, m, 3-H), 4.46 (1H, d, J 8,
1Ј-H), 6.05 (1H, d, J 16.5, 8-H), 7.15 (1H, br d, J 16.5, 7-H)
[Found: (M ϩ H)ϩ, 371.2069. C19H31O7 requires M ϩ H,
371.2068].
J 6.5, CHMe2), 1.11 (6H, s, gem-Me), 1.12–1.40 (18H, m, CH2 ×
9), 1.51 (1H, nonet, J 6.5, CHMe2), 1.60 (1H, br t, J 12.5,
2-Hax), 1.64 (2H, m, CH2CH2CO), 1.77 (3H, s, 5-Me), 1.91 (1H,
br ddd, J 12.5, 3.5 and 2, 2-Heq), 2.15 (1H, br dd, J 17 and 9,
4-Hax), 2.30 (3H, s, 9-Me), 2.33–2.42 (2H, m, CH2CO), 2.48
(1H, m, 4-Heq), 3.45 (2H, m, 2Ј-H and 5Ј-H), 3.60 (1H, dd,
J 12.5 and 5, 6Ј-H), 3.73 (1H, dd, J 12.5 and 2.5, 6Ј-H), 3.74
(1H, t, J 9, 3Ј-H), 4.06 (1H, m, 3-H), 4.48 (1H, d, J 8, 1Ј-H),
4.87 (1H, t, J 9, 4Ј-H), 6.10 (1H, d, J 16.5, 8-H), 7.19 (1H, d,
J 16.5, 7-H) [Found: (M ϩ Na)ϩ, 617.4011. C34H58O8Na
requires M ϩ Na, 617.4026].
Acylation of the glucoside 25 (Scheme 2)
Method A. To an ice-cooled solution of the glucoside 25
(180 mg, 0.49 mmol), the fatty acid 2917 (121 mg, 0.50 mmol)
and DMAP (61 mg, 0.50 mmol) in dry CH2Cl2 (15 ml) was
added DCC (103 mg, 0.50 mmol). After being stirred at rt for
3 h, the reaction mixture was diluted with AcOEt. The organic
layer was washed successively with aq. 5% HCl, saturated aq.
NaHCO3 and brine. Evaporation of the dried extracts provided
a residue, which was purified by SCC (CH2Cl2–MeOH, 97 : 3)
and then PTLC (CH2Cl2–ether–MeOH, 4 : 4 : 1) to afford the
6Ј-acylate 26 (8 mg, 3%) and a mixture of the 3Ј-acylate 27 and
the 4Ј-acylate 28 (130 mg, 45%; 27–28 ∼5 : 4) as yellow foams.
Synthesis of thermozeaxanthin-15 1a
In the same manner as described for the acylation of the gluco-
side 25 by method B, zeaxanthin-mono-β-glucoside 3 (28 mg)
was treated with the acyl chloride 24 to give crude products,
which were purified by PTLC (CH2Cl2–ether–MeOH, 4 : 5 : 1)
to provide TZ-15 1a (8 mg, 22%) as a red solid. Spectral proper-
ties of the synthetic TZ-15 1a were in agreement with those2 of
a natural specimen; λmax(acetone)/nm 479, 453, 429sh; νmax/cmϪ1
3580 and 3487 (OH), 1728 (OCO); δH(300 MHz) 0.86 (6H, d,
J 6.5, CHMe2), 1.07 (12H, s, 1-gem-Me and 1Ј-gem-Me), 1.10–
1.40 (18H, m, CH2 × 9), 1.42–1.71 (5H, m, 2-Hax, 2Ј-Hax,
CH2CH2CO and CHMe2), 1.78 (1H, m, 2Ј-Heq), 1.92 (1H, m, 2-
Heq), 1.97 (12H, s, 9-Me, 9Ј-Me, 13-Me and 13Ј-Me), 2.04 (1H,
br dd, J 17 and 8.5, 4Ј-Hax), 2.14 (1H, br dd, J 17 and 8, 4-Hax),
2.36 (2H, t, J 7.5, CH2CO), 2.40 (2H, m, 4-Heq and 4Ј-Heq), 3.37
(1H, dd, J 9 and 8, 2Љ-H), 3.40 (1H, t, J 9, 4Љ-H), 3.49 (1H, ddd,
J 9, 4.5 and 2, 5Љ-H), 3.59 (1H, t, J 9, 3Љ-H), 4.03 (2H, m, 3-H
and 3Ј-H), 4.30 (1H, dd, J 12 and 2, 6Љ-H), 4.44 (1H, d, J 8,
1Љ-H), 4.49 (1H, dd, J 12 and 4.5, 6Љ-H), 6.04–6.14 (4H, m, 7-H,
7Ј-H, 8-H and 8Ј-H), 6.15 (2H, br d, J 11, 10-H and 10Ј-H),
6.25 (2H, br d-like, J 10, 14-H and 14Ј-H), 6.36 (2H, d, J 15,
12-H and 12Ј-H), 6.57–6.70 (4H, m, 11-H, 11Ј-H, 15-H and
15Ј-H); CD[ether–2-methylbutane–EtOH (5 : 5 : 2)] nm (∆ε)
213 (0), 224 (Ϫ9.8), 238 (0), 250 (ϩ5.5), 263 (0), 285 (Ϫ11.9),
343 (0) (Found: Mϩ, 954.6953. C61H94O8 requires M, 954.6944).
Method B. A solution of the acyl chloride 24 prepared from
the corresponding acid 2917 (53 mg, 0.22 mmol) in CH2Cl2
(1 ml) was added to a solution of the glucoside 25 (200 mg, 0.22
mmol) and Py (1.5 ml) in CH2Cl2 (1.5 ml). After being stirred at
rt for 30 min, the reaction mixture was diluted with AcOEt. The
organic layer was washed successively with aq. 5% HCl, satur-
ated aq. NaHCO3 and brine. Evaporation of the dried solution
provided a residue, which was purified by SCC (CH2Cl2–
MeOH, 95 : 5) to afford the 6Ј-acylate 26 (129 mg, 40%) and a
mixture of the 3Ј-acylate 27 and the 4Ј-acylate 28. This mixture
was then purified by PTLC (CH2Cl2–MeOH, 94 : 6) to afford
the 3Ј-acylate 27 (42 mg, 13%) and the 4Ј-acylate 28 (9 mg, 3%).
Compound 26
λmax(EtOH)/nm 291, 218; νmax/cmϪ1 3590 and 3434 (OH), 1732
(OCO), 1669 (conj. CO), 1606 (C᎐C); δ (300 MHz) 0.86 (6H, d,
᎐
H
Synthesis of thermocryptoxanthin-15 2a
J 6.5, CHMe2), 1.10 and 1.12 (each 3H, s, gem-Me), 1.10–1.36
(18H, m, CH2 × 9), 1.51 (1H, nonet, J 6.5, CHMe2), 1.57 (1H, t,
J 12, 2-Hax), 1.62 (2H, m, CH2CH2CO), 1.77 (3H, s, 5-Me), 1.93
(1H, br d, J 12, 2-Heq), 2.16 (1H, br dd, J 17 and 9, 4-Hax), 2.30
In the same manner as described for the acylation of the gluco-
side 25 by method B, cryptoxanthin-glucoside 4 (32 mg) was
treated with the acyl chloride 24 to give crude products, which
2012
J. Chem. Soc., Perkin Trans. 1, 2002, 2006–2013