impact mode at 70 eV with continuous scans (every 0.5 s) in the
range m/z 29–350. Data were analyzed using the GC-MS
solution software.
HPLC-UV/Vis-MS: tR 13.02 min; lmax/nm 396, 418, 444
ꢀꢀꢀ
(main absorption band is underlined), m/z 379.5 ([M + H]+),
361.5 ([M + H]+-H2O).
NMR. H and 13C NMR spectra were recorded on a Bruker
1
(2E,4E,6E,8E,10E,12E,14E,16E,20E)-4,9,13,17,21-Pentamethyl-
Advance DRX 500 MHz spectrometer. Chemical shifts are given
in ppm relative to peak solvent (CDCl3).40 J values are given
in Hz. Signal assignments were deduced from a combination of
heteronuclear single quantum coherence (HSQC), distortionless
enhancement by polarization transfer quantum (DEPTQ 135),
nuclear overhauser effect spectroscopy (NOESY), correlation
spectroscopy (COSY) and heteronuclear multiple bond coherence
(HMBC) spectra.
docosa-2,4,6,8,10,12,14,16,20-nonaenal
(apo-100-lycopenal,
100-CHO). Compound 100-CH2OH (90 mg, 0.24 mmol) was
dissolved in AcOEt (5 ml). After addition of MnO2 (510 mg,
5 mmol), the heterogeneous mixture was vigorously stirred at
room temperature for 2 h. Then, the mixture was filtered off
through Celite, dried over Na2SO4 and concentrated. The
residue was purified by filtration through a silica gel chromato-
graphic column (eluent hexane/AcOEt (2/8, v/v)). Compound
100-CHO was obtained as a red powder (40 mg, 44%).
dH (500 MHz; CDCl3) 1.61 (3H, s, C(21)Me), 1.69 (3H, s,
C(22)H3), 1.82 (3H, s, C(17)Me), 1.96 (3H, s, C(4)Me), 1.98
(3H, s, C(13)Me), 2.01 (3H, s, C(9)Me), 2.12 (4H, m, C(18,
19)H2), 5.11 (1H, m, C(20)H), 5.95 (1H, d, J 11.0, C(16)H),
6.18 (1H, dd, J 7.8 and 15.3, C(2)H), 6.18 (1H, d, J 11.6,
C(12)H), 6.25 (1H, d, J 15.1, C(14)H), 6.28 (1H, d, J 12.1,
C(8)H), 6.36 (1H, d, J 14.9, C(10)H), 6.53 (1H, dd, J 11.0 and
15.1, C(15)H), 6.61 (1H, m, C(6)H), 6.61 (1H, m, C(5)H), 6.73
(1H, dd, J 11.6 and 14.9, C(11)H), 6.86 (1H, m, C(7)H), 7.15
(1H, d, J 15.3, C(3)H), 9.58 (1H, d, J 7.8, C(1)H).
HRMS. High-resolution mass analysis was carried out using
a QStar Elite (Applied Biosystems SCIEX) with positive
electrospray-TOF ionisation. High-resolution mass analysis
was carried out on an Ultraflextreme TOF/TOF (Bruker) with
NALDIt ionisation for compound 140-CH2OH.
Synthesis of apo-100-, apo-140- and apo-11-lycopenoids
All reactions were carried out under dim light and argon
atmosphere.
Synthesis of apo-100-lycopenoids
(2E,4E,6E,8E,10E,12E,14E,16E,20E)-4,9,13,17,21-Pentamethyl-
docosa-2,4,6,8,10,12,14,16,20-nonaen-1-ol (apo-100-lycopenol,
100-CH2OH). Ethyl apo-100-lycopenoate (100-COOEt)25 (287 mg,
0.68 mmol) was dissolved in dry THF (5 ml). A solution of
DIBAH (1.7 mmol) in toluene (1.4 ml) was carefully added
over 30 min at 0 1C. The mixture was stirred for 4 h, then a
MeOH/water (3 ml, 1/1, v/v) mixture was slowly added at
0 1C. The gel formed was destroyed by addition of a 2 M
potassium sodium tartrate aqueous solution (10 ml) and
vigorous stirring for 10 h. Then, the product was extracted
with diethylether (3 ꢃ 10 ml). The combined organic phases
were dried over Na2SO4 and concentrated. The crude product
was purified by filtration through a silica gel chromatographic
column (eluent hexane/AcOEt (1/1, v/v)), then crystallized
from CH2Cl2/hexane. Compound 100-CH2OH was obtained
as a red powder (80 mg, 31%).
dC (125 MHz; CDCl3) 12.9 (C(4)Me), 13.1 (C(9)Me), 13.1
(C(13)Me), 17.1 (C(17)Me), 17.8 (C(21)Me), 25.8 (C(22)), 26.8
(C(19)), 40.4 (C(18)), 124.0 (C(20)), 125.7 (C(15)), 125.8 (C(16)),
127.2 (C(2)), 127.2 (C(11)), 128.6 (C(6)), 131.3 (C(12)), 131.7
(C(8)), 131.8 (C(21)), 133.8 (C(4)), 135.3 (C(14)), 135.5 (C(7)),
136.8 (C(10)), 137.7 (C(13)), 140.2 (C(9)), 140.3 (C(17)), 141.3
(C(5)), 156.7 (C(3)), 193.8 (C(1)).
HRMS: m/z 377.2823 ([M + H]+) (377.2839 calculated for
C27H37O).
HPLC-UV/Vis-MS: tR 13.61 min, lmax/nm 458, m/z 377.5
([M + H]+).
Synthesis of apo-140-lycopenoids
(2E,4E,6E,8E,10E,12E,16E)-5,9,13,17-Tetramethyloctadeca-
2,4,6,8,10,12,16-heptaen-1-ol (apo-140-lycopenol, 140-CH2OH).
A solution of DIBAH (3.5 mmol) in toluene (3.5 ml) was
carefully added over 1 h to a solution of methyl apo-140-
lycopenoate (140-COOMe)25 (500 mg, 1.47 mmol) in dry
THF (20 ml) at 0 1C and the resulting mixture stirred for 3 h
at 0 1C. The reaction was quenched by careful addition of
MeOH/water (5 ml, 1/1, v/v) at 0 1C. The gel thus formed was
dissociated by addition of aqueous 2 M potassium sodium
tartrate (20 ml) and vigorous stirring for 10 h. Then, the
product was extracted with diethylether (3 ꢃ 10 ml) and the
combined organic phases dried over Na2SO4 and concentrated.
The residue was purified by filtration through a silica gel
chromatographic column (eluent hexane/AcOEt (1/1, v/v)),
then crystallized from CH2Cl2/hexane. Compound 140-CH2OH
was obtained as an orange powder (163 mg, 35%).
dH (500 MHz; CDCl3) 1.39 (1H, t, J 5.85, OH), 1.61 (3H, s,
C(21)Me), 1.69 (3H, s, C(22) H3), 1.82 (3H, s, C(17)Me), 1.91
(3H, s, C(4)Me), 1.97 (6H, s, C(9, 13)Me), 2.12 (4H, m,
C(18, 19) H2), 4.25 (2H, t, J 6.1, C(1)H), 5.11 (1H, m, C(20)H),
5.88 (1H, dt, J 6.1 and 15.6, C(2)H), 5.95 (1H, d, J 11.0, C(16)H),
6.18 (1H, d, J 11.5, C(12)H), 6.21 (1H, d, J 11.5, C(8)H), 6.23 (1H,
d, J 11.0, C(5)H), 6.25 (1H, d, J 15.2, C(14)H), 6.34 (1H, d, J 15.6,
C(3)H), 6.35 (1H, d, J 15.0, C(10)H), 6.49 (1H, dd, J 11.0 and
15.2, C(15)H), 6.59 (1H, m, C(6)H), 6.61 (1H, m, C(7)H),
6.64 (1H, m, C(11)H).
dC (125 MHz; CDCl3) 13.0 (C(4)Me), 13.0 (C(9)Me), 13.0
(C(13)Me), 17.1 (C(17)Me), 17.9 (C(21)Me), 25.9 (C(22)), 26.8
(C(19)), 40.4 (C(18)), 64.1 (C(1)), 124.1 (C(20)), 125.0 (C(15)),
125.5 (C(11)), 125.9 (C(16)), 127.5 (C(2)), 129.6 (C(6)), 130.6
(C(7)), 131.6 (C(12)), 131.9 (C(21)), 132.4 (C(8)), 132.5 (C(5)),
134.9 (C(4)), 135.5 (C(14)), 136.4 (C(13)), 136.5 (C(3)), 136.9
(C(9)), 137.4 (C(10)), 139.7 (C(17)).
dH (500 MHz; CDCl3) 1.4 (1H, t, J 5.8, HO), 1.61 (3H, s,
C(17)Me), 1.69 (3H, s, C(18)H3), 1.82 (3H, s, C(13)Me), 1.94
(3H, s, C(5)Me), 1.95 (3H, s, C(9)Me), 2.12 (4H, m, C(14,
15)H2), 4.25 (2H, t, J 5.9, C(1)H2), 5.11 (1H, m, C(16)H), 5.89
(1H, dt, J 5.9 and 14.9, C(2)H), 5.95 (1H, d, J 11.0, C(12)H),
6.12 (1H, d, J 11.4, C(4)H), 6.16 (1H, d, J 11.4, C(8)H),
HRMS: m/z 379.2978 ([M + H]+) (379.2995 calculated for
C27H39O).
c
584 New J. Chem., 2012, 36, 575–587
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012