3758
Y. Shikichi et al. / Tetrahedron 68 (2012) 3750e3760
with LiAlH4 (1.22 g, 32.1 mmol) in dry THF (4 mL) and dry diglyme
(199 mg, 0.877 mmol) in CH2Cl2 (13 mL) and water (1.3 mL) to give
(23 mL) to give 2.16 g (96%) of (R)-21 as a colorless solid. Mp
158 mg (54%) of (3R,11E,19Z)-1 as an oil, which solidified in a deep
37e38 ꢁC; ½a 2D2
ꢃ
þ0.51 (c 4.04, CHCl3); nmax (film): 3305 (br, OeH),
freezer. n2D5 1.4679; ½a 2D6
ꢀ7.03 (c 1.07, hexane); nmax (film): 3447
ꢃ
3002 (m), 2916 (s), 2850 (s), 1467 (s), 1118 (m), 1049 (m), 963 (m),
721 (m); dH (CDCl3): 0.88 (3H, t, J 6.8), 1.18e1.56 (32H, br), 1.61e1.77
(2H, m), 1.89e2.08 (8H, m), 2.49e2.79 (2H, br), 3.78e3.94 (3H, br),
5.29e5.44 (4H, m, 2ꢂ CH]CH). HRMS of (R)-21: calcd for C28H55O2
[(MþH)þ]: 423.4197, found: 423.4197.
(br, OeH), 3004 (w), 2925 (s), 2853 (s), 1739 (s, C]O), 1464 (m),
1375 (m), 1245 (s, CeO), 1055 (m), 1022 (m), 966 (m), 721(w); dH
(CDCl3): 0.88 (3H, t, J 6.8), 1.07e1.39 (30H, br), 1.47e1.71 (3H, m),
1.78e1.88 (1H, br), 1.88e2.07 (8H, m), 2.07 (3H, s, COCH3),
2.42e2.54 (1H, br), 3.48e3.58 (1H, br, CHHOH), 3.58e3.68 (1H, br,
CHHOH), 4.97e5.07 (1H, br, CHOAc), 5.29e5.43 (4H, m, 2ꢂ CH]
CH); dC (CDCl3): 14.0, 21.1, 22.7, 25.4, 27.1, 27.2, 29.0, 29.1, 29.26,
29.32, 29.47, 29.56, 29.57, 29.69, 29.72, 31.9, 32.52, 32.54, 34.6, 37.5,
58.5, 71.6, 129.8, 129.9, 130.2, 130.3, 171.9; GCeMS [same conditions
as for (3R,11E,19E)-1]: tR 23.62 min (92.7%). MS of (3R,11E,19Z)-1
(70 eV, EI): m/z: 464 (3) [Mþ, C30H56O3], 446 (8), 404 (7), 386 (11),
374 (2), 357 (3), 287 (5), 273 (7), 259 (6), 247 (8), 233 (7), 219 (5),
207 (5), 194 (5), 177 (6), 163 (13), 149 (28), 135 (49), 121 (52), 109
(49), 95 (87), 81 (100), 67 (89), 55 (85), 43 (75). HRMS of
(3R,11E,19Z)-1: calcd for C30H57O3 [(MþH)þ]: 465.4302, found:
465.4303.
4.15.2. (S)-Isomer. In the same manner, (S)-20 (2.57 g, 3.92 mmol)
gave 1.66 g (quant.) of (S)-21 as a colorless solid. Mp 36e38 ꢁC; ½a D20
ꢃ
ꢀ0.58 (c 3.88, CHCl3). Its IR and 1H NMR spectra were identical to
those of (R)-21. HRMS of (S)-21: calcd for C28H55O2 [(MþH)þ]:
423.4197, found: 423.4196.
4.16. (11E,19Z)-11,19-Octacosadiene-1,3-diol 1-PMB ether (22)
4.16.1. (R)-Isomer. In the same manner as described above for (R)-
18, (R)-21 (2.00 g, 4.73 mmol) in dry THF (25 mL) and dry DMF
(5 mL) was treated with PMBCl (0.71 mL, 5.2 mmol) and t-BuOK
(694 mg, 5.68 mmol) to give 889 mg (35%) of (R)-22 as a colorless
oil, which solidified in a deep freezer. Subsequent elution with
EtOAc afforded 900 mg (45%) of recovered diol (R)-21. Properties of
4.18.2. (S)-Isomer. Similarly, (S)-23 (313 mg, 0.535 mmol) afforded
123 mg (49%) of (3S,11E,19Z)-1 as an oil, which solidified in a deep
freezer. n2D4 1.4681; ½a 2D7
ꢃ
þ7.36 (c 1.02, hexane). Its IR, 1H and 13C
(R)-22: n2D5 1.4922; ½a 2D6
ꢃ
þ5.74 (c 2.80, hexane); nmax (film): 3445
NMR spectra were identical to those of (3R,11E,19Z)-1. GCeMS
[same conditions as for (3R,11E,19E)-1]: tR 23.61 min (90.4%). MS of
(3S,11E,19Z)-1 (70 eV, EI): m/z: 464 (3) [Mþ, C30H56O3], 446 (7), 404
(7), 386 (10), 374 (2), 357 (3), 287 (5), 273 (7), 259 (6), 247 (8), 233
(7), 219 (5), 207 (7), 194 (5), 177 (6), 163 (13), 149 (27), 135 (50), 121
(53), 109 (48), 95 (90), 81 (100), 67 (89), 55 (87), 43 (81). HRMS of
(3S,11E,19Z)-1: calcd for C30H57O3 [(MþH)þ]: 465.4302, found:
465.4303.
(br, OeH), 3002 (w), 2925 (s), 2853 (s), 1613 (m, arom. C]C), 1586
(w), 1514 (s), 1464 (m), 1249 (s), 1092 (m), 1039 (m), 967 (m), 822
(m), 722 (m); dH (CDCl3): 0.88 (3H, t, J 6.8), 1.08e1.54 (32H, br),
1.68e1.78 (2H, m), 1.90e2.09 (8H, m), 2.82e2.94 (1H, br),
3.58e3.72 (2H, m), 3.74e3.87 (1H, br), 3.80 (3H, s, OCH3), 4.45 (2H,
s, OCH2Ar), 5.30e5.44 (4H, m, 2ꢂ CH]CH), 6.87 (2H, d, J 8.6, arom.
H), 7.25 (2H, d, J 8.3, arom. H). HRMS of (R)-22: calcd for C36H63O3
[(MþH)þ]: 543.4772, found: 543.4776.
4.19. (E)-19-Octacosen-11-yne-1,3-diol 1-PMB ether (24)
4.16.2. (S)-Isomer. Similarly, (S)-21 (1.55 g, 3.67 mmol) afforded
621 mg (31%) of (S)-22 as a colorless oil, which solidified in a deep
freezer and 686 mg (44%) of recovered (S)-21. Properties of (S)-22:
4.19.1. (R)-Isomer. A solution of TBAF in THF (1.0 M, 5 mL, 5 mmol)
was added to a solution of (S)-16 (2.50 g, 3.82 mmol) in dry THF
(5 mL). After stirring overnight at room temperature, an additional
amount of TBAF in THF (1.0 M, 5 mL, 5 mmol) was added to the
mixture to complete the reaction. The mixture was stirred for 2 d at
room temperature. It was then diluted with ice-water and extracted
with Et2O. The Et2O solution was successively washed with water
and brine, dried (MgSO4), and concentrated in vacuo. The residue
(2.41 g) was chromatographed over SiO2 (50 g). Elution with hex-
ane/EtOAc (5:1) gave 1.88 g (91%) of (R)-24 as a colorless solid. Mp
n2D3 1.4911; ½a 2D7
ꢃ
ꢀ5.72 (c 2.86, hexane). Its IR and 1H NMR spectra
were identical to those of (R)-22. HRMS of (S)-22: calcd for
C36H63O3 [(MþH)þ]: 543.4772, found: 543.4764.
4.17. (11E,19Z)-3-Acetoxy-11,19-octacosadien-1-ol PMB
ether (23)
4.17.1. (R)-Isomer. In the same manner as described above for (R)-
19, (R)-22 (375 mg, 0.691 mmol) gave 394 mg (98%) of (R)-23 as
32e34 ꢁC; ½a 2D4
þ6.17 (c 4.12, hexane); nmax (film): 3507 (br, OeH),
ꢃ
a colorless oil, n2D5 1.4856; ½a D27
ꢃ
ꢀ12.0 (c 3.00, hexane); nmax (film):
2924 (vs), 2850 (s), 1613 (m, arom. C]C), 1586 (w), 1517 (m), 1464
(s), 1252 (s), 1126 (m), 1091 (m), 1035 (m), 963 (m), 813 (s), 723 (m);
dH (CDCl3): 0.88 (3H, t, 6.8), 1.17e1.53 (32H, br), 1.67e1.76 (2H, m),
1.90e2.03 (4H, br), 2.13 (4H, t, J 6.8, 2ꢂ C^CCH2), 2.89 (1H, d, J 3.2),
3.57e3.65 (1H, m), 3.65e3.73 (1H, m), 3.73e3.84 (1H, br), 3.80 (3H,
s, OCH3), 4.45 (2H, s, OCH2Ar), 5.31e5.44 (2H, m, CH]CH), 6.88 (2H,
d, J 8.4, arom. H), 7.25 (2H, d, J 8.4, arom. H). HRMS of (S)-24: calcd
for C36H61O3 [(MþH)þ]: 541.4615, found: 541.4613.
3002 (w), 2925 (s), 2854 (s), 1738 (s, C]O), 1613 (m, arom. C]C),
1586 (w), 1514 (m), 1464 (m), 1371 (m), 1246 (s), 1098 (m), 1038 (m),
967 (m), 821 (m), 724 (w); dH (CDCl3): 0.88 (3H, t, J 6.8), 1.17e1.38
(30H, br), 1.45e1.60 (2H, br), 1.77e1.87 (2H, m), 1.90e2.07 (8H, m),
2.00 (3H, s, COCH3), 3.40e3.51 (2H, m), 3.80 (3H, s, OCH3), 4.40 (2H,
s, OCH2Ar), 4.96e5.05 (1H, m), 5.30e5.43 (4H, m, 2ꢂ CH]CH), 6.87
(2H, d, J 8.8, arom. H), 7.25 (2H, d, J 8.8, arom. H). HRMS of (R)-23:
calcd for C38H65O4 [(MþH)þ]: 585.4877, found: 585.4879.
4.19.2. (S)-Isomer. In the same manner, (S)-16 (2.50 g, 3.82 mmol)
4.17.2. (S)-Isomer. Similarly, (S)-22 (348 mg, 0.641 mmol) afforded
gave 1.76 g (85%) of (S)-24 as a colorless solid. Mp 32e34 ꢁC; ½a D24
ꢃ
355 mg (95%) of (S)-23 as a colorless oil, n2D3 1.4855; ½a D22
ꢃ
þ12.5 (c
ꢀ6.23 (c 3.97, hexane). Its IR and 1H NMR spectra were identical to
those of (S)-24. HRMS of (R)-24: calcd for C36H61O3 [(MþH)þ]:
541.4615, found: 541.4592.
2.70, hexane). Its IR and 1H NMR spectra were identical to those of
(R)-23. HRMS of (S)-23: calcd for C38H65O4 [(MþH)þ]: 585.4877,
found: 585.4871.
4.20. (11Z,19E)-11,19-Octacosadiene-1,3-diol 1-PMB ether (25)
4.18. (11E,19Z)-3-Acetoxy-11,19-octacosadien-1-ol (CH503)
[(11E,19Z)-1]
4.20.1. (R)-Isomer. In the same manner as described above for 8,
(R)-24 (1.73 g, 3.20 mmol) was stirred with Lindlar’s Pd catalyst on
4.18.1. (R)-Isomer. In the same manner as described above for
(3R,11E,19E)-1, (R)-23 (366 mg, 0.626 mmol) was treated with DDQ
CaCO3 with Pb2þ (Aldrich, 35 mg) and quinoline (69
mL) in cyclo-
hexane (17 mL) under an H2 atmosphere for 3 h to gave 1.69 g (97%)