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H. Makabe et al. / Tetrahedron 60 (2004) 10651–10657
being stirred for a further 8 h, the reaction was quenched
with saturated aqueous NH4Cl. The organic materials were
extracted with ether and the extract was washed with brine.
Drying over MgSO4 and the evaporation of the solvent gave
an oil, which was chromatographed over silica gel (hexane–
AcOEtZ4:1) to give 10 (87 mg, 86%) as a colorless oil. IR
(film) nmax cmK1: 2920, 2850, 2200, 1765, 1460, 1430,
1150, 1100, 1040, 920, 745, 690; 1H NMR (500 MHz,
CDCl3) d: 0.88 (3H, t, JZ6.6 Hz), 1.19 (2.4H, d, JZ
6.2 Hz), 1.39 (0.6H, d, JZ6.2 Hz), 1.20–1.95 (39H, m),
2.00–2.10 (2H, m), 2.20–2.55 (3H, m), 3.38 (3H, s), 3.39
(3H, s), 3.49 (1H, m), 3.62 (1H, m), 3.86–3.93 (2H, m),
4.46–4.65 (1H, m), 4.67 (1H, d, JZ6.5 Hz), 4.69 (1H, d, JZ
6.5 Hz), 4.81 (1H, d, JZ6.5 Hz), 4.82 (1H, d, JZ6.5 Hz),
5.40–5.45 (1H, m), 5.96–6.05 (1H, m), 7.30–7.45 (3H, m),
7.50–7.60 (2H, m); HRFABMS calcd for C45H72O7SNa
[(MCNa)C] 779.4896, found 778.4894.
1470, 1320, 1110, 1080, 1030, 960, 840, 750, 715; 1H NMR
(500 MHz, CDCl3) d: 0.88 (3H, t, JZ6.6 Hz), 1.20–2.05
(48H, m), 1.41 (3H, d, JZ6.6 Hz), 2.27 (2H, t, JZ7.3 Hz),
2.39 (2H, br., –OH), 3.41 (2H, m), 3.81 (2H, m), 4.99 (1H,
dq, JZ6.7, 1.6 Hz), 6.98 (1H, d, JZ1.6 Hz); 13C NMR
(125 MHz, CDCl3) d: 14.12, 19.23, 22.70, 25.20, 25.73,
27.43, 28.15 (2!C), 29.20, 29.31, 29.37, 29.51 (2!C),
29.61, 29.64, 29.66 (2!C), 29.68, 29.69, 29.84, 29.72 (2!
C), 30.32, 31.94, 32.54, 34.00 (2!C), 34.16, 74.39, 77.40,
82.70, 134.40, 148.83, 173.89 ppm; HREIMS calcd for
C35H64O5 [MC] 564.4753, found 564.4720.
3.1.8.1. Diastereomer of cis-solamin (1b). Mp 63–
:
66 8C; [a]2D1ZC42 (c 0.50, CHCl3); IR (film) nmax cmK1
3420, 2920, 2850, 1760, 1470, 1320, 1110, 1080, 1030, 960,
1
840, 750, 715; H NMR (500 MHz, CDCl3) d: 0.88 (3H, t,
JZ6.6 Hz), 1.20–2.05 (48H, m), 1.41 (3H, d, JZ6.6 Hz),
2.00 (1H, br., –OH), 2.27 (2H, t, JZ7.3 Hz), 2.35 (1H, br.,
–OH), 3.42 (2H, m), 3.81 (2H, m), 4.99 (1H, dq, JZ6.7,
1.6 Hz), 6.98 (1H, d, JZ1.6 Hz); 13C NMR (125 MHz,
CDCl3) d: 14.11, 19.24, 22.70, 25.20, 25.73, 27.44, 28.16
(2!C), 29.20, 29.32, 29.37, 29.52 (2!C), 29.61, 29.63,
29.65 (2!C), 29.68, 29.70, 29.72 (2!C), 30.32, 31.94,
32.54, 34.00 (2!C), 34.16, 74.40, 77.40, 82.70, 134.41,
148.83, 173.90 ppm; HRFABMS calcd for C35H64O5Na
[MCNaC] 587.4651, found 587.4650.
3.1.7. (1000S,200R,3RS,5S,500S,130R)-3-{130-Methoxymeth-
oxy-130-[500-(1000-methoxymethoxytridecyl)tetrahydro-
furan-200-yl]tridecyl}-5-methyl-3-(phenylsulphanyl)-
tetrahydrofuran-2-one (11). To a refluxing solution of 10
(15 mg, 0.2 mmol) and p-toluenesulfonylhydrazide (2.62 g,
13.4 mmol) in diethoxyethane (15 mL) was added sodium
acetate (1.36 g, 16.6 mmol) in water (20 mL) over a 4 h
period at 120 8C. After being cooled to room temperature,
the reaction mixture was quenched with water and extracted
with AcOEt. The organic layer was washed with brine, dried
over MgSO4, filtered and concentrated. The residue was
chromatographed over silica gel (hexane–AcOEtZ4:1)
to give 11 (13 mg, 89%) as a colorless oil. IR (film) nmax
cmK1: 2920, 2850, 1765, 1460, 1430, 1150, 1100, 1040,
3.1.9. Preparation of the bis-(R)-MTPA ester of 1a. To a
stirred solution of 1a (1.0 mg, 1.8 mmol) in CH2Cl2
(0.2 mL) was sequentially added Et3N (0.4 mg, 2.5 mmol),
DMAP (0.1 mg, 0.8 mmol), and (S)-MTPACl (w5 mL,
27 mmol) at room temperature. After the mixture was
stirred for 8 h, saturated aqueous NaHCO3 and Et2O were
added. This mixture was stirred vigorously for 1 h. The
organic phase was extracted with Et2O and the extract was
washed with brine. Drying over MgSO4 and the evaporation
of the solvent gave an oil, which was purified with
preparative TLC (hexane–AcOEtZ4:1) to give bis-(R)-
1
920, 740; H NMR (500 MHz, CDCl3) d: 0.88 (3H, t, JZ
6.6 Hz), 1.19 (2.4H, d, JZ6.2 Hz), 1.38 (0.6H, d, JZ
6.2 Hz), 1.20–1.90 (49H, m), 1.95–2.10 (2H, m), 2.32
(0.2H, dd, JZ13.9, 5.5 Hz), 2.52 (0.8H, dd, JZ13.9,
7.5 Hz), 3.38 (3H, s), 3.39 (3H, s), 3.49 (2H, m), 3.89
(2H, m), 4.46–4.65 (1H, m), 4.67 (1H, d, JZ6.5 Hz), 4.69
(1H, d, JZ6.5 Hz), 4.81 (1H, d, JZ6.5 Hz), 4.82 (1H, d,
JZ6.5 Hz), 7.30–7.45 (3H, m), 7.50–7.60 (2H, m);
1
MTPA ester of 1a (1.2 mg, 90%) as a light yellow oil. H
NMR (500 MHz, CDCl3) d: 0.88 (3H, t, JZ6.6 Hz), 1.20–
2.05 (50H, m), 1.39 (3H, d, JZ6.2 Hz), 2.26 (2H, t, JZ
7.6 Hz), 3.60 (3H, s), 3.68 (3H, s), 3.87 (1H, m), 4.08 (1H,
m), 4.92 (1H, m), 4.98 (1H, dq, JZ6.2, 1.4 Hz), 5.06 (1H,
m), 6.97 (1H, d, JZ1.4 Hz), 7.35–7.65 (10H, m) ppm.
HRFABMS calcd for C45H78O7SNa [(MCNa)C
]
785.5366, found 785.5368.
3.1.8. cis-Solamin (1a). To a solution of 11 (10 mg,
13.6 mmol) in CH2Cl2 (1 mL) was added mCPBA (80%,
5.4 mg, 25 mmol) at 0 8C. After the mixture had been stirred
at this temperature for 10 min, Na2S2O3/NaHCO3 (1:1,
1.0 mL) was added. After stirring at 23 8C for 1 h, the
mixture was extracted with ether and the extract was washed
with brine. Drying over MgSO4 and subsequent concen-
tration gave an oil, which was then dissolved in toluene
(2.0 mL) and the solution was refluxed for 1 h. After
completion of the reaction, concentration of the mixture
gave an oil, which was dissolved in dimethyl sulfide
(0.5 mL) at 0 8C and BF3$Et2O was added. After the
mixture had been stirred for 10 min at this temperature, the
reaction mixture was quenched with saturated aqueous
NaHCO3 and diluted with AcOEt. The mixture was washed
with water and brine. Drying over MgSO4 and evaporation
of the solvent gave a colorless solid, which was purified by
silica gel chromatography (AcOEt) gave 1a (3.4 mg, 60%)
as a colorless solid. Mp 66–68 8C; [a]2D1ZC26 (c 0.45,
CHCl3); IR (film) nmax cmK1: 3420, 2920, 2850, 1760,
3.1.9.1. Bis-(S)-MTPA ester of 1a. 1H NMR (500 MHz,
CDCl3) d: 0.88 (3H, t, JZ6.6 Hz), 1.20–2.05 (50H, m), 1.39
(3H, d, JZ6.2 Hz), 2.26 (2H, t, JZ7.6 Hz), 3.60 (3H, s),
3.68 (3H, s), 3.86 (1H, m), 4.09 (1H, m), 4.93 (1H, m), 4.98
(1H, dq, JZ6.2, 1.4 Hz), 5.06 (1H, m), 6.97 (1H, d, JZ
1.4 Hz), 7.35–7.65 (10H, m) ppm.
3.1.9.2. Bis-(R)-MTPA ester of 1b. 1H NMR (500 MHz,
CDCl3) d: 0.88 (3H, t, JZ6.6 Hz), 1.20–2.05 (50H, m), 1.39
(3H, d, JZ6.2 Hz), 2.26 (2H, t, JZ7.6 Hz), 3.60 (3H, s),
3.68 (3H, s), 3.86 (1H, m), 4.09 (1H, m), 4.93 (1H, m), 4.98
(1H, dq, JZ6.2, 1.4 Hz), 5.06 (1H, m), 6.97 (1H, d, JZ
1.4 Hz), 7.35–7.65 (10H, m) ppm.
3.1.9.3. Bis-(S)-MTPA ester of 1b. 1H NMR (500 MHz,
CDCl3) d: 0.88 (3H, t, JZ6.6 Hz), 1.20–2.05 (50H, m), 1.39
(3H, d, JZ6.2 Hz), 2.26 (2H, t, JZ7.6 Hz), 3.60 (3H, s),
3.68 (3H, s), 3.87 (1H, m), 4.08 (1H, m), 4.92 (1H, m), 4.98