K. Goto et al.
1.04 (m, 4H), 1.31–1.43 (m, 1H), 1.36 (s, 3H), 1.39 (d, J =
3.0Hz, 1H), 1.45 (d, J = 12.0Hz, 1H), 1.56–1.63 (m, 3H),
1.68 (s, 3H), 1.79–1.93 (m, 3H), 2.01–2.05 (m, 1H), 3.61 (s,
3H), 3.70–3.75 (m, 2H), 3.85 (d, J = 11.8Hz, 1H), 4.67 (d,
J = 2.8Hz, 1H), 4.81 (dd, J = 11.6, 4.9Hz, 1H), 6.46 (s,
1H), 7.41 (dd, J = 8.0, 4.9Hz, 1H), 8.11 (m, 1H), 8.68 (dd,
J = 4.8, 1.2Hz, 1H), 8.99 (d, J = 1.9Hz, 1H); MS (ESI) m/z
608 (M + H)+; HRMS (ESI) m/z calcd. for C34H42NO9
608.2860, found 608.2859 (M + H)+.
3.5Hz, 1H), 2.11–2.14 (m, 1H), 2.25 (dd, J = 17.1, 12.8Hz,
1H), 2.54 (dd, J = 17.1, 4.6Hz, 1H), 3.45 (d, J = 10.3Hz,
1H), 3.68 (dd, J = 11.2, 5.0Hz, 1H), 3.75 (d, J = 10.3Hz,
1H), 6.42 (s, 1H), 7.39 (dd, J = 8.0, 4.8Hz, 1H), 8.10 (dt,
J = 8.0, 2.0Hz, 1H), 8.65 (dd, J = 4.8, 1.6Hz, 1H), 8.99 (d,
J = 2.0Hz, 1H); MS (ESI) m/z 426 (M + H)+.
1, 11-Di-O-cyclopropylcarbonyl-1, 11-di-deacetylpyr-
ipyropene O (34)
Reaction of 33 (22 mg, 0.0517 mmol) with cyclopropane-
carbonyl chloride (22 mg, 0.207 mmol) gave 34 (17 mg,
0.0310 mmol) as a solid in 60% yield by a similar procedure
to 6. 1H NMR (CDCl3) δ 0.88 (s, 3H), 0.99 (s, 3H), 0.84–1.08
(m, 8H), 1.21 (dt, J = 13.4, 3.6Hz, 1H), 1.28 (s, 3H),
1.43–1.48 (m, 2H), 1.56–1.73 (m, 6H), 1.81–1.85 (m, 2H),
2.13–2.16 (m, 1H), 2.26 (dd, J = 17.1, 12.8Hz, 1H), 2.55 (dd,
J = 17.1, 4.6Hz, 1H), 3.71 (d, J = 11.7Hz, 1H), 3.93 (d, J =
11.7Hz, 1H), 4.82 (dd, J = 12.0, 4.7Hz, 1H), 6.44 (s, 1H),
7.41 (dd, J = 8.0, 4.8Hz, 1H), 8.12 (ddd, J = 8.0Hz, 1H, 2.0,
1.4), 8.66 (dd, J = 4.8, 1.4Hz, 1H), 9.00 (d, J = 2.0Hz, 1H);
MS (ESI) m/z 562 (M + H)+; HRMS (ESI) m/z calcd. for
C33H40NO7 562.2805, found 562.2809 (M + H)+.
1, 11, 13-Tri-O-cyclopropylcarbonyl-1, 11-di-deace-
tylpyripyropene A (31)
To a cold (0 °C) solution of 17a (1.0 g, 1.57 mmol) in
AcOEt (10 ml) were added pyridine (3.73 g, 47.1 mmol)
and cyclopropanecarbonyl chloride (4.90 g, 47.1 mmol) and
the mixture was stirred at 40 °C for 8 h. The reaction was
quenched with MeOH and the mixture was concentrated
under reduced pressure and the residue was dissolved in
AcOEt. The organic layer was washed with water and brine,
dried over anhydrous Na2SO4, filtered and concentrated in
vacuo. The resulting residue was purified by chromato-
graphy on silica gel (acetone: hexane) to afford 31 (0.223 g,
1
0.317 mmol) as a solid in 20% yield. H NMR (CDCl3) δ
1-Deacetylpyripyropene E (35)
0.83–0.92 (m, 6H), 0.87 (s, 3H), 0.96–1.16 (m, 6H), 1.14 (s,
3H), 1.24–1.30 (m, 1H), 1.53–1.66 (m, 4H), 1.67–1.74 (m,
1H), 1.73 (s, 3H), 1.75–1.90 (m, 3H), 2.18 (s, 3H),
2.42–2.45 (m, 1H), 3.73–3.79 (m, 2H), 4.82 (dd, J = 12.0,
4.7Hz, 1H), 5.01–5.05 (m, 1H), 6.39 (d, J = 3.0Hz, 1H),
6.41 (s, 1H), 7.40 (dd, J = 8.0, 4.1Hz, 1H), 8.10 (dt, J =
8.2, 1.9Hz, 1H), 8.68 (dd, J = 4.8, 1.6Hz, 1H), 9.00 (d, J =
2.2Hz, 1H); MS (ESI) m/z 704 (M + H)+.
Reaction of PP-E (29 mg, 0.0643 mmol) with potassium
carbonate (53 mg, 0.384 mmol) gave 35 (18 mg, 0.0440
mmol) as a solid in 68% yield by a similar procedure to 23.
1H NMR (CDCl3) δ 0.82 (s, 3H), 0.92 (s, 3H), 0.99–1.02
(m, 1H), 1.03 (s, 3H), 1.12 (dt, J = 12.8, 4.0Hz, 1H), 1.27
(s, 3H), 1.40-1.46 (m, 1H), 1.50 (dd, J = 12.8, 4.4Hz, 1H),
1.62–1.74 (m, 3H), 1.79–1.83 (m, 2H), 2.14 (dt, J = 12.4,
3.2Hz, 1H), 2.24 (dd, J = 16.8, 12.4Hz, 1H), 2.53 (dd, J =
16.8, 4.8Hz, 1H), 3.25 (dd, J = 11.2, 4.0Hz, 1H), 6.42 (s,
1H), 7.38 (dd, J = 8.0, 4.8Hz, 1H), 8.10 (dt, J = 8.0, 2.0Hz,
1H), 8.65 (dd, J = 4.8, 1.6Hz, 1H), 8.99 (d, J = 2.0Hz, 1H);
MS (ESI) m/z 410 (M + H)+.
1, 11, 13-Tri-O-cyclopropylcarbonyl-1, 7, 11-tri-dea-
cetylpyripyropene A (32)
Reaction of 31 (430 mg, 0.612 mmol) with potassium
carbonate (24 mg, 0.184 mmol) gave 32 (328 mg, 0.496
mmol) as a solid in 81% yield by a similar procedure to 23.
1H NMR (CDCl3) δ 0.84–0.92 (m, 6H), 0.88 (s, 3H),
0.95–1.03 (m, 6H), 1.23 (s, 3H), 1.24–1.26 (m, 1H),
1.45–1.48 (m, 1H), 1.54–1.62 (m, 4H), 1.65 (d, J = 3.5Hz,
1H), 1.70 (s, 3H), 1.72–1.75 (m, 1H), 1.84–1.88 (m, 2H),
2.31 (br s, 1H), 2.42 (dt, J = 13.2, 3.0Hz, 1H), 3.72 (d, J =
12.0Hz, 1H), 3.79–3.82 (m, 1H), 3.86 (d, J = 11.8Hz, 1H),
4.82 (dd, J = 12.0, 4.7Hz, 1H), 6.38 (d, J = 3.4Hz, 1H),
6.48 (s, 1H), 7.41 (dd, J = 8.5, 5.0Hz, 1H), 8.11 (dt, J = 8.1,
1.9Hz, 1H), 8.69 (dd, J = 4.8, 1.6Hz, 1H), 9.00 (d, J =
1.7Hz, 1H); MS (ESI) m/z 662 (M + H)+; HRMS (ESI) m/z
calcd. for C37H44NO10 662.2965, found 662.2955 (M + H)+.
1, 11-Di-deacetylpyripyropene O (33)
1-O-Cyclopropylcarbonyl-1 -deacetylpyripyropene E
(36)
Reaction of 35 (10 mg, 0.0244 mmol) with cyclopropa-
necarbonyl chloride (10 mg, 0.0976 mmol) gave 36 (8.3 mg,
0.0174 mmol) as a solid in 71% yield by a similar procedure
1
to 6. H NMR (CDCl3) δ 0.84–0.88 (m, 2H), 0.91 (s, 3H),
0.92 (s, 3H), 0.95 (s, 3H), 0.98–1.01 (m, 2H), 1.07–1.11 (m,
1H), 1.18 (dt, J = 13.1, 3.6Hz, 1H), 1.27 (s, 3H), 1.40–1.48
(m, 1H), 1.52 (dd, J = 12.8, 4.8Hz, 1H), 1.59–1.74 (m, 4H),
1.79–1.83 (m, 2H), 2.14 (dt, J = 12.6, 3.1Hz, 1H), 2.24 (dd,
J = 17.2, 13.0Hz, 1H), 2.52 (dd, J = 17.2, 4.7Hz, 1H), 4.51
(dd, J = 11.6, 4.8Hz, 1H), 6.43 (s, 1H), 7.39 (dd, J = 8.0,
4.8Hz, 1H), 8.11 (ddd, J = 8.0, 1.6, 1.6Hz, 1H), 8.66 (dd,
J = 4.8, 1.6Hz, 1H), 9.00 (d, J = 1.6Hz, 1H); MS (FAB) m/
z 478 (M + H)+; HRMS (ESI) m/z calcd. for C29H36NO5
478.2593, found 478.2589 (M + H)+.
Reaction of PP-O (30 mg, 0.0589 mmol) with potassium
carbonate (20 mg, 0.145 mmol) gave 33 (23 mg, 0.0541
mmol) as a solid in 92% yield by a similar procedure to 23.
1H NMR (CDCl3) δ 0.89 (s, 3H), 0.97 (s, 3H), 1.14 (dt, J =
12.8, 4.2Hz, 1H), 1.20–1.25 (m, 1H), 1.28 (s, 3H),
1.45–1.59 (m, 3H), 1.64–1.75 (m, 3H), 1.82 (dt, J = 9.6,
1, 7, 11-Tri-deacetyl-13-deoxypyripyropene A (38)
The crude 38 (5.0 g), including 2 as a major component,
which was obtained by the method previously reported [6],