Structural Modifications of Plumieride
300.2 (45), 331.2 (31), 708.3 (MH+, 30); HRMS (FAB) calcd for
washed with water, dried over Na2SO4, filtered, and concen-
trated. The residua were purified with column chromatography
over silica gel eluting with MeOH/CH2Cl2 (v/v 1/9) to afford
11 (260 mg, 72.5%) as colorless gummy solid: 1H NMR (CDCl3)
δ 7.48 (2H, m), 7.43 (1H, s), 7.36 (3H, m), 7.06 (1H, s), 6.46
(1H, dd, J ) 5.4, 2.2 Hz), 5.53 (1H, s), 5.47 (1H, d, J ) 5.6
Hz), 5.07 (1H, d, J ) 3.8 Hz), 4.75 (1H, d, J ) 7.8 Hz), 4.67
(1H, q, J ) 6.4 Hz), 4.36 (1H, dd, J ) 11.0, 4.7 Hz), 3.90 (1H,
br d, J ) 7.8 Hz), 3.84-3.72 (5H, m), 3.53 (1H, dd, J ) 11.1,
11.1 Hz), 3.46 (2H, m), 3.03 (1H, dd, J ) 7.7, 4.3 Hz), 2.93
(1H, s), 2.87 (1H, s), 1.47 (3H, d, J ) 6.5 Hz); 13C NMR (CDCl3/
CD3OD, 7/1) δ 171.6 (C), 167.0 (C), 150.8 (CH), 148.3 (CH),
140.2 (CH), 137.3 (C), 137.0 (C), 129.3 (CH), 128.8 (CH), 128.3
(CH), 126.3 (CH), 110.1 (C), 101.9 (CH), 99.0 (CH), 96.5 (C),
92.8 (CH), 80.4 (CH), 74.0 (CH), 73.1 (CH), 68.5 (CH2), 66.7
(CH), 62.4 (CH), 51.6 (CH3), 49.1 (CH), 38.7 (CH), 21.7 (CH3);
MS (FAB) m/z 559.1 (MH+, 100); HRMS (FAB) calcd for
C
33H42NO16 (M + H) 708.2504, found 708.2503.
Com p ou n d 9. To a solution of 7 (105 mg, 0.16 mmol) and
hexylamine (0.1 mL, 0.76 mmol) in dry CH2Cl2 (4 mL) were
added Et3N (15 drops) and BOP reagent (84 mg, 0.19 mmol).
The mixture was stirred under N2 at room temperature for 2
h. It was then diluted with CH2Cl2 (30 mL), washed with
water, dried over Na2SO4, filtered, and concentrated. The
residue was purified with preparative silica TLC using CH2-
Cl2/acetone (v/v 8/1) as developing solvent to provide 9 (62 mg,
52%) as a yellowish gummy solid: 1H NMR (CDCl3) δ 7.12
(1H, s, 3-H), 7.02 (1H, s, 10-H), 6.31 (1H, dd, J ) 5.3, 3.3 Hz,
6-H), 5.74 (1H, t, J ) 5.4 Hz, 17-H), 5.66 (1H, q, J ) 6.6 Hz,
14-H), 5.50 (1H, d, J ) 5.6 Hz, 7-H), 5.21 (1H, dd, J ) 9.4, 9.4
Hz, 3′-H), 5.09 (1H, dd, J ) 9.8, 9.8 Hz, 4′-H), 5.04 (1H, d, J )
3.3 Hz, 1-H), 4.95 (1H, dd, J ) 9.9, 8.4 Hz, 2′-H), 4.84 (1H, d,
J ) 8.0 Hz, 1′-H), 4.33 (1H, dd, J ) 12.5, 4.6 Hz, one proton of
6′-H), 4.11 (1H, dd, J ) 12.5, 2.1 Hz, one proton of 6′-H), 3.81
(1H, br d, J ) 6.0 Hz, 5-H), 3.74 (1H, m, 5′-H), 3.39 and 3.27
(2H, m, ABX, H-18), 3.14 (1H, dd, J ) 8.7, 3.3 Hz, 9-H), 2.11
(3H, s, -OAc), 2.09 (3H, s, -OAc), 2.03 (3H, s, -OAc), 2.01 (3H,
s, -OAc), 1.94 (3H, s, -OAc), 1.55 (2H, m, 19-H), 1.52 (3H, d, J
) 6.6 Hz, 15-H), 1.33 (6H, m, 20-H, 21-H, 22-H), 0.90 (3H, t,
J ) 7.0 Hz, 23-H); 13C NMR (CDCl3) δ 170.6 (C), 170.2 (C),
169.9 (C), 169.8 (C), 169.5 (C), 169.3 (C), 165.5 (C), 148.6 (CH),
144.4 (CH), 137.7 (CH), 134.5 (C), 130.4 (CH), 114.6 (C), 95.9
(CH), 95.7 (C), 92.0 (CH), 72.5 (CH), 72.4 (CH), 70.9 (CH), 68.2
(CH), 65.2 (CH), 61.8 (CH2), 49.1 (CH), 39.9 (CH2), 38.2 (CH),
31.6 (CH2), 29.8 (CH2), 26.8 (CH2), 22.7 (CH2), 21.2 (CH3), 20.8
(CH3), 20.7 (2 × CH3), 20.5 (CH3), 19.4 (CH3), 14.1 (CH3); MS
(FAB) m/z 109.0 (83), 127.1 (33), 169.1 (100), 229.3 (33), 331.1
C
28H31O12 (M + H) 559.1816, found 559.1815.
Com p ou n d 12. Acetylation of compound 11 with acetic
anhydride in pyridine provided 12 as colorless gummy solid
in quantitative yield: 1H NMR (CDCl3) δ 7.43 (2H, m), 7.38
(1H, s), 7.35 (3H, m), 6.92 (1H, s), 6.45 (1H, dd, J ) 5.5, 2.3
Hz), 5.66 (1H, q, J ) 6.6 Hz), 5.51 (1H, s), 5.44 (1H, d, J ) 5.8
Hz), 5.31 (1H, dd, J ) 10.5, 9.3 Hz), 5.08 (1H, d, J ) 2.2 Hz),
4.96 (1H, dd, J ) 9.9, 8.8 Hz), 4.88 (1H, d, J ) 7.6 Hz), 4.40
(1H, dd, J ) 10.8, 4.9 Hz), 3.81 (1H, dd, J ) 11.1, 10.2 Hz),
3.76 (4H, s), 3.70 (1H, dd, J ) 10.6, 9.3 Hz), 3.55 (1H, m), 3.14
(1H, dd, J ) 8.8, 2.2 Hz), 2.10 (3H, s), 2.04 (3H, s), 1.93 (3H,
s), 1.52 (3H, d, J ) 6.6 Hz); 13C NMR (CDCl3) δ 170.2 (C), 169.9
(C), 169.8 (C), 169.2 (C), 166.3 (C), 149.4 (CH), 148.7 (CH),
138.9 (CH), 136.8 (C), 134.4 (C), 129.5 (CH), 129.3 (CH), 128.4
(CH), 126.3 (CH), 111.7 (C), 101.7 (CH), 96.5 (CH), 95.9 (C),
92.3 (CH), 78.3 (CH), 71.7 (CH), 71.5 (CH), 68.5 (CH2), 66.9
(CH), 65.1 (CH), 51.7 (CH3), 48.9 (CH), 37.7 (CH), 21.2 (CH3),
20.9 (CH3), 20.3 (CH3), 19.3 (CH3); MS (FAB) m/z 91.0 (30),
149.1 (92), 273.1 (76), 333.1 (100), 685.1 (MH+, 81); HRMS
(FAB) calcd for C34H37O15 (M + H) 685.2133, found 685.2132.
Com p ou n d 13. To a solution of 12 (260 mg, 0.38 mmol)
and triethylsilane (0.53 mL, 3.32 mmol) in dry CH2Cl2 (3 mL)
was added Et2O‚BF3 (0.107 mL, 0.844 mmol) dropwise. The
mixture was stirred under N2 at room temperature for 5 h. It
was then diluted with CH2Cl2 (20 mL) and washed with
saturated NaHCO3 solution. The organic layer was dried over
Na2SO4, filtered, and concentrated. The residua were purified
with preparative silica plates using acetone/CH2Cl2 (v/v 1/9)
as developing solvent to provide 13 (205 mg, 78.6%) as
yellowish gummy solid: 1H NMR (CDCl3) δ 7.39-7.27 (6H,
m), 6.94 (1H, s), 6.44 (1H, dd, J ) 5.5, 2.7 Hz), 5.64 (1H, q, J
) 6.6 Hz), 5.43 (1H, d, J ) 5.6 Hz), 5.07 (1H, s), 5.04 (1H, dd,
J ) 11.4, 7.8 Hz), 4.88 (1H, dd, J ) 10.3, 8.4 Hz), 4.78 (1H, d,
J ) 8.2 Hz), 4.58 (2H, dd, AB system, J ) 12.0 Hz), 3.84-3.72
(7H, m), 3.55 (1H, m), 3.11 (1H, dd, J ) 8.8, 2.2 Hz), 2.92 (1H,
d, J ) 2.6 Hz), 2.08 (3H, s), 2.06 (3H, s), 1.91 (3H, s), 1.48
(3H, d, J ) 6.5 Hz); 13C NMR (CDCl3) δ 171.1 (C), 169.84 (C),
169.81 (C), 169.2 (C), 166.3 (C), 149.6 (CH), 148.7 (CH), 139.2
(CH), 137.5 (C), 134.2 (C), 129.2 (CH), 128.6 (CH), 128.0 (CH),
127.8 (CH), 111.3 (C), 95.9 (C), 95.8 (CH), 92.1 (CH), 75.2 (CH),
74.9 (CH), 73.8 (CH2), 70.8 (CH), 70.0 (CH), 69.5 (CH2), 65.0
(CH), 51.6 (CH3), 48.9 (CH), 38.0 (CH), 21.0 (CH3), 20.8 (CH3),
20.3 (CH3), 19.3 (CH3); MS (FAB) m/z 91.0 (100), 337.1 (45),
381.1 (6), 687.1 (MH+, 11); HRMS (FAB) calcd for C34H39O15
(M + H) 687.2289, found 687.2290.
(30), 342.2 (45), 750.3 (MH+, 39); HRMS (FAB) calcd for C36H48
-
NO16 (M + H) 750.2973, found 750.2967.
Com p ou n d 10. To a solution of 7 (86 mg, 0.13 mmol) and
dodecylamine (128 mg, 0.69 mmol) in dry CH2Cl2 (4 mL) were
added Et3N (15 drops) and BOP reagent (68 mg, 0.15 mmol).
The mixture was stirred under N2 at room temperature for 2
h. It was then diluted with CH2Cl2 (30 mL), washed with
water, dried over Na2SO4, filtered, and concentrated. The
residue was purified with preparative silica TLC using CH2-
Cl2/acetone (v/v 9/1) as developing solvent to provide 10 (40
mg, 37%) as yellowish gummy solid: 1H NMR (CDCl3) δ 7.11
(1H, s, 3-H), 7.00 (1H, s, 10-H), 6.29 (1H, dd, J ) 5.3, 2.6 Hz,
6-H), 5.65 (1H, q, J ) 6.8 Hz, 14-H), 5.61 (1H, t, J ) 5.5 Hz,
17-H), 5.49 (1H, d, J ) 5.9 Hz, 7-H), 5.22 (1H, dd, J ) 9.8, 9.8
Hz, 3′-H), 5.09 (1H, dd, J ) 9.8, 9.8 Hz, 4′-H), 5.04 (1H, d, J )
3.3 Hz, 1-H), 4.95 (1H, dd, J ) 10.2, 8.2 Hz, 2′-H), 4.83 (1H, d,
J ) 8.2 Hz, 1′-H), 4.32 (1H, dd, J ) 12.5, 4.6 Hz, one proton of
6′-H), 4.11 (1H, dd, J ) 12.5, 2.1 Hz, one proton of 6′-H), 3.79
(1H, br d, J ) 8.3 Hz, 5-H), 3.73 (1H, m, 5′-H), 3.38 and 3.26
(2H, m, ABX, H-18), 3.15 (1H, dd, J ) 8.2, 2.1 Hz, 9-H), 2.11
(3H, s, -OAc), 2.08 (3H, s, -OAc), 2.03 (3H, s, -OAc), 2.00 (3H,
s, -OAc), 1.94 (3H, s, -OAc), 1.54 (2H, m, 19-H), 1.51 (3H, d, J
) 6.6 Hz, 15-H), 1.39-1.22 (18H, m, 20-H, 21-H, 28-H), 0.88
(3H, t, J ) 7.0 Hz, 29-H); 13C NMR (CDCl3) δ 170.7 (C), 170.2
(C), 169.9 (C), 169.8 (C), 169.5 (C), 169.4 (C), 165.5 (C), 148.6
(CH), 144.4 (CH), 137.5 (CH), 134.5 (C), 130.5 (CH), 114.6 (C),
96.0 (CH), 95.7 (C), 92.0 (CH), 72.5 (CH), 72.4 (CH), 71.0 (CH),
68.3 (CH), 65.2 (CH), 61.8 (CH2), 49.1 (CH), 40.0 (CH2), 38.2
(CH), 32.1 (CH2), 29.89 (CH2), 29.78 (CH2), 29.76 (CH2), 29.70
(CH2), 29.51 (CH2), 29.46 (CH2), 27.2 (CH2), 22.9 (CH2), 21.2
(CH3), 20.9 (CH3), 20.7 (CH3), 20.6 (CH3), 19.4 (CH3), 14.3
(CH3); MS (FAB) m/z 109.0 (75), 127.1 (31), 169.1 (100), 331.1
(26), 397.4 (43), 426.3 (36), 730.8 (37), 834.4 (MH+, 31); HRMS
(FAB) calcd for C42H60NO16 (M + H) 834.3912, found 834.3910.
Com p ou n d 15. A mixture of 13 (176 mg, 0.256 mmol),
galactose imidate 14 (203 mg, 0.424 mmol), and molecular
sieve powder (500 mg) in dry CH2Cl2 (7 mL) was stirred at
room temperature under N2 for 1 h. It was then cooled to -45
°C. Et2O‚BF3 (0.046 mL, 0.363 mmol) was added to the above
mixture dropwise. The resultant reaction mixture was stirred
at -45 °C for 4 h. Triethylamine (0.5 mL) was added to quench
the reaction. The mixture was filtered, and the filtrate was
washed with water, dried over Na2SO4, filtered, and concen-
trated. The residue was purified with preparative silica plates
Com p ou n d 11. To a solution of plumieride 3 (302 mg, 0.64
mmol) and p-toluenesulfonic acid monohydrate (62 mg, 0.32
mmol) in dry DMF (4 mL) was added benzaldehyde dimethyl
acetal (0.2 mL, 1.33 mmol) upon stirring. After the mixture
was stirred under N2 at room temperature for 24 h, the
reaction was quenched with triethylamine (0.2 mL). The
reaction mixture was then diluted with CH2Cl2 (30 mL),
J . Org. Chem, Vol. 69, No. 19, 2004 6171