I. R. Nascimento et al. / Tetrahedron 56 (2000) 9181±9193
9191
(6H, 2s, 2Me-TBS), 0.99 (9H, s, 3Me-TBS), 1.00 (3H, d,
J6.6 Hz, H-10), 1.38 (3H, d, J6.9 Hz, Me-3), 3.27
(OMe-8), 3.48 (1H, m, H-3), 3.80 (3H, s, OMe-30), 3.90
(3H, s, OMe-7), 4.1±3.7 (2H, m, H-8, H-9), 5.12 (1H, d,
J9.6 Hz, H-2), 6.68, 6.71 (2H, 2 br s, H-4, H-6), 6.82 (1H,
d, J8.1 Hz, H-50), 6.87 (1H, dd, J8.1, 1.8 Hz, H-60), 6.97
(1H, d, J1.8 Hz, H-20). 13C NMR: d 25.4 (2Me-TBS),
17.4 (Me-3), 18.2 (C-10), 18.5 (C-TBS), 25.8 (3Me-TBS),
45.5 (C-3), 55.5, 56.0 (OMe-30, OMe-7), 56.7 (OMe-8),
71.5 (C-9), 2£89.5 (C-8), 93.9 (C-2), 109.5, 114.0 (C-4,
C-6), 110.4 (C-20), 119.3 (C-60), 120.6 (C-50), 131.1,
131.7, 133.2, (C-3a, C-5, C-10), 144.1, 145.0, 147.5 (C-7a,
C-30, C-7), 150.9 (C-40). EIMS 70 eV m/z (rel. int.): 488
H-60), 6.97 (1H, br s, H-20). 13C NMR: d 17.6 (Me-3),
19.0 (C-10), 45.6 (C-3), 2£56.0 (OMe-30, OMe-7), 72.3
(C-9), 2£79.7 (C-8), 93.8 (C-2), 108.9 (C-20), 2£110.1,
114.8 (C-4, C-6), 114.0 (C-50), 119.9 (C-60), 131.8 (C-10),
133.2, 134.5 (C-3a, C-5), 144.1, 145.7, 146.5, 147.1 (C-7a,
C-40, C-7, C-30). EIMS 70 eV m/z (rel. int.): 360 (M1, 10%),
342 (20), 315 (45), 163 (20), 137 (21), 87 (62), 85 (97), 83
KBr
max
(100). IR n
cm21: 3467, 2967, 2927, 1608, 1509, 1457,
1282, 1130, 754.
22. Amorphous solid. Anal. Calcd for C22H26O7: C, 65.66;
H, 6.51. Found: C, 65.13; H, 6.02. 1H NMR (CDCl3): d 1.11
(3H, d, J6.3 Hz, H-10), 1.37 (3H, d, J6.9 Hz, Me-3),
1.59 (1H, br s, OH-8), 2.13 (3H, s, OAc-9), 3.45 (1H, m,
H-3), 3.89, 3.90 (6H, s, OMe-30, OMe-7), 4.56 (1H, br d,
J7.5 Hz, H-8), 4.95 (1H, dq, J7.5, 6.3 Hz, H-9), 5.12
(1H, d, J9.6 Hz, H-2), 6.77, 6.81 (2H, 2 br s, H-4, H-6),
6.90 (2H, br s, H-50, H-60), 6.97 (1H, br s, H-20). 13C NMR:
d 17.0 (C-10), 17.8 (Me-3), 21.7 (OAc-9), 45.8 (C-3),
2£56.2 (OMe-30, OMe-7), 75.1, 75.2 (C-8, C-9), 94.1
(C-2), 109.0 (C-20), 110.4, 114.6 (C-4, C-6), 114.2 (C-50),
120.1 (C-60), 131.7, 133.4, 133.6 (C-3a, C-5, C-10), 144.3,
145.9, 146.6, 146.7 (C-7a, C-40, C-7, C-30), 171.0 (OAc-9).
(M1 ,1%), 443 (65), 399 (25), 329 (50), 186 (45), 85
KBr
max
(93), 83 (100). IR n
cm21: 3500, 2950, 2860, 1618,
1510, 1460, 1282, 1130.
20. Amorphous solid: Anal. Calcd for C29H42O7Si: C, 65.63;
H, 7.98. Found: C, 65.93; H, 8.32. H NMR (CDCl3): d
1
0.14, 0.15 (6H, 2s, 2Me-TBS), 0.99 (9H, s, 3Me-TBS),
1.09, 1.11 (3H, 2d, J6.6 Hz, H-10), 1.38 (3H, d,
J6.6 Hz, Me-3), 2.08 (3H, s, OAc-9) 3.27, 3.28 (OMe-
8), 3.49 (1H, m, H-3), 3.80 (3H, s, OMe-30), 2£3.90 (6H,
2s, OMe-7), 4.07 (1H, br d, J6.0 Hz, H-8), 5.10 (1H, m,
H-9), 5.11 (1H, d, J9.6 Hz, H-2), 2£6.69, 6.74, 6.75 (2H,
4br s, H-4, H-6), 6.82 (1H, d, J8.1 Hz, H-50), 6.87 (1H, br
d, J8.1 Hz, H-60), 6.97 (1H, br s, H-20). 13C NMR: d 25.4
(2Me-TBS), 16.9, 16.7 (C-10), 17.5 (Me-3), 18.5 (C-TBS),
21.4 (OAc-9), 25.8 (3Me-TBS), 45.5 (C-3), 55.5, 56.0
(OMe-30, OMe-7), 57.3 (OMe-8), 2£73.0 (C-9), 2£86.0
(C-8), 93.9 (C-2), 110.4 (C-20), 115.0, 115.2 (C-4, C-6),
119.3 (C-60), 120.6 (C-50), 131.6, 133.2, 133.4 (C-3a, C-5,
C-10), 144.0, 145.1, 147.5 (C-7a, C-30, C-7), 150.9 (C-40),
170.6 (OAc-9). EIMS 70 eV m/z (rel. int.): 530 (M1 ,1%),
EIMS 70 eV m/z (rel. int.): 402 (M1 ,1%), 315 (2), 87 (30),
KBr
max
85 (95), 83 (100). IR n
cm21: 3533, 2936, 2868, 1728,
1606, 1508, 1458, 1252, 1134, 755.
23. Amorphous solid: Anal. Calcd for C22H26O7: C, 65.66;
H, 6.51. Found: C, 65.87; H, 6.78. 1H NMR (CDCl3): d 1.11
(3H, d, J6.8 Hz, H-10), 1.37 (3H, d, J6.9 Hz, Me-3),
1.59 (1H, br s, OH-8), 2.14 (3H, s, OAc-8) 3.45 (1H, m,
H-3), 3.89, 3.90 (6H, s, OMe-30, OMe-7), 4.07 (1H, m, H-9),
5.48 (1H, 2d, J5.1, 7.2 Hz, H-8), 5.12 (1H, d, J9.6 Hz,
H-2), 6.77, 6.81 (2H, 2 br s, H-4, H-6), 6.90 (2H, br s, H-50,
H-60), 6.97 (1H, br s, H-20). 13C NMR: d 17.0 (C-10), 17.6
(Me-3), 21.6 (OAc-9), 45.9 (C-3), 2£56.2 (OMe-30, OMe-
7), 2£81.1 (C-8), 70.5 (C-9), 94.1 (C-2), 109.0 (C-20),
2£110.5, 115.0 (C-4, C-6), 114.2 (C-50), 120.1 (C-60),
131.4, 132.5, 133.6 (C-3a, C-5, C-10), 144.3, 145.9, 146.6,
146.7 (C-7a, C-40, C-7, C-30), 170.0 (OAc-9). EIMS 70 eV
443 (3), 429 (2), 399 (5), 385 (6), 219 (9), 87 (78), 85 (96),
KBr
max
83 (100). IR n
cm21: 2937, 2868, 1734, 1604, 1508,
1460, 1244, 1130, 846, 782.
Compounds 21±24
m/z (rel. int.): 402 (M1,1%), 315 (2), 87 (31), 85 (96), 83
Compounds 16 (0.17 mmol), 17 (0.025 mmol), 18
(0.025 mmol), and 19 (0.16 mmol) were individually
dissolved in dry THF (20 mL) at 08 to which was added a
KBr
max
(100). IR n
cm21: 3500, 2940, 2870, 1730, 1605, 1508,
1458, 1255, 1134, 755.
n
solution of 1.0 M Bu4NF in THF (2.2 mL). The resulting
24. Amorphous solid. EIMS, 1H and 13C NMR spectral data
for 24 were similar to those previously reported for
fragransol A.14 Anal. Calcd for C21H26O6: C, 67.36; H,
solutions were stirred for 60 min, and then partitioned
between saturated aqueous NH4Cl (25 mL) and CH2Cl2
(20 mL). The organic phases from each treatment were
combined with the aqueous phases then extracted with
CH2Cl2 (3£25 mL).15 The respective combined organic
extracts were washed with saturated aqueous NaCl
(30 mL), dried (Na2SO4) and concentrated. Individual puri-
®cation of the products by TLC (hexanes:EtOAc, 1:1) gave
21 (35.7 mg, 58.3%), 22 (8.1 mg, 80.0%), 23 (8.3 mg,
81.1%) and 24 (7.5 mg, 12.5%).
1
7.00. Found: C, 67.34; H, 6.52. H NMR (CDCl3): d 1.00
(3H, d, J7.2 Hz, H-10), 1.39 (3H, d, J6.9 Hz, Me-3),
3.27 (3H, s, OMe-8), 3.48 (1H, m, H-3), 2£3.90 (6H, s,
OMe-7, OMe-30), 4.1±3.7 (2H, m, H-8, H-9), 5.13 (1H, d,
J9.9 Hz, H-2), 5.68 (1H, s, OH), 6.68, 6.71 (2H, 2 br s,
H-4, H-6), 6.91 (2H, br s, H-50, H-60), 7.00 (1H, br s, H-20).
13C NMR: d 17.4 (Me-3), 18.2 (C-10), 45.6 (C-3), 2£56.0
(OMe-30, OMe-7), 56.7 (OMe-8), 71.6 (C-9), 2£89.5
(C-8), 93.9 (C-2), 108.9 (C-20), 110.4, 115.0 (C-4, C-
6), 114.0 (C-50), 119.9 (C-60), 131.7, 131.8, 133.1, (C-
3a, C-5, C-10), 144.1, 2£145.7, 146.5, (C-7a, C-30, C-40,
C-7). EIMS 70 eV m/z (rel. int.): 374 (M1, 4%), 343
21. Amorphous solid. Anal. Calcd for C20H24O6: C, 66.65;
H, 6.71. Found: C, 66.63; H, 6.60. 1H NMR (CDCl3): d 1.10
(3H, d, J6.3 Hz, H-10), 1.38 (3H, d, J6.9 Hz, Me-3),
3.49 (1H, m, H-3), 3.89 (3H, s, OMe-30), 3.90 (3H, s,
OMe-7), 4.0±3.8 (1H, m, H-9), 4.34 (1H, d, J7.2 Hz,
H-8), 5.12 (1H, d, J9.6 Hz, H-2), 5.67 (1H, s, OH-40),
6.75, 6.80 (2H, 2 br s, H-4, H-6), 6.90 (2H, br s, H-50,
(5), 329 (36), 186 (45), 87 (50), 85 (100), 83 (95). IR
cm21: 3460, 2968, 2934, 1605, 1519, 1460, 1277,
KBr
max
n
1133, 756.