G. B. Evans et al. / Bioorg. Med. Chem. 7 (1999) 1953±1964
1961
1.02 (3H, s, H-18), 1.00 (3H, s, H-19); 13C NMR
(CDCl3) d 156.4, 143.1, 133.7, 133.4, 122.8, 109.6 (Ar),
55.1 (OCH3), 49.7 (C-5), 41.7 (C-3), 39.7 (C-1), 37.8 (C-
10), 33.3 (C-4), 33.3 (C-18), 28.6 (C-7), 27.4 (C-15), 25.3
(C-20), 21.7 (C-19), 20 .5, 20.5 (C-16, C-17), 19.6 (C-6),
19.5 (C-2).
acetyl-a-d-galactopyranosyloxy)-totara-8,11,13-triene
(15) as a chromatographically pure oil (65 mg, 15%); 1H
NMR (CDCl3) d 7.08, 6.98 (2H, 2d, J=9.0 Hz, H-11,
H-12), 5.79 (1H, d, J=3.2 Hz, H-10), 5.69 (1H, 2d,
J=10.9, 3.2 Hz, H-20), 5.55 (1H, d, J=2.9 Hz, H-40),
5.35 (1H, dd, J=10.9, 3.6 Hz, H-30), 4.27 (1H, t,
J=6.6 Hz, H-50), 4.12 (2H, m, H-60), 3.35 (1H, br s, H-
15), 2.99 (1H, dd, J=17.1, 6.3 Hz, H-7b), 2.75 (1H, m,
H-7a), 2.18, 2.04, 2.01, 1.94 (4Â3H, 4s, COCH3), 1.39,
1.36 (2Â3H, d, J=7.0 Hz, H-16, H-17), 1.16 (3H, s, H-
20), 0.95 (3H, s, H-18), 0.93 (3H, s, H-19); 13C NMR
(CDCl3) d 170.2, 170.1, 170.0, 169.9 (COCH3), 152.7,
144.9, 134.0, 133.5, 123.0, 111.6 (Ar), 93.9 (C-10), 67.9
(C-30), 67.8 (C-20), 67.8 (C-40), 66.9 (C-50), 61.1 (C-60),
49.3 (C-5), 41.5 (C-3), 39.5 (C-1), 37.7 (C-10), 33.2 (C-
4), 33.1 (C-18), 28.7 (C-7), 27.3 (C-15), 25.0 (C-20), 21.5
(C-19), 20.9, 20.6, 20.5, 20.5 (COCH3), 20.6, 20.6 (C-16,
C-17), 19.3 (C-6), 19.2 (C-2); m/z 616 (M+, 3%), 331
(100), 169 (94), 127 (13), 109 (39), 43 (97); HRMS, calcd
for C34H48O10 (M+) 616.3247, found 616.3255. This
was followed by 13-(2,3,4,6-tetra-O-acetyl-b-d-galacto-
pyranosyloxy)-totara-8,11,13-triene (16) as a chromato-
graphically pure oil (180 mg, 42%); 1H NMR (CDCl3) d
7.08, 6.82 (2H, 2d, J=8.9 Hz, H-11, H-12), 5.54 (1H,
dd, J=10.3, 8.0 Hz, H-20), 5.45 (1H, d, J=3.3 Hz, H-40),
5.14 (1H, d, J=8.0 Hz, H-10), 5.11 (1H, dd, J=10.3,
3.3 Hz, H-30), 4.14 (3H, m, H-50, 2H-60), 3.29 (1H, br s,
H-15), 2.93 (1H, dd, J=17.1, 6.1 Hz, H-7b), 2.78 (1H,
ddd, J=17.1, 10.8, 7.8 Hz, H-7a), 2.20, 2.07, 2.02, 2.01
(4Â3H, s, COCH3), 1.32, 1.21 (2Â3H, d, J=7.1 Hz, H-
16, H-17), 1.19 (3H, s, H-20), 0.96 (3H, s, H-18), 0.92
(3H, s, H-19); 13C NMR (CDCl3) d 170.4, 170.4, 170.2,
169.3 (COCH3), 153.2, 145.2, 134.4, 134.0, 122.9, 112.0
(Ar), 98.2 (C-10), 71.5 (C-30), 70.9 (C-50), 68.8 (C-20),
67.2 (C-40), 61.5 (C-60), 49.6 (C-5), 41.6 (C-3), 39.6 (C-
1), 37.9 (C-10), 33.4 (C-4), 33.3 (C-18), 29.0 (C-7), 27.3
(C-15), 25.3 (C-20), 21.7 (C-19), 21.0, 20.8, 20.7, 20.6
(COCH3), 20.6, 20.5 (C-16, C-17), 19.5 (C-6), 19.4 (C-
2); m/z 616 (M+, 3%), 331 (83), 169 (78), 127 (13), 109
(34), 43 (100); HRMS, calcd for C34H48O10 (M+)
616.3247, found 616.3257.
13-Acetoxytotara-8,11,13-triene (12).17,36 Acetic anhy-
dride (20 mL) was added to a stirred solution of totarol
(1, 8.6 g, 30 mmol) in pyridine (20 mL) at 0ꢀC. The
resulting solution was allowed to warm to room tem-
perature, stirred for 14 h, diluted with water (400 mL)
and ®ltered to yield a solid. Chromatography on silica
gel using petrol/ethyl acetate (50/1) as the eluant gave 12
(7.8 g, 79%), mp 120ꢀC, lit.36 121±121.5ꢀC; 13C NMR
spectral chemical shifts identical to published data
(d0.1 ppm).17
13-(2,3,4,6-Tetra-O-acetyl-ꢁ-D-glucopyranosyloxy)-totara-
8,11,13-triene (14). A solution of tetra-O-acetyl-a-d-
glucopyranosyl bromide37 (431 mg, 1.1 mmol) in toluene
(5 mL) was added dropwise to a stirred suspension of 1
(200 mg, 0.7 mmol), activated sieves (3 A, 1.0 g), and
sodium hydrogen phosphate (1.0 g) in toluene under
argon in a ¯ask masked from the light. After 30 min
silver tri¯ate (270 mg, 1.1 mmol) in toluene (5 mL) was
added via a cannula, the mixture was stirred for 2 h, ®l-
tered through Celite and concentrated in vacuo. Chro-
matography on silica gel using petrol/ethyl acetate (3/1)
as the eluant gave 14 (270 mg, 63%), mp 175ꢀC; IR umax
1746 (CO), 1640 (CC) cm 1; 1H NMR (CDCl3) d 7.07,
6.79 (2H, 2d, J=8.9 Hz, H-11, H-12), 5.33 (1H, t,
J=9.1 Hz, H-20), 5.30 (1H, t, J=9.1 Hz, H-30), 5.18 (1H,
t, J=9.1 Hz, H-40), 5.18 (1H, d, J=9.1 Hz, H-10), 4.25
1H dd, J=12.2, 5.6 Hz, H-60a), 4.16 (1H, dd, J=12.2,
2.6 Hz, H-60b) 3.86 (1H, m, H-50), 3.27 (1H, br s, H-15),
2.92, (1H, dd, J=17.0, 6.1 Hz, H-7b), 2.76 (1H, ddd,
J=17.0, 10.9, 7.8 Hz, H-7a), 2.06, 2.04, 2.02, 2.00
(4Â3H, 4s, COCH3), 1.28, 1.19 (2Â3H, d, J=7.0 Hz, H-
16, H-17), 1.18 (3H, s, H-20), 0.94 (3H, s, H-18), 0.91
(3H, s, H-19); 13C NMR (CDCl3) d 170.6, 170.3, 169.4,
169.3 (COCH3), 153.0, 145.2, 134.4, 134.0, 122.9, 111.8
(Ar), 97.5 (C-10), 73.4 (C-20), 71.8 (C-30), 71.4 (C-40),
68.6 (C-50), 62.2 (C-60), 49.5 (C-5), 41.5 (C-3), 39.6 (C-
1), 37.9 (C-10), 33.3 (C-4), 33.2 (C-18), 28.9 (C-7), 27.2
(C-15), 25.2 (C-20), 21.6 (C-19), 20.8, 20.7 (COCH3),
20.6, 20.6 (C-16, C-17), 20.4, 20.4 (COCH3), 19.5 (C-6),
19.4 (C-2); m/z 616 (M+, 1%), 331 (42), 271 (13), 169
(100), 109 (38), 69 (6), 43 (38); HRMS, calcd for
C34H48O10 (M+) 616.3247, found 616.3257.
13-(2,3,4,6-Tetra-O-acetyl-ꢀ-D-mannopyranosyloxy)-
totara-8,11,13-triene (17). A solution of glycosyl donor
tetra-O-acetyl-a-d-mannopyranosyl bromide37 (470 mg,
1.2 mmol) in toluene (5 mL) was added dropwise to a
stirred suspension of 1 (200 mg, 0.7 mmol), activated
sieves (3 A, 1 g), and sodium hydrogen phosphate (1 g)
in toluene under argon in a ¯ask masked from the light.
After 30 min silver tri¯ate (270 mg, 1.1 mmol) in toluene
(5 mL) was added via cannula, the mixture was stirred
for 2 h, ®ltered through Celite and concentrated in
vacuo. Chromatography on silica gel using petrol/ethyl
acetate (5.6/1) as the eluant gave 17 (320 mg, 74%), mp
205ꢀC; 1H NMR (CDCl3) d 7.08 (2H, 2d, J=8.9 Hz, H-
11, H-12), 5.48 (2H, m, H-10, H-20), 5.59 (1H, dd,
J=10.0, 2.6 Hz, H-30), 5.42 (1H, t, J=10.0 Hz, H-40),
4.33 (1H, dd, J=12.8, 5.7 Hz, H-60a), 4.11 (2H, m, H-50,
H-60b), 3.34 (1H, sept J=7.0 Hz, H-15), 2.96 (1H, dd,
J=17.1, 6.2 Hz, H-7b), 2.77 (1H, ddd, J=17.1, 11.1,
7.9 Hz, H-7a) 2.19, 2.08, 2.07, 2.04 (4Â3H, 4s, COCH3),
1.42, 1.35 (2Â3H, d, J=7.0 Hz, H-16, H-17), 1.20 (3H,
s, H-20), 0.96 (3H, 4s, H-18), 0.89 (3H, s, H-19); 13C
13-(2,3,4,6-Tetra-O-acetyl-ꢀ- and ꢁ-D-galactopyranosyl-
oxy)-totara-8,11,13-triene (15 and 16). A solution of
tetra-O-acetyl-a-d-galactopyranosyl bromide37 (431 mg,
1.1 mmol) in toluene (5 mL) was added dropwise to a
stirred suspension of 1 (200 mg, 0.7 mmol), activated
sieves (3 A, 1 g), and sodium hydrogen phosphate (1 g)
in toluene under argon in a ¯ask masked from the light.
After 30 min silver tri¯ate (270 mg, 1.1 mmol) in toluene
(5 mL) was added via a cannula, the mixture was stirred
for 2 h, ®ltered through Celite and concentrated in
vacuo. Chromatography on silica gel using petrol/ethyl
acetate (5.6/1) as the eluant gave: 13-(2,3,4,6-tetra-O-