J.-M. Vateꢀle / Tetrahedron 63 (2007) 10921–10929
10925
7.4 (t, 1H, J¼7.9 Hz, Ar), 7.58 (t, 1H, J¼7.8 Hz, Ar), 7.68
(d, 1H, J¼8 Hz, Ar), 8.09 (d, 1H, J¼7.8 Hz, Ar), 9.7 (br s,
1H, CO2H). 13C NMR: 18.1, 25.9, 67.4, 70.2, 120.8,
127.6, 127.7, 128.21, 131.7, 133.2, 137.7, 141.3, 172.2.
Anal. Calcd for C13H16O3: C, 70.89; H, 7.32; O, 21.79.
Found: C, 70.64; H, 7.17; O, 21.99.
and 9.7 Hz, H-2), 5.36 (br t, 1H, J¼6.8 Hz, CH]CMe2),
5.61 (s, 1H, CHPh), 6.06 (t, 1H, J¼9.65 Hz, H-3), 7.20–
7.68 (m, 12H, Ar), 7.8 (dd, 1H, J¼1 and 7.8 Hz, Ar), 8.07
(d, 1H, J¼7.8 Hz, Ar). 13C NMR: 18.1, 25.8, 55.6, 62.6,
67.3, 69.0, 69.5, 69.7, 72.6, 79.5, 97.3, 101.7, 121.2, 126.2
(3C), 126.7, 127.2, 127.8, 128.3 (2C), 128.5 (2C), 129.2,
130.1 (3C), 132.4, 133.5, 136.8, 137.0, 141.3, 166.0,
166.2. Anal. Calcd for C34H36O9: C, 69.37; H, 6.16; O,
24.46. Found: C, 69.05; H, 6.22; O, 24.63.
4.3. General procedure for the esterification of alcohols
4a–4h
To a cooled (0 ꢀC) solution of alcohol (1 mmol) and 2-(pre-
nyloxymethyl)benzoic acid 3 (0.264 g, 1.2 equiv) in CH2Cl2
(4 mL) were successively added DCC (0.268 g, 1.3 equiv)
and DMAP (0.018 g, 0.15 equiv). After stirring the mixture
overnight at room temperature, the precipitate of urea was
filtered and the filtrate was evaporated. The residue was pu-
rified by flash chromatography on silica gel.
4.3.4. Methyl 2,3,4-tri-O-acetyl-6-O-[2-(prenyloxyme-
thyl)benzoyl]-a-D-glucopyranoside 5d. Ether–petroleum
ether (3:1), 92% yield, [a]2D0 +104 (c 0.9, CHCl3). IR (neat):
1
1750, 1720, 1670, 1600, 1580 cmꢂ1. H NMR: 1.67 (s, 3H,
Me), 1.76 (s, 3H, Me), 2.0 (s, 3H, Me), 2.02 (s, 3H, Me),
2.07 (s, 3H, Me), 3.42 (s, 3H, OMe), 4.07 (d, 2H, J¼6.7 Hz,
CH2–CH]), 4.14 (m, 1H, H-5), 4.34 (dd, 1H, J¼4.5 and
12.1 Hz, H-6a), 4.42 (dd, 1H, J¼3.1 and 12.1 Hz, H-6b),
4.9 (s, 2H, CH2Ar), 4.91 (dd, 1H, J¼3.7 and 9.6 Hz, H-2),
4.96 (d, 1H, J¼3.7 Hz, H-1), 5.14 (t, 1H, J¼9.8 Hz, H-4),
5.42 (br t, 1H, J¼6.8 Hz, CH]CMe2), 5.51 (t, 1H, J¼
9.6 Hz, H-3), 7.33 (t, 1H, J¼7.8 Hz, Ar), 7.53 (td, 1H,
J¼1.3 and 7.7 Hz, Ar), 7.69 (d, 1H, J¼7.2 Hz, Ar), 7.97
(dd, 1H, J¼1.2 and 7.8 Hz, Ar). 13C NMR: 18.1, 20.7 (3C),
25.8, 55.5, 62.6, 67.2, 67.3, 69.0, 69.9, 70.2, 70.9, 96.8,
121.2, 126.9, 127.5, 127.6, 130.5, 132.6, 137.0, 141.7,
166.5, 169.6, 170.1, 170.2. Anal. Calcd for C26H34O11: C,
59.76; H, 6.56; O, 33.68. Found: C, 59.96; H, 6.55; O, 33.46.
4.3.1. (1R,2S,5R)-Menthyl 2-(prenyloxymethyl)benzoate
5a. Ether–petroleum ether (1:9), 94% yield, oil, [a]2D0 ꢂ61
(c 1.7, CHCl3). IR (film): 1710, 1600, 1570 cmꢂ1 1H
.
NMR: 0.81 (d, 3H, J¼6.9 Hz, Me), 0.92 (d, 3H, J¼7 Hz,
Me), 0.95 (d, 3H, J¼6.4 Hz, Me), 0.96–1.2 (m, 3H), 1.5–
1.62 (m, 4H), 1.69 (s, 3H, Me), 1.77 (s, 3H, Me), 1.9–2.1
(m, 2H), 4.1 (d, 2H, J¼6.84 Hz, CH2–CH]C), 4.91 (s,
2H, Ar), 4.93 (td, 1H, J¼4.2 and 10.4 Hz, CHOCO), 5.45
(br t, 1H, J¼6.9 Hz, CH]CMe2), 7.33 (t, 1H, J¼7.8 Hz,
Ar), 7.52 (br t, 1H, J¼7.8 Hz, Ar), 7.7 (d, 1H, J¼7.7 Hz,
Ar), 7.92 (br d, 1H, J¼7.8 Hz, Ar). 13C NMR: 16.3, 18.1,
20.9, 22.1, 20.9, 23.5, 25.9, 26.4, 31.6, 34.4, 41.1, 47.3,
67.4, 69.9, 74.8, 121.3, 126.8, 127.6, 130.2, 132.1, 136.8,
141.2, 166.8. Anal. Calcd for C23H34O3: C, 77.05; H, 9.56;
O, 13.39. Found: C, 77.02; H, 9.72; O, 13.26.
4.3.5. Methyl 2,3-di-O-benzyl-4,6-di-O-[2-(prenyloxyme-
thyl)benzoyl]-a-D-glucopyranoside 5e. Dichloromethane,
97% yield, glass, [a]D20 +14.6 (c 0.7, CHCl3). IR (neat):
1720, 1670, 1600, 1570 cmꢂ1 1H NMR: 1.66 (s, 6H,
.
2Me), 1.74 (s, 6H, 2Me), 3.47 (s, 3H, OMe), 3.7 (dd, 1H,
J¼3.5 and 9.6 Hz, H-2), 4.02–4.2 (m, 6H, 2CH2–CH]C,
H-3, H-5), 4.33 (dd, 1H, J¼5 and 12 Hz, H-6a), 4.47 (dd,
1H, J¼2.4 and 12 Hz, H-6b), 4.62–4.71 (m, 3H, CH2Ph,
H-1), 4.82–4.91 (m, 6H, 2CH2Ar, CH2Ph), 5.36 (t, 1H,
J¼9.8 Hz, H-4), 5.38–5.46 (m, 2H, 2CH]CMe2), 7.3–
7.76 (m, 16H, Ar), 7.88 (d, 1H, J¼7.8 Hz, Ar), 7.98 (d,
1H, J¼7.7 Hz, Ar). 13C NMR: 18.1 (2C), 25.8 (2C), 63.2,
67.3, 67.4, 67.7, 69.9 (2C), 70.5, 73.7, 75.6, 79.1, 79.8,
98.3, 121.2 (2C), 126.7, 126.8, 126.9, 127.4, 127.5, 127.6
(2C), 128.0 (2C), 128.2 (6C), 128.3 (2C), 128.6 (2C),
130.4, 130.6, 132.8, 137.0, 137.9, 138.0, 141.6, 142.3,
165.3, 166.5. Anal. Calcd for C47H54O10: C, 72.47; H,
6.99; O, 20.54. Found: C, 72.62; H, 7.0; O, 20.28.
4.3.2. 6-O-[2-(Prenyloxymethyl)benzoyl]-1,2,3,4-di-O-
isopropylidene-a-D-galactopyranose 5b. Ether–petroleum
ether (1:4), 92% yield, oil, [a]2D0 ꢂ45.5 (c 1.9, CHCl3). IR
1
(film): 1715, 1670, 1600, 1570 cmꢂ1. H NMR: 1.31 (s,
3H, Me), 1.33 (s, 3H, Me), 1.46 (s, 3H, Me), 1.66 (s, 3H, Me),
1.49 (s, 3H, Me), 1.74 (s, 3H, Me), 4.05 (d, 2H, J¼6.8 Hz,
CH2–CH]C), 4.16 (m, 1H, H-5), 4.3 (dd, 1H, J¼1.8 and
7.85 Hz, H-4), 4.33 (dd, 1H, J¼2.4 and 5 Hz, H-2), 4.38
(dd, 1H, J¼7.3 and 11.5 Hz, H-6a), 4.49 (dd, 1H, J¼5 and
11.5 Hz, H-6b), 4.63 (dd, 1H, J¼2.4 and 7.85 Hz, H-3),
4.9 (s, 2H, CH2Ar), 5.41 (br t, 1H, J¼6.8, CH]CMe2),
5.55 (d, 1H, J¼5 Hz, H-1), 7.29 (t, 1H, J¼7.7 Hz, Ar),
7.49 (td, 1H, J¼1.2 and 7.7 Hz, Ar), 7.66 (d, 1H,
J¼7.7 Hz, Ar), 7.93 (dd, 1H, J¼1.2 and 7.7 Hz, Ar). 13C
NMR: 18.1, 24.5, 25.0, 25.8, 26.0, 26.1, 64.0, 66.1, 67.3,
70.0, 70.5, 70.8, 71.2, 96.4, 108.8, 109.7, 121.3, 126.8,
127.5, 128.1, 130.6, 132.3, 136.8, 141.3, 167.0. Anal. Calcd
for C25H34O8: C, 64.92; H, 7.41; O, 27.27. Found: C, 65.17;
H, 7.39; O, 27.44.
4.3.6. Testosterone 2-(prenyloxymethyl)benzoate 5f.
Ether–petroleum ether (3:2), 90% yield, white solid, mp
77–79 ꢀC (hexane), [a]D20 +113.3 (c 1.8, CHCl3). IR (KBr):
1
1720, 1670, 1613, 1600, 1580 cmꢂ1. H NMR: 0.96–2.07
(m, 26H), 2.27–2.44 (m, 5H), 4.08 (d, 2H, J¼6.8 Hz,
CH2–CH]), 4.85 (t, 1H, J¼8.7 Hz, CHOPOMB), 4.9 (s,
2H, CH2Ph), 5.43 (br t, 1H, J¼6.7 Hz, CH]CMe2), 5.74
(s, 1H, COCH]C), 7.31 (t, 1H, J¼7.7 Hz, Ar), 7.52 (t,
1H, J¼7.6 Hz, Ar), 7.7 (d, 1H, J¼7.8 Hz, Ar), 7.93 (d, 1H,
J¼7.6 Hz). 13C NMR: 12.5, 17.5, 18.1, 20.6, 23.6, 25.9,
27.7, 31.5, 32.8, 34.0, 35.5, 35.7, 36.9, 38.7, 42.8, 50.3,
53.8, 67.3, 70.0, 83.2, 121.2, 124.0, 126.8, 127.6, 128.6,
130.4, 132.2, 137.0, 141.2, 167.1, 170.9, 199.5. Anal. Calcd
for C32H42O4: C, 78.33; H, 8.63; O, 13.04. Found: C, 78.07;
H, 8.58; O, 13.06.
4.3.3. Methyl 2-O-benzoyl-3-O-[2-(prenyloxymethyl)-
benzoyl]-4,6-O-benzylidene-a-D-glucopyranoside 5c.
Ether–petroleum ether (1:2), 93% yield, glass, [a]2D0 +72 (c
1
0.7, CHCl3). IR (neat): 1720, 1600, 1580 cmꢂ1. H NMR:
1.63 (s, 3H, Me), 1.75 (s, 3H, Me), 3.46 (s, 3H, OMe),
3.83–3.96 (m, 4H, 2H-6, CH2–CH]), 4.11 (td, 1H, J¼4.5
and 9.7 Hz, H-5), 4.4 (dd, 1H, J¼4.5 and 10.1 Hz, H-4),
4.76 (d, 1H, J¼14.9 Hz, CHaAr), 4.85 (d, 1H, J¼14.9 Hz,
CHbAr), 5.2 (d, 1H, J¼3.7 Hz, H-1), 5.27 (dd, 1H, J¼3.7