T. Sunazuka et al. / Tetrahedron 60 (2004) 7845–7859
7857
and the mixture was stirred for 15 min. The resultant
mixture was concentrated, and flash chromatography
(CH2Cl2/MeOH 20/1) furnished 1-keto-23b (21.7 mg,
48.2 mmol, 100% yield) as a yellow crystal: [a]2D2 þ162.98
(c 0.41, CHCl3); TLC Rf 0.32 (CH2Cl2/MeOH 20/1); mp
the reaction mixture was stirred for 2 days, quenched with
NaHSO3 (400 mg). The mixture was then extracted with
CHCl3 (3£30 mL) and the combined extracts were dried
over Na2SO4, filtered and concentrated. Flash chromato-
graphy (CHCl3) furnished 26b (70.6 mg, 134 mmol, 38%
yield) and 27b (55.3 mg, 118 mmol, 33% yield) as colorless
crystals. 26b: [a]2D3 þ112.98 (c 0.56, CHCl3); TLC Rf 0.47
(benzene/acetone 2/1); mp 206–207 8C; IR (KBr) 3440,
1
220 8C; IR (KBr) 3440, 1713, 1551, 1516, 1259 cm21; H
NMR (400 MHz, CDCl3) d 1.08 (3H, s), 1.19 (3H, s), 1.53
(3H, s), 1.64 (3H, s), 1.69 (1H, ddd, J¼14.0, 7.0, 5.5 Hz),
1.83 (1H, ddd, J¼14.5, 5.0, 2.5 Hz), 1.94 (1H, dd, J¼14.0,
4.0 Hz), 2.02 (1H, m), 2.06 (1H, ddd, J¼14.0, 10.0, 5.0 Hz),
2.31 (1H, dt, J¼14.0, 5.0 Hz), 2.61 (1H, ddd, J¼14.5, 7.0,
5.0 Hz), 2.81 (1H, ddd, J¼14.5, 10.0, 5.5 Hz), 3.86 (3H, s),
6.34 (1H, s), 6.94 (2H, d, J¼9.0 Hz), 7.76 (2H, d,
J¼9.0 Hz), 7.45 (1H, s); 13C NMR (100.6 MHz, CDCl3) d
24.4, 25.7, 26.7, 27.3, 28.0, 33.7, 36.4, 37.1, 37.7, 55.5,
57.1, 79.1, 79.5, 95.7, 100.7, 114.3 (2C), 119.4, 123.9, 127.3
(2C), 133.7, 160.4, 161.7, 161.8, 162.6, 211.0; HRMS Calcd
for C27H31O6 [MþH]þ 451.2121, found 451.2078.
1728, 1674, 1633, 1574, 1514, 1257 cm21 1H NMR
;
(270 MHz, CDCl3) d 0.96 (3H, s), 1.05 (3H, s), 1.09 (1H,
m), 1.25 (3H, s), 1.45 (3H, s), 1.61–1.97 (4H, m), 2.05–
2.17 (2H, m), 2.05 (3H, s), 2.56 (1H, dt, J¼13.0, 4.6 Hz),
3.86 (3H, s), 4.64 (1H, brs), 5.00 (1H, s), 5.39 (1H, dd,
J¼9.9, 5.6 Hz), 6.35 (1H, s), 6.96 (2H, d, J¼8.9 Hz), 7.73
(2H, d, J¼8.9 Hz); 13C NMR (67.5 MHz, CDCl3) d 18.6,
21.9, 22.6, 24.3, 24.9, 25.6, 27.1, 29.9, 33.7, 38.8, 48.0,
55.4, 61.7, 71.8, 78.2, 79.8, 83.5, 96.5, 99.9, 114.4 (2C),
123.0, 127.4 (2C), 160.4, 162.1, 164.3, 165.2, 170.7; HRMS
Calcd for C29H36O9Na [MþNa]þ 551.2257, found
551.2276, and 27b: [a]2D3 236.98 (c 0.51, CHCl3); TLC Rf
0.37 (benzene/acetone 2/1); mp 113–114 8C; IR (KBr)
3460, 1695, 1633, 1574, 1514, 1261, 1178 cm21; 1H NMR
(270 MHz, CDCl3) d 0.88 (3H, s), 0.95 (3H, s), 1.23 (1H,
m), 1.27 (3H, s), 1.65 (3H, s), 1.65–1.90 (5H, m), 1.97–
2.07 (2H, m), 3.85 (3H, s), 4.60 (1H, dd, J¼11.0, 5.0 Hz),
4.90 (1H, s), 6.30 (1H, s), 6.93 (2H, d, J¼8.6 Hz), 7.74 (2H,
d, J¼8.6 Hz); 13C NMR (67.5 MHz, CDCl3) d 14.5, 23.6,
24.1, 25.8, 26.0, 26.3, 30.5, 35.5, 36.2, 49.9, 55.4, 70.9,
73.2, 79.7, 84.0, 88.4, 96.0, 98.1, 114.2 (2C), 123.6, 127.3
(2C), 160.5, 161.8, 164.0, 164.4; HRMS Calcd for
C27H32O7Na [MþNa]þ 491.2046, found 491.2060.
4.1.27. (1R,4aR,6aR,12bS)-1,3,4,4a,5,6,6a,12b-Octa-
hydro-1,4a-dihydroxy-4,4,6a,12b-tetramethyl-9-(40-
methoxyphenyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]
pyran-11-one (25b). A solution of NaBH(OAc)3 was
prepared by adding NaBH4 (15.9 mg, 420 mmol) to glacial
acetic acid (420 mL) while keeping the temperature below
20 8C (ice bath). After the H2 evolution ceased, a solution of
1-keto-23b (18.9 mg, 42.0 mmol) in THF (840 mL) was
added in one portion and the reaction mixture was stirred for
1.5 h at room temperature, and then quenched with 0.2 N
HCl (5 mL). The resultant mixture was extracted with
CHCl3 (3£10 mL) and the combined extracts were dried
over Na2SO4, filtered and concentrated. Flash chromato-
graphy (hexane/EtOAc 1/2) furnished 25b (18.6 mg,
41.2 mmol, 98% yield) as a yellow crystal: [a]2D3 þ2.48 (c
0.34, CHCl3); TLC Rf 0.24 (CHCl3/MeOH 20/1); mp 90–
4.1.29. (1R,4aR,6aR,12aR,12bS)-1,3,4,4a,5,6,6a,12,12a,
12b-Decahydro-1,4a,12a-trihydroxy-4,4,6a,12b-tetra-
methyl-9-(40-methoxyphenyl)-2H,11H-naphtho[2,1-b]
pyrano[3,4-e]pyran-11-one (29b). At room temperature a
solution of 26b (6.3 mg, 11.9 mmol) in ClCH2CH2Cl
(600 mL) was treated with Et3SiH (22.9 mL, 143 mmol)
and TFA (9.2 mL, 119 mmol) and the reaction mixture was
stirred for 3 h at 50 8C, quenched with saturated aqueous
NaHCO3 (3 mL). The resultant mixture was extracted with
CHCl3 (3£5 mL), and the combined extracts were dried
over Na2SO4, filtered and concentrated. The crude mixture
of 12-deoxydiol and 29b was used for the next step without
purification.
1
95 8C; IR (KBr) 3430, 1691, 1558, 1512, 1255 cm21; H
NMR (400 MHz, CDCl3) d 0.95 (3H, s), 1.00 (3H, s), 1.17
(1H, dt, J¼13.0, 3.5 Hz), 1.33 (3H, s), 1.56 (3H, s), 1.69
(1H, s), 1.73 (1H, ddt, J¼13.0, 6.5, 3.5 Hz), 1.74 (1H, ddd,
J¼13.0, 6.0, 2.0 Hz), 1.80 (1H, dddd, J¼13.0, 10.0, 3.5,
2.0 Hz), 1.94 (1H, ddd, J¼13.0, 3.5, 2.0 Hz), 1.95 (1H, ddd,
J¼14.0, 13.0, 5.0 Hz), 2.07 (1H, ddd, J¼14.0, 5.0, 2.0 Hz),
2.33 (1H, dt, J¼14.0, 6.0 Hz), 3.85 (3H, s), 4.36 (1H, dd,
J¼10.0, 6.5 Hz), 6.30 (1H, s), 6.92 (2H, d, J¼9.0 Hz), 6.99
(1H, s), 7.73 (2H, d, J¼9.0 Hz); 13C NMR (100.6 MHz,
CDCl3) d 21.2, 23.6, 24.6, 27.1, 28.2, 28.9, 34.6, 35.6, 37.9,
49.9, 55.4, 71.6, 77.3, 81.1, 95.8, 99.6, 114.2, 114.7 (2C),
123.9, 127.2 (2C), 140.4, 160.0, 161.7, 161.9, 162.6; HRMS
Calcd for C27H33O6 [MþH]þ 453.2277, found 453.2280.
To a solution of the crude mixture in MeOH (600 mL) at
room temperature was added K2CO3 (3.3 mg, 24.0 mmol).
The solution was stirred for 6 h at room temperature,
quenched with saturated aqueous NH4Cl (3 mL). The
resultant mixture was extracted with CHCl3 (3£5 mL) and
the combined extracts were dried over Na2SO4, filtered and
concentrated. Preparative TLC (CHCl3/MeOH 20/1) furn-
ished 29b (4.6 mg, 9.79 mmol, 82% yield) as a colorless
crystal; [a]2D4 þ65.58 (c 0.11, CHCl3/MeOH 10/1); TLC Rf
0.31 (CHCl3/MeOH 10/1); mp 257–258 8C; IR (KBr) 3392,
1699, 1643, 1583, 1514, 1255, 1215, 1176 cm21; 1H NMR
(400 MHz, pyridine-d5) d 1.13 (3H, s), 1.14 (3H, s), 1.21
(1H, ddd, J¼13.5, 4.0, 2.5 Hz), 1.42 (3H, s), 1.53 (3H, s),
1.87 (2H, m), 2.00 (1H, m), 2.06 (1H, m), 2.15 (1H, m), 2.41
(1H, dt, J¼13.5, 5.0 Hz), 2.93 (1H, m), 3.39 (1H, d,
J¼18.0 Hz), 3.66 (3H, s), 4.22 (1H, d, J¼18.0 Hz), 5.27
(1H, dd, J¼11.0, 5.0 Hz), 6.65 (1H, s), 6.99 (2H, d,
4.1.28. (1R,4aR,6aR,12R,12aR,12bS)-1-Acetoxy-
1,3,4,4a,5,6,6a,12,12a,12b-decahydro-4a,12,12a-tri-
hydroxy-4,4,6a,12b-tetramethyl-9-(40-methoxyphenyl)-
2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-11-one (26b)
and (1R,4aR,6aR,12S,12aS,12bS)-12,12a-epoxy-
1,3,4,4a,5,6,6a,12,12a,12b-decahydro-1,4a-dihydroxy-
4,4,6a,12b-tetramethyl-9-(40-methoxyphenyl)-2H,11H-
naphtho[2,1-b]pyrano[3,4-e]pyran-11-one (27b). A solution
of 25b (160 mg, 354 mmol) in CH2Cl2:KH2PO4–Na2HPO4
buffer (prepared by dissolving 340 mg of KH2PO4 and
355 mg of Na2HPO4 in 100 mL of total aqueous
solution)¼5:1 (17.7 mL) at room temperature was treated
with 32% peracetic acid in AcOH (750 mL, 3.54 mmol), and