(iii)
(2ЈS,3ЈR,5ЈR)-2,2Љ-[5-(tert-Butyldimethylsilyloxy)-3-
amine (0.1 ml, 0.71 mmol) and the mixture was stirred at
hydroxy-2-(phenylmethoxy)hexane-1,1-diyl]bis-(4,8-dimethoxy-
1-naphthol) 28 (42 mg, 6%) as a pale brown solid (Found: C,
69.3; H, 7.4. C43HϪ54O9Si requires C, 69.5; H, 7.3%); [α]D
Ϫ14.29 (c 0.364, CHCl3); νmax (film)/cmϪ1 3395br s (OH), 2952,
room temperature for 6 h. The solvent was removed at
reduced pressure and the residue purified by flash chromato-
graphy, using hexane–ethyl acetate (9:1) then (4:1) as eluent to
afford:
2930, 2855s (C–H), 1608s (C᎐C), 1070br s (C–O); δ (400 MHz;
(i)
(2ЈR,3ЈR,5ЈR)-2-[3-Acetoxy-5-(tert-butyldimethylsilyl-
᎐
H
CDCl3) Ϫ0.18, Ϫ0.09 (6H, s, SiMe2), 0.71 (9H, s, But), 1.02
(3H, d, J6Ј,5Ј 6.0, H3-6Ј), 1.67–1.73 (1H, m, H-4ЈA), 2.11–2.21
(1H, m, H-4ЈB), 3.62, 3.74, 3.83, 3.90 (12H, s, 4 × OMe), 3.84–
3.87 (1H, m, H-3Ј), 3.88 (1H, br s, OH), 3.91–3.94 (1H, m, H5Ј),
4.29 (1H, d, Jgem 11.6, OCHAPh), 4.39–4.42 (1H, m, H-2Ј), 4.69
(1H, d, Jgem 11.6, OCHBPh), 5.42 (1H, d, J1Ј,2Ј 7.6, H-1Ј), 6.66,
6.68 (2H, d, J6,7 8.0 and J6Љ,7Љ 8.0, H-7, H-7Љ), 6.95 (1H, s, H-3 or
H-3Љ), 6.96–7.17 (5H, m, Ph), 7.13–7.16 (2H, m, H-6 or H-6Љ),
7.40 (1H, s, H-3Љ or -3), 7.65, 7.70 (2H, d, J5,6 8.6 and J5Љ,6Љ 8.6,
H-5, H-5Љ) and 9.35, 9.43 (2H, s, 2 × OH); δC (100 MHz;
CDCl3) Ϫ5.0, Ϫ4.3 (CH3, SiMe2), 17.9 (quat, CMe3), 24.2
(CH3, C-6), 25.8 (CH3, CMe3), 38.4 (CH, C-1Ј), 41.3 (CH2,
C-4Ј), 55.7, 55.8, 55.9, 56.0 (CH3, 4 × OMe), 65.8 (CH, C-5Ј),
73.2 (CH, C-3Ј), 74.4 (CH2, OCH2Ph), 85.3 (CH, C-2Ј), 104.8,
104.9 (CH, C-7, -7Љ), 108.2, 108.9 (CH, C-3, -3Љ), 115.5, 115.6
(quat, C-2, -2Љ), 115.7, 115.8 (CH, C-5, -5Љ), 122.0, 122.4 (quat,
C-8a, -8aЉ), 124.4, 124.5 (CH, C-6, -6Љ), 126.7, 126.8 (quat,
C-4a, -4aЉ), 126.9, 127.3, 127.8 [CH, Ph (last 2 peaks coinci-
dental)], 139.3 (quat, OCH2Ph), 144.6, 145.5 (quat, C-4, -4Љ),
147.3, 147.6 (quat, C-1, -1Љ) and 155.8 (quat, C-8, -8Љ); m/z (EI)
742 (Mϩ, 17%), 710 (M Ϫ CH3OH, 2), 634 (M Ϫ HOC7H7, 2),
538 (M Ϫ C12H12O3, 2), 419 (C25H23O6, 100), 387 (C24H19O5,
10), 159 (C8H19OSi, 6), 145 (CH2OSiMe2But, 5) and 91 (CH2Ph,
29).
oxy)-2-(phenylmethoxy)hexanoyl]-4,8-dimethoxy-1-naphthol
31 (37 mg, 41%) as a fluorescent yellow oil (Found: C, 66.5; H,
7.5. C33H44O8Si requires C, 66.4; H, 7.4%); [α]D Ϫ14.10 (c 0.156,
CHCl3); νmax (film)/cmϪ1 3327br w (OH), 2955, 2855m (C–H),
1732s (C᎐O, acetate), 1626s (C᎐O), 1244br s (C–O, acetate) and
᎐
᎐
1074s (C–O); δH (200 MHz; CDCl3) Ϫ0.20, Ϫ0.09 (6H, s,
SiMe2), 0.68 (9H, s, But), 1.01 (3H, d, J6Ј,5Ј 12.5, H3-6Ј), 1.79
(1H, ddd, Jgem 14.7, J4ЈA,5Ј 6.2 and J4ЈA,3Ј 2.8, H-4ЈA), 2.00 (3H, s,
OCOCH3), 2.03 (1H, ddd, Jgem 14.7, J4ЈB,3Ј 9.2 and J4ЈB,5Ј 2.8,
H-4ЈB), 3.78–3.81 (1H, m, H-5Ј), 3.98, 4.05 (6H, s, 2 × OMe),
4.38 (1H, d, Jgem 12.3, H-1ЉA), 4.84 (1H, d, Jgem 12.3, H-1ЉB),
5.21 (1H, d, J2Ј,3Ј 2.8, H-2Ј), 5.40 (1H, ddd, J3Ј,4ЈB 9.2, J3Ј,2Ј 2.8
and J3Ј,4ЈA 2.8, H-3Ј), 6.97 (1H, dd, J6,7 8.1 and J7,5 0.8, H-7),
7.30–7.36 (6H, m, H-3, Ph), 7.57 (1H, dd, J7,6 8.1 and J6,5 8.1,
H-6), 7.82 (1H, dd, J5,6 8.1 and J5,7 0.8, H-5) and 14.20 (1H, s,
OH); δC (50 MHz; CDCl3) Ϫ5.2, Ϫ4.7 (CH3, SiMe2), 17.8
(quat, CMe3), 21.1 (CH3, COCH3), 23.1 (CH3, C-6Ј), 25.5
(CH3, CMe3), 37.4 (CH2, C-4Ј), 56.1, 56.3 (CH3, 2 × OMe),
65.6 (CH, C-5Ј), 71.8 (CH, C-3Ј), 72.2 (CH2, C-1Љ), 81.2 (CH,
C-2Ј), 101.1 (CH, C-3), 107.5 (CH, C-7), 112.0 (quat, C-2),
114.7 (CH, C-5), 116.6 (quat, C-8a), 127.9, 128.0, 128.3 [CH,
Ph (last 2 peaks coincidental)], 130.8 (CH, C-6), 133.1 (quat,
C-4a), 137.5 (quat, OCH2Ph), 147.2 (quat, C-4), 159.6, 160.0
(quat, C-1, -8), 170.7 (quat, C᎐O) and 200.3 (quat, C-1Ј); m/z
᎐
(CI) 597 (MHϩ, 3%), 566 (MH Ϫ HOCH3, 1), 537 (MH Ϫ
HOCOCH3, 2), 465 (MH Ϫ HOSiMe2But, 2), 431 (MH Ϫ
C9H10O3, 5), 404 (M Ϫ HOCOCH3 Ϫ HOSiMe2But, 4), 378
(C23H21O5, 61), 300 (43), 279 (100), 219 (C13H15O3, 30) and 205
(C12H13O3, 32).
(2ЈR,3ЈR,5ЈR)-2-[5-(tert-Butyldimethylsilyloxy)-3-hydroxy-2-
(phenylmethoxy)hexanoyl]-4,8-dimethoxy-1-naphthol 29
Manganese dioxide (130 mg, 1.50 mmol) was added to a solu-
tion of alcohol 26 (167 mg, 0.30 mmol) in dichloromethane (3
ml) and the reaction mixture was stirred for 5 h at room tem-
perature under an atmosphere of nitrogen. The reaction mix-
ture was filtered through Celite and the solvent removed under
reduced pressure. The residue was purified by flash chromato-
graphy using hexane–ethyl acetate (8:2) as eluent to yield the
title compound 29 (103 mg, 62%) as a bright yellow oil (Found:
C, 66.8; H, 7.6. C31H42O7Si requires C, 67.1; H, 7.6%); [α]D
ϩ21.19 (c 0.800, CHCl3); νmax (film)/cmϪ1 3494br w (OH), 2952,
(ii) (2ЈR,3ЈR,5ЈR)-2-[3-Acetoxy-5-(tert-butyldimethylsilyl-
oxy)-2-(phenylmethoxy)hexanoyl]-4,8-dimethoxy-1-naphthyl
acetate 30 (23 mg, 25%) as a pale yellow oil (Found: Mϩ,
638.2928. C35H46O9Si requires Mϩ, 638.2911); [α]D Ϫ12.75
(c 1.992, CHCl3); νmax (film)/cmϪ1 2930, 2856m (C–H), 1740s
(C᎐O, acetate), 1618s (C᎐O), 1243, 1215br s (C–O, acetate) and
᎐
᎐
1073s (C–O); δH (400 MHz; CDCl3) Ϫ0.08, Ϫ0.02 (6H, s,
SiMe2), 0.79 (9H, s, But), 1.05 (3H, d, J6Ј,5Ј 6.1 Hz, H3-6Ј),
1.70–1.77 (1H, m, H-4ЈA), 1.98 (3H, s, 3Ј-OCOCH3), 2.01–
2.08 (1H, m, H-4ЈB), 2.35 (3H, s, 1-OCOCH3), 3.80–3.82 (1H,
m, H-5Ј), 3.97, 4.01 (6H, s, 2 × OMe), 4.50 (1H, d, Jgem 12.3,
H-1ЉA), 4.85 (1H, d, Jgem 12.3, H-1ЉB), 5.00 (1H, d, J2Ј,3Ј 3.2,
H-2Ј), 5.20–5.27 (1H, m, H-3Ј), 6.95 (1H, dd, J6,7 8.0 and J5,5
0.7, H-7), 7.14 (1H, s, H-3), 7.31–7.38 (5H, m, Ph), 7.51 (1H,
dd, J7,6 8.0 and J6,5 8.0, H-6) and 7.90 (1H, dd, J5,6 8.0 and
J5,7 0.7, H-5); δC (50 MHz; CDCl3) Ϫ5.2, Ϫ4.9 (CH3, SiMe2),
17.8 (quat, CMe3), 20.1, 20.9 (CH3, 2 × COCH3), 23.0 (CH3,
C-6Ј), 25.6 (CH3, CMe3), 38.4 (CH2, C-4Ј), 55.8, 56.1 (CH3,
2 × OMe), 65.6 (CH, C-5Ј), 71.5 (CH, C-3Ј), 72.3 (CH2,
C-1Љ), 81.5 (CH, C-2Ј), 102.4 (CH, C-3), 107.7 (CH, C-7), 114.7
(CH, C-5), 119.6 (quat, C-2), 125.4 (quat, C-8a), 127.8 (quat,
C-4a), 128.0, 128.3, 128.4 [CH, Ph (last 2 peaks coinci-
dental)], 130.2 (CH, C-6), 137.3 (quat, OCH2Ph), 139.8 (quat,
C-4), 152.8, 156.7 (quat, C-1, -8), 170.1, 170.3 (quat,
2850m (C–H), 1616m (C᎐O), 1600m (C᎐C) and 1074s (C–O);
᎐
᎐
δH (400 MHz; CDCl3) 0.02, 0.04 (6H, s, SiMe2), 0.83 (9H, s,
But), 1.15 (3H, d, J6Ј,5Ј 6.0, H3-6Ј), 1.78–1.80 (2H, m, H2-4Ј),
3.90, 4.06 (6H, s, 2 × OMe), 4.00–4.05 (2H, m, H-5Ј, OH),
4.28–4.32 (1H, m, H-3Ј), 4.56 (1H, d, Jgem 11.7, H-1ЉA), 4.75
(1H, d, Jgem 11.7, H-1ЉB), 5.04 (1H, d, J2Ј,3Ј 4.5, H-2Ј), 6.95 (1H,
d, J6,7 8.0, H-7), 7.22 (1H, s, H-3), 7.24–7.38 (5H, m, Ph), 7.54
(1H, dd, J7,6 8.0 and J6,5 8.0, H-6), 7.83 (1H, dd, J5,6 8.0 and J5,7
0.7, H-5) and 12.90 (1H, br s, 1-OH); δC (100 MHz; CDCl3)
Ϫ5.0, Ϫ4.2 (CH3, SiMe2), 17.7 (quat, CMe3), 24.2 (CH3, C-6Ј),
25.7 (CH3, CMe3), 40.9 (CH2, C-4Ј), 55.6, 56.2 (CH3, 2 × OMe),
69.4, 72.1 (CH, C-5Ј, -3Ј), 72.4 (CH2, C-1Љ), 85.7, 102.5, 107.0
(CH, C-2Ј, -3, -7), 114.4 (quat, C-2), 115.0 (CH, C-5), 116.1
(quat, C-8a), 127.6, 127.9, 128.2 [CH, Ph (last 2 peaks coinci-
dental)], 129.8 (CH, C-6), 132.2, 137.7 (quat, C-4a, OCH2Ph),
147.0, 156.9, 158.6 (quat, C-1, -4, -8) and 201.1 (quat, C-1Ј); m/z
(EI) 554 (Mϩ, 3%), 445 (M Ϫ C7H9O, 2), 406 (M Ϫ C6H16O2Si,
3), 352 (C21H20O5, 24), 261 (C14H13O5, 23), 246 (C14H14O4, 11),
231 (C13H11O4, 100), 205 (C12H13O3, 11), 160 (C8H20OSi, 14),
145 (CH2OSiMe2But, 57), 131 (C6H15OSi, 9) and 91 (CH2Ph,
89).
2 × C᎐O) and 197.2 (quat, C-1Ј); m/z (CI) 639 (MHϩ, 19%),
᎐
507 (MH Ϫ C6H16OSi, 23), 337 (C19H33O3Si, 6), 273
(C16H19O4, 55), 231 (C13H11O4, 15), 159 (C8H9OSi, 28), 143
(C7H15OSi, 66) and 107 (C7H7O, 100).
(iii)
(2ЈR,3ЈR,5ЈR)-2-[5-(tert-Butyldimethylsilyloxy)-3-
hydroxy-2-(phenylmethoxy)hexanoyl]-4,8-dimethoxy-1-naph-
thyl acetate 32 (18 mg, 20%) as a pale yellow oil (Found:
Mϩ, 596.2821. C33H44O8Si requires M, 596.2805); [α]D Ϫ13.28
(c 0.256, CHCl3); νmax (film)/cmϪ1 3496br w (OH), 2930, 2855m
Acetylation of diol 29
Without using DMAP as a catalyst. To a solution of diol 29
(79 mg, 0.14 mmol) in dichloromethane (2.8 ml) was added
acetic anhydride (0.067 ml, 0.71 mmol) followed by triethyl-
(C–H), 1766m (C᎐O, acetate), 1600m (C᎐O), 1265br s (C–O,
᎐
᎐
acetate) and 1071s (C–O); δH (400 MHz; CDCl3) 0.02, 0.04 (6H,
J. Chem. Soc., Perkin Trans. 1, 2000, 697–709 707