V.M. Tanis et al. / Tetrahedron 64 (2008) 10649–10663
10661
The crude product was purified by chromatography using the
flash technique (50 mm OD; 40 g 230–400 mesh silica gel, packed
hexanes; run hexanes (100 mL), hexanes/CH2Cl2 (98:2, 100 mL),
hexanes/CH2Cl2 (96:4, 75 mL), hexanes/CH2Cl2 (94:6, 80 mL), hex-
anes/CH2Cl2 (92:8, 80 mL), hexanes/CH2Cl2 (90:10, 750 mL)) to
afford 456 mg (1.21 mmol, 79%) of 5-(5-methylhex-4-enyl)-5,6,7,8-
(8.91 mL, 4.45 mmol, 10 equiv). The mixture was placed in a 40 ꢀC oil
bath and was allowed to stir, under argon, for 2 h. The mixture was
allowed to cool to room temperature, and then the methanol was
removed in vacuo andthe residue was dissolved inwater (85 mL). The
pH was adjusted to ca. pH¼6 with 0.1 N aqueous HCl to produce
a cloudy aqueous phase. The mixture was transferred to a separatory
funnel with CHCl3 (100 mL), the aqueous phase was saturated with
salt, and the organic phase was separated. The aqueous layer was
extracted with CHCl3 (2ꢁ100 mL) and the combined organic phases
were dried (Na2SO4). Filtration and concentration in vacuo gave the
crude product as a yellow, glassy, semi-solid. TLC (hexanes/EtOAc
50:50, UV, PMA): Rf¼0.08.
tetrahydronaphthalene-1,2-diol-2-tert-butyldimethylsilyl
ether
(34) as a clear, colorless oil. IR (neat): 3542 (br), 2929, 2858, 1491,
1462, 1282, 1255, 1232, 976, 873, 833, 782 cmꢂ1. 1H NMR (400 MHz,
CDCl3):
d 0.25 (s, 3H, Si–CH3), 0.26 (s, 3H, Si–CH3), 1.00 (s, 9H, Si–t-
Bu), 1.30–1.95 (8H, C2/3/9/10–H), 1.57 (s, 3H, C15–H), 1.69 (S, 3H,
C14–H), 2.00 (m, 2H, C11–H), 2.55–2.77 (3H, C1/4–H), 5.13 (m, 1H,
C12–H), 6.57 (d, J¼8.3 Hz, 1H, C7–H), 6.62 (d, J¼8.3 Hz, 1H, C8–H).
The crude product was purified using the flash technique
(15 mm OD; 10 g 230–400 mesh silica gel, packed CH2Cl2; run
CH2Cl2 50 mL; CH2Cl2/MeOH, 98:2, 75 mL; CH2Cl2/MeOH, 97:3,
500 mL) to afford 100 mg (0.255 mmol, 57%) of 2-(5-(5-methylhex-
13C NMR (100 MHz, CDCl3):
d 144.4, 139.3, 135.9, 131.6, 125.0, 124.1,
119.3, 114.6, 37.3, 36.7, 28.5, 28.3, 27.9, 27.3, 26.0, 23.5, 19.0, 18.4,
18.0, ꢂ4.0, ꢂ4.1. EIMS (þ): 374 (Mþ, 45), 317 (77), 277 (27), 261 (23),
219 (base), 179 (49). HRMS (EI, þ): calcd for C23H38O2Si 374.2641,
found 374.2674.
4-enyl)-5,6,7,8-tetrahydronaphthalen-2-hydroxy-1-yloxy)-
pyranoside (4a) as a clear pale yellow glass. IR (neat): 3367 (br),
2925, 2858, 1606, 1486, 1452, 1265, 1039, 815, 738 cmꢂ1 1H NMR
(400 MHz, CDCl3): 1.25–1.87 (8H, C2/3/9/10–H), 1.60 (s, 3H, C15–
b-D-xylo-
.
3.31. Preparation of 2-(5-(5-methylhex-4-enyl)-5,6,7,8-
d
tetrahydronaphthalen-2-tert-butyldimethylsilyloxy-1-yloxy)-
2,3,4-tri-O-acetyl-b-D-xylopyranoside
H), 1.69 (s, 3H, C14–H), 1.97 (m, 2H, C11–H), 2.42–2.85 (4H, C1/4–H,
OH), 3.12 (br t, J¼8.7 Hz,1H, C20–H), 3.60 (m,1H, C20–H), 3.65–3.85
(3H, C18/19–H, OH), 3.95 (m, 1H, C17–H), 4.46 (m, 1H, C16–H), 4.80
(br, 1H, OH), 5.12 (br t, J¼6.8 Hz, 1H, C12–H), 5.70 (br, 2H, OH), 6.67
(d, J¼8.0 Hz, 1H, C7–H), 6.79 (m, 1H, C8–H). 13C NMR (100 MHz,
The procedure was identical to that described for the reaction of
structures 13 and 14; hence, only those items that differ from that
procedure are provided in the following: 5-(5-methylhex-4-enyl)-
5,6,7,8-tetrahydronaphthalene-1,2-diol-2-tert-butyldimethylsilyl
CDCl3):
d 146.9, 146.7, 145.9, 142.4, 142.3, 134.7, 131.7, 131.6, 131.5,
126.3, 124.9, 124.8, 114.2, 106.0, 105.9, 77.5, 76.7, 74.1, 69.6, 66.0,
53.6, 50.7, 37.1, 36.8, 28.5, 28.4, 27.8, 27.0, 25.9, 24.3, 19.1, 17.9, 14.9.
ESI-MS (TOF, þ): 415 (MþþNa, base), 387 (11). HRMS (ESI/TOF, þ):
calcd for C22H32O6þNa 415.2091, found 415.2109.
ether (34) (133 mg, 0.355 mmol) and 2,3,4-tri-O-acetyl-D-xylopyr-
anose-1-trichloroacetimidate (14) (179 mg, 0.426 mmol, 1.2 equiv);
4 Å molecular sieves (0.587 g); BF3$OEt2 (four drops); NaHCO3
(5 mL). The mixture was diluted with dichloromethane (15 mL), the
organic phase was separated, and filtered through a pad of anhy-
drous sodium sulfate and CeliteÒ. The filter cake was rinsed with
dichloromethane (15 mL) and the combined filtrates were con-
centrated in vacuo to afford the crude material as a clear viscous
yellow oil. TLC (pentane/Et2O 60:40, UV, PMA): Rf¼0.30.
3.33. Preparation of 2-(5-(5-methylhex-4-enyl)-5,6,7,8-
tetrahydronaphthalen-2-tert-butyldimethylsilyloxy-1-yloxy)-
2,3,4-tri-O-acetyl-b-L-arabinopyranoside
The procedure was identical to that described for the reaction of
structures 13 and 14; hence, only those items that differ from that
procedure are provided in the following: 5-(5-methylhex-4-enyl)-
5,6,7,8-tetrahydronaphthalene-1,2-diol-2-tert-butyldimethylsilyl
The crude product was purified by chromatography using the
flash technique (30 mm OD; 40 g 230–400 mesh silica gel, packed
pentane/Et2O 75:25; compound was applied on silica gel (7.5 g);
run pentane/Et2O 70:30, 125 mL, 10 mL fractions; pentane/Et2O
60:40, 500 mL,10 mL fractions) to afford 54 mg (0.144 mmol, 40% of
recovered phenol) and 143 mg (0.227 mmol, 64%) of 2-(5-(5-
methylhex-4-enyl)-5,6,7,8-tetrahydronaphthalen-2-tert-butyldi-
ether (34) (150 mg, 0.40 mmol) and 2,3,4-tri-O-acetyl-
L-arabino-
pyranose-1-trichloroacetimidate (15) (202 mg, 0.48 mmol,
1.2 equiv); dichloromethane (5 mL); 4 Å molecular sieves (482 mg);
BF3$OEt2 (four drops); saturated aqueous NaHCO3 (20 mL); diluted
with dichloromethane (25 mL). The filter cake was rinsed with
dichloromethane (50 mL), and the combined filtrates were con-
centrated in vacuo to afford the crude material as a clear, viscous
yellow oil. TLC (pentane/Et2O 60:40, UV, PMA): Rf¼0.32.
methylsilyloxy-1-yloxy)-2,3,4-tri-O-acetyl-b-D-xylopyranoside as
a clear pale yellow glass. IR (neat): 2931, 2858, 1756, 1486, 1369,
1246, 1216, 1070, 1037, 836, 734 cmꢂ1. 1H NMR (400 MHz, CDCl3):
d
0.20 (6H, Si–CH3), 1.01 (s, 9H, Si–t-Bu), 1.30–1.90 (8H, C2/3/9/10–
H), 1.60 (s, 3H, C15–H),1.68 (s, 3H, C14–H),1.99 (m, 2H, C11–H), 2.03
(s, 3H, OAc), 2.04 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.50–2.85 (m, 3H,
C1/4–H), 3.24 (m,1H, C20–H), 4.07 (dm, J¼12.3 Hz,1H, C20–H), 4.98
(m, 1H, C12–H), 5.14 (m, 1H, C19–H), 5.15–5.26 (2H, C17/18–H), 5.42
(m, 1H, C16–H), 6.63 (d, J¼8.3 Hz, 1H, C7–H), 6.82 (m, 1H, C8–H). 13C
The crude product was purified by chromatography using the
flash technique (30 mm OD; 30 g 230–400 mesh silica gel, packed
pentane/Et2O 75:25; compound was applied on silica gel (5 g); run
pentane/Et2O 70:30, 100 mL; pentane/Et2O 60:40, 400 mL; 10 mL
fractions) to afford 39 mg (0.104 mmol, 26% of recovered phenol).
Fractions 18–25 gave 139 mg (0.22 mmol, 55%) of 2-(5-(5-methyl-
hex-4-enyl)-5,6,7,8-tetrahydronaphthalen-2-tert-butyldimethylsi-
NMR (100 MHz, CDCl3):
d 170.3, 170.0, 169.6, 145.0, 144.9, 142.7,
142.6, 135.7, 135.6, 133.0, 132.9, 131.4, 125.0, 124.9, 124.8, 124.7,
124.6, 117.6, 117.5, 99.2, 99.0, 72.2, 72.1, 71.9, 71.8, 69.3, 62.7, 62.7,
37.3, 37.1, 36.7, 36.5, 28.5, 28.3, 27.8, 27.7, 27.1, 26.1, 26.0, 25.9, 24.6,
24.5, 21.0, 20.9, 20.8, 19.3, 19.1, 18.5, 17.9, ꢂ3.8, ꢂ3.9, ꢂ4.0. ESI-MS
(TOF, þ): 655 (MþþNa, base), 633 (MþþH, 15), 259 (14). HRMS (ESI/
TOF, þ): calcd for C28H38O8þNa 655.3278, found 655.3289.
lyloxy-1-yloxy)-2,3,4-tri-O-acetyl-
colorless glass. IR (neat): 2931, 2858, 1749, 1602, 1489, 1369, 1297,
1247, 1218, 1091, 1047, 974, 782, 734 cmꢂ1 1H NMR (400 MHz,
CDCl3): 0.19 (s, 6H, Si–CH3), 0.99 (s, 9H, Si–t-Bu),1.25–1.92 (8H, C2/
b-L-arabinopyranoside as a clear,
.
d
3/9/10/11–H), 1.59 (s, 3H, C15–H), 1.68 (s, 3H, C14–H), 1.96 (m, 2H,
C11–H), 2.04 (s, 3H, –OAc), 2.05 (s, 3H, –OAc), 2.06 (s, 3H, OAc), 2.50–
3.00 (m, 3H, C1/4–H), 3.53 (br d, J¼12.9 Hz, 1H, C20–H), 4.00 (dm,
J¼12.9 Hz,1H, C20–H), 5.05 (m,1H, C17–H), 5.14 (m,1H, C12–H), 5.18
(m, 1H, C18–H), 5.24 (m, 1H, C19–H), 5.43 (m, 1H, C16–H), 6.64 (d,
J¼8.4 Hz,1H, C9–H), 6.81 (m,1H, C8–H). 13C NMR (100 MHz, CDCl3):
3.32. Preparation of 2-(5-(5-methylhex-4-enyl)-5,6,7,8-tetra-
hydronaphthalen-2-hydroxy-1-yloxy)-b-D-xylopyranoside (4a)
To a solution of (5,6,7,8-tetrahydronaphthalen-2-tert-butyldime-
thylsilyloxy-1-yloxy)-2,3,4-tri-O-acetyl- -xylopyranoside (282 mg,
0.446 mmol) in methanol (35 mL) was added 0.5 M NaOMe in MeOH
b-D
d
170.5, 170.3, 169.6, 145.2, 145.1, 143.1, 143.0, 135.7, 135.6, 132.7,
132.6,131.5,124.9,124.6,117.8,117.7, 99.5, 99.3, 70.4, 70.3, 70.0, 67.9,