1756 J . Org. Chem., Vol. 64, No. 5, 1999
Notes
1.47 (s, 3 H), 4.02-4.14 (m, 3 H), 4.38-4.42 (m, 1 H), 5.57 (s, 1
H), 5.65 (s, 1 H), 6.43 (s, 1 H), 7.13-7.49 (m, 13 H), 7.62-7.68
(m, 2 H); 13C NMR (CD2Cl2, 100.6 MHz) δ 19.70 (q′), 28.39 (q′),
60.41 (t′), 72.66 (d′), 75.58 (d′), 84.30 (d′), 89.10 (d′), 98.18 (s′),
123.09 (d′), 127.51 (d′), 129.36 (d′), 130.35 (d′), 132.68 (s′), 133.64
(d′), 163.19 (s′); exact mass (electrospray) m/z calcd for C28H28N2-
NaO5Se (M + Na) 575.1061, found 575.1067.
(d′), 147.43 (s′), 174.79 (s′); exact mass m/z calcd for C19H20N2O4
340.1423, found 340.1422.
Compound 10b: [R]D ) -48.7 (c 0.94, CHCl3); FTIR (CH2Cl2
cast) 3455, 1781 cm-1; 1H NMR (CD2Cl2, 400 MHz) δ 1.28 (d, J
) 6.4 Hz, 3 H), 2.02 (d, J ) 4.3 Hz, 1 H), 3.75 (d, J ) 5.7 Hz, 1
H), 4.08-4.15 (m, 1 H), 4.20-4.24 (m, 1 H), 4.60 (dd, J ) 5.7,
4.0 Hz, 1 H), 4.77 (d, J ) 4.0 Hz, 1 H), 4.89 (s, 1 H), 7.00-7.05
(m, 2 H), 7.25-7.34 (m, 8 H); 13C NMR.(CD2Cl2, 100.6 MHz) δ
13.35 (q′), 60.14 (d′), 75.64 (d′), 76.43 (d′), 77.80 (d′), 85.79 (d′),
120.93 (d′), 123.09 (d′), 129.47 (d′), 147.46 (s′), 174.95 (s′); exact
mass m/z calcd for C19H20N2O4 340.1423, found 340.1422.
2,5-An h yd r o-1,6-d id eoxy-7-O-[(1,1-d im eth yleth yl)d ip h e-
n ylsilyl]-6-(2,2-d ip h en ylh yd r a zin o)-D-glycer o-L-id o-h ep ti-
tol (12). A solution of 10a (186.0 mg, 0.547 mmol) in THF (1
mL, plus 2 × 1 mL as a rinse) was added to a stirred and cooled
(0 °C) suspension of LiAlH4 (68.5 mg, 1.81 mmol) in THF (2 mL).
Stirring was continued for 0.5 h at 0 °C and then for 1.5 h after
removal of the ice bath. MeOH (0.3 mL) was added carefully to
quench the reaction, followed by saturated aqueous NaHCO3 (0.3
mL). The mixture was stirred for 15 min, diluted with THF (5
mL), and filtered through a pad (2 mm × 1 cm) of Celite, using
THF (40 mL). Evaporation of the filtrate gave the expected triol
11, which was used directly in the next step.
t-BuPh2SiCl (151 µL, 0.5813 mmol) was added dropwise to a
stirred solution of the triol (all the material from the above
experiment) and imidazole (69.6 mg, 1.02 mmol) in THF (4 mL).
Stirring was continued for 6 h, and the solvent was evaporated.
Flash chromatography of the residue over silica gel (1.6 × 28
cm), using 30% EtOAc-hexane, gave 12 (236.0 mg, 74%) as a
colorless oil: [R]D ) -42.1 (c 1.19, CHCl3); FTIR (CH2Cl2 cast)
3439 cm-1; 1H NMR (CD2Cl2, 300 MHz) δ 1.01 (s, 9 H), 1.25 (d,
J ) 6.5 Hz, 3 H), 1.71 (d, J ) 5.0 Hz, 1 H), 3.51 (td, J ) 9.0, 2.4
Hz, 1 H), 3.58-3.65 (m, 1 H), 3.79 (d, J ) 2.1 Hz, 1 H), 3.94 (dd,
J ) 10.1, 2.5 Hz, 1 H), 4.00-4.05 (m, 2 H), 4.27-4.38 (m, 2 H),
4.78 (s, 1 H), 6.91-7.00 (m, 6 H), 7.17-7.63 (m, 14 H); 13C NMR
(CD2Cl2, 100.6 MHz) δ 13.89 (q′), 19.17 (s′), 26.95 (q′), 59.44 (d′),
64.24 (t′), 76.65 (d′), 78.54 (d′), 78.67 (d′), 82.88 (d′), 120.63 (d′),
122.56 (d′), 128.28 (d′), 129.27 (d′), 130.41 (d′), 130.47 (d′), 132.42
(s′), 132.52 (s′), 135.85 (d′), 135.96 (d′), 148.26 (s′); exact mass
(electrospray) m/z calcd for C35H43N2O4Si (M + H) 583.2992,
found 583.2994.
2,5-An h yd r o-7-O-[(1,1-d im et h ylet h yl)d ip h en ylsilyl]-6-
[[(p h en ylm eth oxy)ca r bon yl]a m in o]-1,6-d id eoxy-D-glycer o-
L-iod o-h ep titol (13). Camphorsulfonic acid (199.0 mg, 0.858
mmol) and then 10% Pd-C (90.0 mg) were added to a solution
of 12 (227.0 mg, 0.390 mmol) in a mixture of EtOAc (5.6 mL)
and MeOH (1.4 mL). The mixture was shaken under H2 (50 psi)
for 2 h (Parr shaker) and then filtered through a pad of Celite.
The pad was washed with EtOAc (3 × 12 mL), and the combined
filtrates were evaporated. THF (7.5 mL), water (2.5 mL), and
NaHCO3 (170.3 mg, 2.027 mmol) were added to the resulting
yellow foam. The mixture was stirred and cooled (0 °C), and
BnOCOCl (84 µL, 0.5846 mmol) was added dropwise. Stirring
was continued for 0.5 h at 0 °C, and then for 0.5 h after removing
the cold bath. The mixture was extracted with CH2Cl2 (50 mL),
and the organic extract was washed with brine (10 mL), dried
(Na2SO4), and evaporated. Flash chromatography of the residue
over silica gel (1.6 × 28 cm), using 40% EtOAc-hexane, gave
13 (171.5 mg, 80%) as a colorless oil: [R]D ) -4.8 (c 1.04, CHCl3);
FTIR (CH2Cl2 cast) 3434, 1700 cm-1; 1H NMR (CD2Cl2, 400 MHz)
δ 1.06 (s, 9 H), 1.19 (d, J ) 6.5 Hz, 3 H), 2.05 (s, 1 H), 3.34 (s,
1 H), 3.62-3.69 (m, 1 H), 3.78 (dd, J ) 10.2, 4.4 Hz, 1 H), 3.95-
4.02 (m, 1 H), 4.03-4.12 (m, 1 H), 4.15-4.22 (m, 2 H), 4.27 (qd,
J ) 6.5, 3.5 Hz, 1 H), 5.06 (s, 2 H), 5.20 (br d, J ) 6.3 Hz, 1 H),
7.28-7.48 (m, 11 H), 7.63-7.72 (m, 4 H); 13C NMR (CD2Cl2,
100.6 MHz) δ 14.14 (q′), 19.40 (s′), 26.95 (q′), 52.69 (d′), 64.93
(t′), 67.11 (t′), 76.56 (d′), 78.67 (d′), 78.99 (d′), 79.26 (d′),128.21
(d′), 128.37 (d′), 128.81 (d′), 130.30 (d′), 133.09 (s′), 135.96 (d′),
137.08 (s′), 156.87 (s′); exact mass (electrospray) m/z calcd for
C31H40NO6Si (M + H) 550.2625, found 550.2641.
P h en yl 2-O-[(Dip h en ylh yd r a zon o)a cetyl]-1-selen o-â-L-
xylofu r a n osid e (8). Camphorsulfonic acid (158.9 mg, 0.684
mmol) was added to a stirred solution of 7 (377.0 mg, 0.684
mmol) in MeOH (225 mL). Stirring was continued for 3.5 h,
NaHCO3 (57.5 mg, 0.684 mmol) was added, and stirring was
continued for 0.5 h. The mixture was then evaporated. Flash
chromatography of the residue over silica gel (1.6 × 28 cm), using
50% EtOAc-hexane, gave 8 (336.0 mg, 96%) as a pale yellow
foam: [R]D ) 132.7 (c 1.12, CHCl3), FTIR (CH2Cl2 cast) 3427,
1706 cm-1; 1H NMR (CD2Cl2, 400 MHz) δ 2.60 (br s, 1 H), 3.92-
4.06 (m, 2 H), 4.15-4.22 (m, 1 H), 4.28 (dd, J ) 8.1, 4.3 Hz, 1
H), 4.43-4.46 (m, 1 H), 5.42 (d, J ) 1.6 Hz, 1 H), 5.71 (d, J )
2.0 Hz, 1 H), 6.45 (s, 1 H), 7.15-7.51 (m, 13 H), 7.62-7.70 (m,
2 H); 13C NMR (CD2Cl2, 100.6 MHz) δ 61.4 (t′), 76.48 (d′), 82.74
(d′), 85.08 (d′), 86.15 (d′), 123.05 (d′), 128.12 (d′), 129.55 (d′),
130.38 (d′), 130.59 (s′), 134.21 (d′), 164.04 (s′); exact mass
(electrospray) m/z calcd for C25H24N2NaO5Se (M + Na) 535.0748,
found 535.0746.
P h en yl 5-Deoxy-2-O-[(Diph en ylh ydr azon o)acetyl]-5-ph e-
n ylselen o-1-selen o-â-L-xylofu r a n osid e (9). Freshly prepared
PhSeCN15 (107.8 mg, 0.592 mmol) in THF (2 mL) was added
over 6 h by syringe pump to a stirred solution of 8 (275.0 mg,
0.538 mmol) and Bu3P (161 µL, 0.6458 mmol) in THF (2 mL).
Stirring was continued for 1.5 h, and the mixture was then
evaporated. Flash chromatography of the residue over silica gel
(1.6 × 26 cm), using first 10% EtOAc-hexane (100 mL) and then
30% EtOAc-hexane, gave 9 [349.8 mg, 75% or 89% after
correction for recovered starting material (44 mg)] as a pale
yellow oil: [R]D ) 135.1 (c 1.04, CHCl3); FTIR (CH2Cl2 cast) 3419,
1705 cm-1; 1H NMR (CD2Cl2, 300 MHz) δ 2.84 (d, J ) 6.1 Hz, 1
H), 3.23-3.35 (m, 2 H), 4.36-4.45 (m, 2 H), 5.43-5.44 (m, 1 H),
5.64 (d, J ) 1.8 Hz, 1 H), 6.44 (s, 1 H), 7.14-7.50 (m, 16 H),
7.53-7.69 (m, 4 H); 13C NMR (CD2Cl2, 100.6 MHz) δ 26.15 (t′),
75.08 (d′), 83.79 (d′), 84.97 (d′), 85.32 (d′), 123.01 (d′), 127.45
(d′), 128.21 (d′), 129.53 (d′), 130.42 (d′), 132.95 (d′), 134.61 (d′),
163.99 (s′); exact mass (electrospray) m/z calcd for C31H28N2-
NaO4Se2 (M + Na) 675.0277, found 675.0264.
3,6-An h yd r o-2,7-d id eoxy-2-(2,2-d ip h en ylh yd r a zin o)-L-
glycer o-D-id o-h ep ton o-1,4-la cton e (10a ) a n d 3,6-An h yd r o-
2,7-d id eoxy-2-(2,2-d ip h en ylh yd r a zin o)-L-glycer o-D-gu lo-
h ep ton o-1,4-la cton e (10b). This experiment was carried out
in a 200 mL round-bottomed flask equipped with a Teflon-coated
stirring bar and a reflux condenser sealed with a rubber septum.
The flask was charged with 9 (858.0 mg, 1.320 mmol), and the
system was flushed with argon for 5-10 min. Dry PhMe (80 mL)
was injected, and the flask was placed in an oil bath preheated
to 110 °C. Solutions of Ph3SnH (2.5483 g, 7.260 mmol) in PhMe
(10 mL) and of AIBN (130.0 mg, 0.792 mmol) in PhMe (10 mL)
were injected simultaneously by syringe pump over 10 h.
Refluxing was continued for 2 h after the addition. The mixture
was cooled, and the solvent was evaporated. Flash chromatog-
raphy of the residue over silica gel (2.5 × 29 cm), using first
20% EtOAc-hexane (300 mL) and then 30% EtOAc-hexane,
gave two fractions which all contained a small amount of
triphenyltin residues (1H NMR). Each fraction was further
purified by flash chromatography over silica gel (1.6 × 28 cm),
using 30% EtOAc-hexane, to give 10a (187.4 mg, 42%) and 10b
(166.1 mg, 37%), both as colorless oils.
Compound 10a : [R]D ) -23.1 (c 1.19, CHCl3); FTIR (CH2Cl2
cast) 3452, 1779 cm-1; 1H NMR (CD2Cl2, 300 MHz) δ 1.23 (d, J
) 6.4 Hz, 3 H), 1.95 (d, J ) 6.1 Hz, 1 H), 3.76 (t, J ) 1.0 Hz, 1
H), 4.02 (qd, J ) 6.3, 2.8 Hz, 1 H), 4.22 (dd, J ) 5.8, 2.8 Hz, 1
H), 4.31 (d, J ) 2.0 Hz, 1 H), 4.86 (d, J ) 4.9 Hz, 1 H), 5.08 (d,
J ) 4.9 Hz, 1 H), 7.05-7.18 (m, 6 H), 7.30-7.38 (m, 4 H); 13C
NMR (CD2Cl2, 100.6 MHz) δ 13.16 (q′), 62.96 (d′), 75.33 (d′),
77.21 (d′), 80.26 (d′), 88.25 (d′), 121.13 (d′), 123.70 (d′), 129.75
2,5-An h yd r o-1,3,4,6-tetr a d eoxy-7-O-[(1,1-d im eth yleth yl)-
diph en ylsilyl]-6-[[(ph en ylm eth oxy)car bon yl]am in o]-D-xylo-
h ep t-3-en itol (14). Ph3P (324.9 mg, 1.239 mmol), CHI3 (243.8
mg, 0.619 mmol), and imidazole (42.2 mg, 0.619 mmol) were
added to a stirred solution of diol 13 (170.0 mg, 0.310 mmol) in
dry PhMe (5 mL). The mixture was refluxed for 22 h, cooled to
room temperature, and extracted with PhMe (50 mL). The
(15) Tomoda, S.; Takeuchi, Y.; Nomura, Y. Chem. Lett. 1981, 1069-
1070.