4244
S.H. Lim et al. / Tetrahedron 71 (2015) 4236e4247
148.7, 152.7, 173.5; HRMS (ES) m/z 443.1678 (MþNa, C22H28O8Na
129.9, 131.8, 132.6, 135.1, 135.6, 135.6, 147.5, 148.3, 158.6; HRMS (ES)
m/z 579.2541 (MþNa, C34H40O5SiNa requires 579.2543).
requires 443.1682).
4.3.2. 24T (diastereomeric mixture, sol mp 103 ꢂC). 1H NMR (CDCl3)
4.5.2. 26T (l). 1H NMR (CDCl3)
d 1.02 (s, 9H), 3.00e3.02 (m, 1H),
d
1.05 (t, 3H, J¼7 Hz), 3.72 (s, 1H), 3.82 (s, 9H), 3.84 (s, 3H), 3.88 (s,
3H), 3.92e4.07 (m, 2H), 5.13 (d, 1H, J¼7.5 Hz), 6.53 (s, 2H),
6.79e6.87 (m, 3H); 13C NMR (CDCl3)
13.9, 55.7, 55.9, 56.0, 59.2,
3.68e3.73 (m, 1H), 3.72 (s, 3H), 3.78 (s, 3H), 3.83e3.86 (m, 1H), 3.86
(s, 3H), 5.18 (dd, 1H, J¼3.5, 6.3 Hz), 6.66 (s, 1H), 6.74 and 6.77 (d, 2H,
J¼8 Hz), 6.80 (d, 2H, J¼8.5 Hz), 7.15 (d, 2H, J¼8.5 Hz), 7.27e7.38 (m,
d
60.9, 61.2, 75.3, 103.7, 111.0, 111.9, 121.5, 127.0, 136.4, 137.5, 148.8,
148.9, 152.9, 172.5; HRMS (ES) m/z 443.1678 (MþNa, C22H28O8Na
requires 443.1682).
6H), 7.46e7.50 (m, 4H); 13C NMR (CDCl3)
d 19.1, 26.8, 55.0, 55.2,
55.7, 55.8, 65.4, 74.3, 110.8, 112.6, 113.4, 121.3, 127.6, 127.8, 129.6,
129.6, 131.5, 133.0, 133.1, 134.4, 135.5, 135.5, 147.9, 148.5, 158.9;
HRMS (ES) m/z 579.2543 (MþNa, C34H40O5SiNa requires 579.2543).
4.4. Diastereomeric 25E and 25T
4.6. Diastereomeric 28E and 28T
To respective solutions of THF containing 1.0 M LiAlH4 (9.5 mL,
9.5 mmol) were added mixture of 21E and 21T (3.15 g, 9.5 mmol) at
room temperature. After stirring for 3 h, 15 mL H2O and 15 mL 1 N
HCl solution at 0 ꢂC were added and the solutions were extracted
with CH2Cl2. The extracts were dried and concentrated in vacuo to
afford mixture of 10E/10T. A mixture solution of 10E/10T (1.5 g,
5.2 mmol) in DMF 50 mL containing imidazole (0.9 g, 13.0 mmol)
and tert-butyldiphenylsilylchloride (1.45 g, 5.3 mmol) was stirred
for 10 h at room temperature and concentrated in vacuo to give
a residue, which was partitioned between CH2Cl2 and H2O. The
organic layer was dried and concentrated in vacuo to give a residue,
which was subjected to column chromatography (EtOAc/hexane
1:3) to yield 25E (1.23 g, 45%) and 25T (0.55 g, 20%).
To respective solutions of THF containing 1.0 M LiAlH4 (8.8 mL,
8.8 mmol) were added mixture of 24E and 24T (3.7 g, 8.8 mmol) at
room temperature. After stirring for 3 h, 15 mL H2O and 15 mL 1 N
HCl solution at 0 ꢂC were added and the solutions were extracted
with CH2Cl2. The extracts were dried and concentrated in vacuo to
afford mixture of 13E/13T. A mixture solution of 13E/13T (0.37 g,
1.0 mmol) in DMF 20 mL containing imidazole (0.17 g, 2.5 mmol)
and tert-butyldiphenylsilylchloride (0.4 g, 1.5 mmol) was stirred for
10 h at room temperature and concentrated in vacuo to give a res-
idue, which was partitioned between CH2Cl2 and H2O. The organic
layer was dried and concentrated in vacuo to give a residue, which
was subjected to column chromatography (EtOAc/hexane 1:3) to
yield 28E (0.43 g, 70%) and 28T (0.6 g, 10%).
4.4.1. 25E (l). 1H NMR (CDCl3)
d 1.08 (s, 9H), 3.03e3.07 (m, 1H),
3.62 (s, 3H), 3.77 (s, 3H), 4.00e4.03 (m, 1H), 4.13e4.17 (m, 1H), 4.31
(s, 1H), 5.11 (dd, 1H, J¼2.5, 8 Hz), 6.35 (s, 1H), 6.51 and 6.62 (d, 2H,
J¼8.5 Hz), 7.13e7.18 (m, 5H), 7.25e7.44 (m, 6H), 7.61e7.66 (m, 4H);
4.6.1. 28E (l). 1H NMR (CDCl3)
d 1.08 (s, 9H), 2.95e2.99 (m, 1H),
3.66 (s, 3H), 3.69 (s, 6H), 3.76 (s, 3H), 3.78 (s, 3H), 4.00e4.03 (m,
1H), 4.11e4.15 (m, 1H), 4.33 (d, 1H, J¼3 Hz), 5.06 (dd, 1H, J¼3,
7.8 Hz), 6.35 (s, 2H), 6.41 (s, 1H), 6.53 (d, 1H, J¼6.5 Hz), 6.65 (d, 1H,
J¼8 Hz), 7.34e7.43 (m, 6H), 7.59e7.64 (m, 4H); 13C NMR (CDCl3)
13C NMR (CDCl3)
d 19.1, 26.9, 54.0, 55.7, 55.7, 67.7, 78.5, 110.7, 112.3,
120.5,126.7,127.1,127.8,129.9,129.9,131.7,132.6,135.6,135.6,142.9,
147.7, 148.4; HRMS (ES) m/z 549.2433 (MþNa, C33H38O4SiNa re-
quires 549.2437).
d
19.1, 26.8, 53.8, 55.8, 55.9, 60.8, 67.4, 78.4,103.6, 110.8,112.2, 120.7,
127.8, 129.9, 130.0, 131.7, 132.5, 135.6, 135.6, 136.8, 138.6, 147.8,
148.4, 152.6; HRMS (ES) m/z 639.2750 (MþNa, C36H44O7SiNa re-
quires 639.2754).
4.4.2. 25T (l). 1H NMR (CDCl3)
d 1.03 (s, 9H), 3.02e3.06 (m, 1H),
3.68 (s, 3H), 3.73e3.76 (m, 1H), 3.84 (s, 3H), 3.88e3.91 (m, 1H), 5.25
(dd, 1H, J¼1, 4.5 Hz), 6.58 (s, 1H), 6.70 and 6.75 (d, 2H, J¼8.5 Hz),
4.6.2. 28T (l). 1H NMR (CDCl3)
d 1.02 (s, 9H), 3.00e3.03 (m, 1H),
7.20e7.38 (m,11H), 7.48e7.52 (m, 4H); 13C NMR (CDCl3)
d 19.2, 26.9,
3.70e3.77 (m,1H), 3.73 (s, 6H), 3.74 (s, 3H), 3.81 (s, 3H), 3.86 (s, 3H),
3.86e3.88 (m, 1H), 5.17 (dd, 1H, J¼3.5, 6.5 Hz), 6.46 (s, 2H), 6.68 (s,
1H), 6.74 and 6.78 (d, 2H, J¼8.5 Hz), 7.26e7.31 (m, 4H), 7.35e7.39
(m, 2H), 7.44 (d, 2H, J¼6.5 Hz), 7.50 (d, 2H, J¼7 Hz); 13C NMR (CDCl3)
54.9, 55.7, 55.8, 65.4, 74.5, 110.9, 112.8, 121.3, 126.6, 127.4, 127.6,
128.0, 131.1, 133.1, 135.5, 142.4, 148.0, 148.5; HRMS (ES) m/z
549.2427 (MþNa, C33H38O4SiNa requires 549.2437).
d
19.1, 26.8, 29.6, 54.8, 55.7, 55.9, 60.8, 65.5, 75.0, 103.6, 110.8, 112.6,
4.5. Diastereomeric 26E and 26T
121.3, 127.6, 129.6,129.7, 131.3, 132.8,133.0, 135.4, 137.1, 138.0,148.0,
148.6, 152.9; HRMS (ES) m/z 693.2747 (MþNa, C36H44O7SiNa re-
quires 639.2754).
To respective solutions of THF containing 1.0 M LiAlH4 (9.4 mL,
9.4 mmol) were added mixture of 22E and 22T (3.4 g, 9.4 mmol) at
room temperature. After stirring for 3 h, 15 mL H2O and 15 mL 1 N
HCl solution at 0 ꢂC were added and the solutions were extracted
with CH2Cl2. The extracts were dried and concentrated in vacuo to
afford mixture of 11E/11T. A mixture solution of 11E/11T (0.9 g,
2.8 mmol) in DMF 40 mL containing imidazole (0.47 g, 6.9 mmol)
and tert-butyldiphenylsilylchloride (1.0 g, 3.6 mmol) was stirred for
10 h at room temperature and concentrated in vacuo to give a res-
idue, which was partitioned between CH2Cl2 and H2O. The organic
layer was dried and concentrated in vacuo to give a residue, which
was subjected to column chromatography (EtOAc/hexane 1:3) to
yield 26E (0.92 g, 60%) and 26T (0.4 g, 26%).
4.7. Diastereomeric 10E and 10T
Each solution of 25 (5.95 g, 11.3 mmol for 25E, 0.7 g, 1.35 mmol
for 25T) in THF (100 mL for 25E and 30 mL for 25T) containing
tetrabutylammonium fluoride (1.0 M THF solution) (16.9 mL,
16.9 mmol for 25E, 2 mL, 2 mmol for 25T) was stirred for 4 h at
room temperature and partitioned between CH2Cl2 and 1 N HCl.
The organic layer of 25E was dried and concentrated in vacuo to
give a residue that was subjected to column chromatography
(EtOAc/hexane 1:1) to yield 10E (2.5 g, 77%). The organic layer of
25T was dried and concentrated in vacuo to give a residue, which
was washed with ether to yield 10T (0.3 g, 80%).
4.5.1. 26E (l). 1H NMR (CDCl3)
d 1.07 (s, 9H), 2.99e3.05 (m, 1H),
3.64 (s, 3H), 3.71 (s, 3H), 3.76 (s, 3H), 3.98e4.01 (m, 1H), 4.11e4.14
(m, 1H), 4.30 (s, 1H), 5.06 (d, 1H, J¼8.5 Hz), 6.34 (s, 1H), 6.48 and
6.61 (d, 2H, J¼8.5 Hz), 6.69 (d, 2H, J¼6.5 Hz), 7.04 (d, 2H, J¼6.5 Hz),
4.7.1. 10E (l). 1H NMR (CDCl3)
d 3.00 (br s, 1H), 3.04e3.08 (m, 1H),
3.68 (s, 3H), 3.78 (s, 3H), 3.93e3.96 (m, 1H), 4.14e4.18 (m, 1H), 4.94
(d, 1H, J¼9 Hz), 6.39 (s, 1H), 6.58 (d, 1H, J¼8 Hz), 6.68 (d, 1H,
7.35e7.42 (m, 6H), 7.61e7.65 (m, 4H); 13C NMR (CDCl3)
d 19.1, 26.8,
54.0, 55.1, 55.7, 67.8, 78.1,110.6,112.1,113.2,120.5,127.8,127.8,129.9,
J¼8.5 Hz), 7.10e7.20 (m, 5H); 13C NMR (CDCl3)
d 54.4, 55.7, 66.3,