5750
S. Sakamaki et al. / Tetrahedron 68 (2012) 5744e5753
compound 12b was isolated in 99% yield as a colorless amorphous
powder. 1H NMR (400 MHz, CDCl3)
1387, 1163, 1127, 1109, 1065. HRMS (ESI, m/z) calcd for
25
d
7.44 (d, J¼9.0 Hz, 2H), 6.84 (d,
C
32H51NNaO4Si2 [MþNa]þ 592.3254, found 592.3255. [
a]
0.0 (c
D
J¼9.0 Hz, 2H), 5.11 (d, J¼2.4 Hz, 1H), 4.57 (dd, J¼2.4, 6.8 Hz, 1H),
4.30 (dd, J¼5.0, 10.5 Hz, 1H), 4.10 (m, 1H), 4.08 (m, 1H), 3.98 (dd,
J¼5.1, 10.5 Hz, 1H), 3.80 (s, 3H), 1.08 (s, 9H), 1.01 (s, 9H), 0.82e1.30
0.2, CHCl3).
4.6. Typical experimental procedure for the synthesis of
glucopyranosyl derivative
b-D-
(m, 21H). 13C NMR (100 MHz, CDCl3)
d 160.0, 150.9, 130.5, 126.5,
113.6, 99.7, 77.7, 72.9, 71.9, 66.2, 55.3, 27.5, 27.0, 22.8, 20.0, 18.2,18.2,
12.5. MS (APCI, m/z) 549 [MþH]þ. IR (KBr, cmꢀ1) 2891, 2862, 1653,
1611, 1513, 1252, 1113. HRMS (ESI, m/z) calcd for C30H53O5Si2
To a solution of compound 12ae12e (1 mmol) in THF (5.8 mL)
was added boraneetetrahydrofuran complex (1.0 M in THF
(2.5 mmol)) dropwise at 0 ꢁC. After being stirred at 0 ꢁC for over-
night, to the mixture were added 30% aqueous hydrogen peroxide
(3.3 mL) and 3 N aqueous sodium hydroxide (3.3 mL), and stirred at
0 ꢁC for 4 h. The reaction mixture was extracted with Et2O, washed
with brine, dried over sodium sulfate, and filtered. The filtrate was
concentrated and dried, then the crude material was purified by
silica gel column chromatography to give compounds 13ae13e.
[MþH]þ 549.3432, found 549.3431. [
a
]
25 ꢀ20.0 (c 0.2, CHCl3).
D
4.5.3. 3-(1,5-Anhydro-2-deoxy-4,6-O-di-(tert-butyl)silanediyl-3-O-
triisopropylsilyl- -arabino-hex-1-enitolyl)benzoic acid tert-butyl es-
D
ter (12c). Following the general method described above, the title
compound 12c was isolated in 99% yield as a colorless oil. 1H NMR
(400 MHz, CDCl3)
d
8.13 (t, J¼1.4 Hz, 1H), 7.92 (td, J¼1.5, 7.8 Hz, 1H),
7.66 (td, J¼1.2, 7.8 Hz, 1H), 7.37 (t, J¼7.8 Hz, 1H), 5.29 (d, J¼2.4 Hz,
1H), 4.60 (dd, J¼2.4, 6.6 Hz, 1H), 4.33 (dd, J¼4.6, 10.8 Hz, 1H), 4.12
(d, J¼10.2 Hz, 1H), 4.09 (dd, J¼3.1, 10.2 Hz, 1H), 4.02 (dd, J¼4.6,
10.5 Hz,1H),1.59 (s, 9H),1.13e1.18 (m, 21H),1.09 (s, 9H),1.02 (s, 9H).
4.6.1. (4aR,6S,7S,8R,8aR)-2,2-Di-tert-butyl-6-phenyl-8-[(triisopro-
pylsilyl)oxy]hexahydropyrano[3,2-d][1,3,2]dioxasilin-7-ol
(13a). Following the general method described above, the title
compound 13a was isolated in 58% yield as a colorless oil. 1H NMR
13C NMR (100 MHz, CDCl3)
d 165.4, 150.3, 134.3, 132.1, 129.5, 128.9,
128.1, 126.2, 101.9, 81.1, 77.5, 73.1, 71.7, 66.1, 28.2, 27.5, 27.0, 22.8,
(400 MHz, CDCl3)
d
7.31e7.39 (m, 5H), 4.23 (d, J¼9.7 Hz, 1H), 4.19
19.9, 18.3, 18.2, 12.5. MS (APCI, m/z) 619 [MþH]þ. HRMS (ESI, m/z)
(dd, J¼5.1, 10.2 Hz, 1H), 3.91 (t, J¼8.3 Hz, 1H), 3.88 (m, 1H), 3.84 (t,
J¼8.5 Hz, 1H), 3.53e3.58 (m, 1H), 3.50 (t, J¼9.0 Hz, 1H), 1.95 (br s,
1H, OH), 1.17e1.29 (m, 3H), 1.10e1.13 (m, 18H), 1.08 (s, 9H), 1.02 (s,
25
calcd for C34H59O6Si2 [MþH]þ 619.3850, found 619.3860. [
ꢀ24.0 (c 0.2, CHCl3).
a]
D
9H). 13C NMR (100 MHz, CDCl3)
d 138.6, 128.5, 128.5, 127.4, 82.2,
4.5.4. 4-(1,5-Anhydro-2-deoxy-4,6-O-di-(tert-butyl)silanediyl-3-O-
triisopropylsilyl- -arabino-hex-1-enitolyl)benzoic acid tert-butyl es-
79.8, 78.2, 76.6, 75.4, 66.7, 27.5, 27.0, 22.8, 20.0, 18.5, 18.4, 13.0. MS
(APCI, m/z) 554 [MþNH4]þ. IR (KBr, cmꢀ1) 3472, 2942, 2863, 1471,
1164, 1109. Anal. Calcd for C29H52O5Si2: C, 64.88; H, 9.76. Found: C,
D
ter (12d). Following the general method described above, the title
compound 12d was isolated in 99% yield as a colorless oil. 1H NMR
64.64; H, 9.99. [
a
]
25 ꢀ10.0 (c 0.2, CHCl3).
D
(400 MHz, CDCl3)
d
7.93 (d, J¼8.6 Hz, 2H), 7.54 (d, J¼8.8 Hz, 2H),
5.33 (d, J¼2.4 Hz, 1H), 4.60 (dd, J¼2.5, 6.7 Hz, 1H), 4.32 (dd, J¼4.9,
10.2 Hz, 1H), 4.11 (dd, J¼6.8, 10.3 Hz, 1H), 4.11 (app t, J¼10.3 Hz, 1H),
4.01 (dd, J¼4.2, 10.0 Hz, 1H), 1.59 (s, 9H), 1.12e1.15 (m, 21H), 1.09 (s,
4.6.2. (4aR,6S,7S,8R,8aR)-2,2-Di-tert-butyl-6-(4-methoxyphenyl)-8-
[(triisopropylsilyl)oxy]hexahydropyrano[3,2-d][1,3,2]dioxasilin-7-ol
(13b). Following the general method described above, the title
compound 13b was isolated in 60% yield as a colorless oil. 1H NMR
9H), 1.01 (s, 9H). 13C NMR (100 MHz, CDCl3)
d 165.4, 150.3, 137.9,
131.9, 129.4, 124.7, 103.1, 81.1, 77.4, 73.1, 71.7, 66.1, 28.2, 27.5, 27.0,
(400 MHz, CDCl3)
d
7.30 (d, J¼8.6 Hz, 2H), 6.89 (d, J¼8.8 Hz, 2H),
22.8, 19.9, 18.2, 18.2, 12.5. MS (APCI, m/z) 619 [MþH]þ. Anal. Calcd
4.18 (d, J¼9.7 Hz, 1H), 4.17 (m, 1H), 3.89 (t, J¼10.0 Hz, 1H), 3.85 (m,
1H), 3.83 (t, J¼8.5 Hz, 1H), 3.79 (s, 3H), 3.53e3.57 (m, 1H),
3.46e3.51 (m, 1H), 1.94 (d, J¼2.7 Hz, 1H, OH), 1.17e1.29 (m, 3H),
1.10e1.13 (m, 18H), 1.08 (s, 9H), 1.02 (s, 9H). 13C NMR (100 MHz,
25
for C34H58O6Si2: C, 65.97; H, 9.44. Found: C, 65.71; H, 9.62. [a]
D
ꢀ11.0 (c 0.2, CHCl3).
4.5.5. 3-(1,5-Anhydro-2-deoxy-4,6-O-di-(tert-butyl)silanediyl-3-O-
triisopropyl silyl- -arabino-hex-1-enito lyl )thiophene
CDCl3) d 159.8, 130.6, 128.6, 114.0, 81.9, 79.8, 78.2, 76.6, 75.3, 66.7,
D
55.3, 27.5, 27.0, 22.8, 20.0, 18.5, 18.4, 13.0. IR (Nujol, cmꢀ1) 3601,
(12e). Following the general method described above, the title
1613, 1514, 1463. MS (APCI, m/z) 584 [MþNH4]þ. Anal. Calcd for
compound 12e was isolated in 99% yield as a colorless oil. 1H NMR
C30H54O6Si2: C, 63.56; H, 9.60. Found: C, 63.73; H, 9.75. [
0.2, CHCl3).
a
]
25 ꢀ5.0 (c
D
(400 MHz, CDCl3)
d
7.36 (dd, J¼1.0, 3.1 Hz, 1H), 7.23e7.30 (m, 1H),
7.14 (dd, J¼1.2, 5.2 Hz, 1H), 5.12 (d, J¼2.2 Hz, 1H), 4.56 (dd, J¼2.4,
6.8 Hz, 1H), 4.30 (dd, J¼4.9, 10.5 Hz, 1H), 4.05e4.11 (m, 2H),
3.94e4.00 (m, 1H), 1.12e1.16 (m, 21H), 1.08 (s, 9H), 1.01 (s, 9H). 13C
4.6.3. tert-Butyl 3-{(4aR,6S,7S,8R,8aR)-2,2-di-tert-butyl-7-hydroxy-
8-[(triisopropylsilyl)oxy]-hexahydropyrano[3,2-d][1,3,2]dioxasilin-6-
yl}benzoate (13c). Following the general method described above,
the title compound 13c was isolated in 52% yield as a colorless oil.
NMR (100 MHz, CDCl3) d 147.8, 136.3, 125.7, 124.8, 121.8, 101.1, 77.5,
72.9, 71.6, 66.1, 27.5, 27.0, 22.8, 19.9, 18.2, 17.7, 12.5. MS (APCI, m/z)
525 [MþH]þ. IR (neat, cmꢀ1) 2941, 2891, 2863, 1657, 1470. Anal.
Calcd for C27H48O4SSi2: C, 61.78; H, 9.22. Found: C, 62.06; H, 9.52.
1H NMR (400 MHz, CDCl3)
d
8.01 (t, J¼1.7 Hz, 1H), 7.94 (td, J¼1.5,
7.7 Hz, 1H), 7.54 (td, J¼1.5, 7.7 Hz, 1H), 7.41 (t, J¼7.7 Hz, 1H), 4.30 (d,
J¼9.5 Hz, 1H), 4.18 (dd, J¼4.9, 10.3 Hz, 1H), 3.92 (t, J¼10.2 Hz, 1H),
3.87e3.89 (m, 1H), 3.85 (t, J¼8.3 Hz,1H), 3.48e3.61 (m, 2H), 2.03 (d,
J¼2.9 Hz, 1H, OH), 1.59 (s, 9H), 1.17e1.31 (m, 3H), 1.13 (d, J¼4.8 Hz,
12H), 1.11 (d, J¼4.8 Hz, 6H), 1.08 (s, 9H), 1.02 (s, 9H). 13C NMR
4.5.6. 8-(1,5-Anhydro-2-deoxy-4,6-O-di-(tert-butyl)silanediyl-3-O-
triisopropylsilyl- -arabino-hex-1-enitolyl)quinoline (12f). Following
D
the general method described above, the title compound 12f was
isolated in 99% yield as a colorless solid. 1H NMR (400 MHz, CDCl3)
(100 MHz, CDCl3) d 165.5, 138.9, 132.4, 131.5, 129.5, 128.3, 128.3,
d
8.94 (dd, J¼2.0, 4.1 Hz, 1H), 8.14 (dd, J¼8.2, 1.8 Hz, 1H), 7.91 (dd,
81.7, 81.1, 79.9, 78.1, 76.6, 75.4, 66.6, 28.2, 27.5, 27.0, 22.8, 20.0, 18.5,
J¼7.3, 1.5 Hz, 1H), 7.76 (dd, J¼1.5, 8.2 Hz, 1H), 7.51 (dd, J¼7.3, 8.2 Hz,
1H), 7.40 (dd, J¼4.2, 8.2 Hz, 1H), 6.11 (d, J¼2.4 Hz, 1H), 4.76 (dd,
J¼2.3, 6.8 Hz, 1H), 4.32 (dd, J¼4.4, 9.6 Hz, 1H), 4.26 (dd, J¼6.9,
10.2 Hz, 1H), 4.20 (td, J¼10.0, 4.3 Hz, 1H), 4.11 (app t, J¼9.7 Hz, 1H),
1.14e1.26 (m, 21H), 1.10 (s, 9H), 1.03 (s, 9H). 13C NMR (100 MHz,
18.4, 13.0. IR (KBr, cmꢀ1) 3499, 1718, 1589, 1463. MS (APCI, m/z) 654
[MþH]þ. Anal. Calcd for C34H60O7Si2: C, 64.11; H, 9.49. Found: C,
25
64.03; H, 9.65. [
a
]
ꢀ50.0 (c 0.2, CHCl3).
D
4.6.4. tert-Butyl 4-{(4aR,6S,7S,8R,8aR)-2,2-di-tert-butyl-7-hydroxy-
8-[(triisopropylsilyl)oxy]-hexahydropyrano[3,2-d][1,3,2]dioxasilin-6-
yl}benzoate (13d). Following the general method described
above, the title compound 13d was isolated in 41% yield as
CDCl3)
d 145.0, 148.9, 145.8, 136.3, 132.9, 128.9, 128.7, 128.5, 125.9,
120.9, 108.8, 77.7, 73.1, 72.1, 66.3, 27.5, 27.0, 22.8, 19.9, 18.2, 12.5. Mp
89e92 ꢁC. MS (APCI, m/z) 570 [MþH]þ. IR (neatþCHCl3, cmꢀ1) 1470,