The Journal of Organic Chemistry
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mL), and the combined organic phase was washed with brine, dried
with Na2SO4, and concentrated in vacuo. The residue was purified on
silica gel (petroleum/EtOAc = 10:1) to afford the corresponding
substates 2a−p.
131 (10), 185 (40), 295 (8), 427 (9), 295 (8), 557 (3). HRMS for
C40H82O8Si3Na (M + Na+): calcd 797.5210, found 797.5202.
Compound 2g: colorless oil, 51% yield (three steps). Rf = 0.75
1
(petroleum/EtOAc = 3:1). [α]26 = +1.6 (c = 6.3, EtOAc). H NMR
D
Compound 2a: colorless oil, 68% yield (three steps). Rf = 0.70
(petroleum/EtOAc = 3:1). [α]26D = +30.7 (c = 1.6, EtOAc). 1H NMR
(400 MHz, CDCl3, ppm): δ 4.80 (d, J = 6.8 Hz, 1 H), 4.68 (d, J = 6.4
Hz, 1 H), 4.03−3.96 (m, 2 H), 3.92−3.89 (m, 3 H), 3.60 (t, J = 6.4
Hz, 2 H), 3.53 (d, J = 3.2 Hz, 1 H), 3.41 (s, 3 H), 2.46−2.38 (m, 3 H),
2.18−2.15 (m, 2 H), 1.72−1.58 (m, 3 H), 1.53−1.45 (m, 2 H), 1.43−
1.42 (m, 1 H), 1.39 (s, 3 H), 0.92 (d, J = 6.0 Hz, 3 H), 0.90 (s, 9 H),
0.89 (s, 9 H), 0.10 (s, 3 H), 0.08 (s, 3 H), 0.04 (s, 6 H). 13C NMR
(100 MHz, CDCl3, ppm): δ 210.7, 110.8, 97.8, 81.4, 70.9, 65.5, 64.6,
62.8, 55.8, 50.0, 43.2, 41.1, 32.3, 26.1, 25.94, 25.88, 22.6, 20.8, 20.2,
18.3, 18.0, −3.9, −4.7, −5.3. MS (EI) m/z: 131 (17), 169 (16), 199
(10), 283 (5), 413 (3). HRMS for C29H60O7Si2Na (M + Na+): calcd
599.3770, found 599.3774.
Compound 2b: colorless oil, 61% yield (three steps). Rf = 0.65
(petroleum/EtOAc = 3:1). [α]19D = +15.0 (c = 2.0, EtOAc). 1H NMR
(400 MHz, CDCl3, ppm): δ 4.81 (d, J = 6.4 Hz, 1 H), 4.69 (d, J = 6.4
Hz, 1 H), 4.03−3.97 (m, 2 H), 3.94−3.90 (m, 3 H), 3.61 (t, J = 6.0
Hz, 2 H), 3.53 (d, J = 3.6 Hz, 1 H), 3.41 (s, 3 H), 2.53−2.42 (m, 3 H),
2.22−2.15 (m, 2 H), 1.81−1.68 (m, 3 H), 1.46−1.42 (m, 1 H), 1.40
(s, 3 H), 0.93 (d, J = 6.0 Hz, 3 H), 0.90 (s, 9 H), 0.89 (s, 9 H), 0.10 (s,
3 H), 0.08 (s, 3 H), 0.04 (s, 6 H). 13C NMR (100 MHz, CDCl3, ppm):
δ 210.6, 110.7, 97.8, 81.5, 70.9, 65.5, 64.6, 62.1, 55.9, 50.1, 41.2, 39.7,
26.7, 25.98, 25.96, 25.92, 22.6, 20.7, 18.3, 18.0, −3.9, −4.7, −5.4. MS
(EI) m/z: 131 (11), 185 (22), 269 (6), 381 (3), 443 (1). HRMS for
C28H58O7Si2Na (M + Na+): calcd 585.3613, found 585.3608.
Compound 2c, colorless oil, 58% yield (three steps). Rf = 0.70
(petroleum/EtOAc = 3:1). [α]22D = +16.0 (c = 2.5, EtOAc). 1H NMR
(400 MHz, CDCl3, ppm): δ 4.81 (d, J = 6.8 Hz, 1 H), 4.69 (d, J = 6.4
Hz, 1 H), 4.03−3.94 (m, 2 H), 3.93−3.90 (m, 3 H), 3.62−3.58 (m, 2
H), 3.53 (d, J = 3.6 Hz, 1 H), 3.41 (s, 3 H), 2.46−2.36 (m, 3 H),
2.18−2.16 (m, 2 H), 1.73−1.69 (m, 1 H), 1.62−1.42 (m, 5 H), 1.40
(s, 3 H), 1.36−1.30 (m, 2 H), 0.93 (d, J = 6.0 Hz, 3 H), 0.90 (s, 9 H),
0.89 (s, 9 H), 0.11 (s, 3 H), 0.09 (s, 3 H), 0.05 (s, 6 H). 13C NMR
(100 MHz, CDCl3, ppm): δ 210.7, 110.8, 97.9, 81.5, 70.9, 65.5, 64.6,
63.0, 62.9, 55.9, 50.1, 43.5, 41.2, 32.7, 26.00, 25.96, 25.5, 23.6, 22.6,
20.7, 18.3, 18.1, −3.9, −4.7, −5.3. MS (EI) m/z: 131 (15), 185 (8),
213 (13), 371 (2), 427 (3). HRMS for C30H62O7Si2Na (M + Na+):
calcd 613.3926, found 613.3933.
(400 MHz, CDCl3, ppm): δ 4.00−3.90 (m, 3 H), 3.87−3.83 (m, 1 H),
3.80−3.76 (m, 1 H), 3.62−3.59 (m, 3 H), 2.41−2.37 (m, 3 H), 2.15−
2.07 (m, 2 H), 1.78−1.71 (m, 1 H), 1.65−1.58 (m, 2 H), 1.53−1.46
(m, 2 H), 1.40−1.32 (m, 1 H), 1.36 (s, 3 H), 0.91 (d, J = 4.4 Hz, 3 H),
0.90 (s, 9 H), 0.888 (s, 9 H), 0.885 (s, 9 H), 0.10 (s, 3 H), 0.08 (s, 3
H), 0.07 (s, 3 H), 0.06 (s, 3 H), 0.04 (s, 6 H). 13C NMR (150 MHz,
CDCl3, ppm): δ 210.6, 110.7, 77.3, 72.0, 65.9, 64.3, 62.8, 50.0, 43.1,
40.3, 32.3, 26.0, 25.91, 25.85, 23.0, 20.7, 20.2, 18.3, 18.1, 18.0, −3.7,
−4.5, −4.7, −5.0, −5.3. MS (EI) m/z: 131 (15), 185 (8), 213 (13),
371 (2), 427 (3). HRMS for C33H70O6Si3Na (M + Na+): calcd
669.4372, found 669.4366.
Compound 2h: colorless oil, 48% yield (three steps). Rf = 0.75
(petroleum/EtOAc = 3:1). [α]23D = +15.0 (c = 2.0, EtOAc). 1H NMR
(400 MHz, CDCl3, ppm): δ 7.21 (d, J = 8.8 Hz, 2 H), 6.85 (d, J = 8.8
Hz, 2 H), 4.80 (d, J = 6.8 Hz, 1 H), 4.68 (d, J = 6.8 Hz, 1 H), 4.44−
4.37 (m, 2 H), 4.02−3.97 (m, 2 H), 3.92−3.85 (m, 4 H), 3.80 (s, 3 H),
3.73−3.70 (m, 2 H), 3.52 (d, J = 3.2 Hz, 1 H), 3.38 (s, 3 H), 2.90−
2.81 (m, 1 H), 2.54 (dd, J = 16.8 Hz, 3.2 Hz, 1 H), 2.27 (dd, J = 16.8
Hz, 9.6 Hz, 1 H), 2.18 (s, 3 H), 1.72−1.57 (m, 2 H), 1.40 (s, 3 H),
1.01 (d, J = 6.8 Hz, 3 H), 0.91 (d, J = 7.6 Hz, 3 H), 0.90 (s, 9 H), 0.88
(s, 9H), 0.10 (s, 3 H), 0.07 (s, 3 H), 0.052 (s, 3 H), 0.049 (s, 3 H). 13C
NMR (100 MHz, CDCl3, ppm): δ 212.9, 130.7, 129.4, 113.7, 110.8,
97.8, 81.3, 77.6, 77.3, 72.0, 71.0, 65.4, 64.7, 59.1, 55.8, 55.3, 50.7, 49.9,
41.2, 34.2, 26.00, 25.95, 25.1, 22.5, 21.0, 18.3, 18.1, 12.2, −3.9, −4.7,
−5.3, −5.4. MS (EI) m/z: 121 (100), 185 (5), 219 (2), 377 (1), 563
(1). HRMS for C38H70O9Si2Na (M + Na+): calcd 749.4451, found
749.4442.
Compound 2i: colorless oil, 65% yield (three steps). Rf = 0.70
(petroleum/EtOAc = 3:1). [α]21D = −30.0 (c = 5.0, EtOAc). 1H NMR
(400 MHz, CDCl3, ppm): δ 4.76 (d, J = 6.8 Hz, 1 H), 4.60 (d, J = 6.8
Hz, 1 H), 4.00−3.86 (m, 4 H), 3.68−3.64 (m, 1 H), 3.61 (t, J = 6.0
Hz, 2 H), 3.55 (d, J = 4.0 Hz, 1 H), 3.39 (s, 3 H), 2.55 (d, J = 12.4 Hz,
1 H), 2.50−2.41 (m, 2 H), 2.19−2.11 (m, 2 H), 1.81−1.74 (m, 2 H),
1.64−1.49 (m, 2 H), 1.36 (s, 3 H), 0.93 (d, J = 6.0 Hz, 3 H), 0.91 (s, 9
H), 0.89 (s, 9 H), 0.11 (s, 3 H), 0.09 (s, 3 H), 0.04 (s, 6 H). 13C NMR
(100 MHz, CDCl3, ppm): δ 210.8, 110.6, 96.9, 76.6, 76.1, 64.9, 64.8,
62.2, 56.0, 49.4, 39.6, 39.4, 26.7, 26.0, 25.9, 21.2, 20.7, 18.3, 18.2, −4.7,
−4.8, −5.4. MS (EI) m/z: 137 (12), 185 (7), 211 (3), 241 (10), 331
(2). HRMS for C28H58O7Si2Na (M + Na+): calcd 585.3613, found
585.3605.
Compound 2d: colorless oil, 52% yield (three steps). Rf = 0.75
(petroleum/EtOAc = 3:1). [α]27D = +40.0 (c = 2.0, EtOAc). 1H NMR
(400 MHz, CDCl3, ppm): δ 4.80 (d, J = 6.4 Hz, 1 H), 4.68 (d, J = 6.4
Hz, 1 H), 4.03−3.96 (m, 2 H), 3.92−3.89 (m, 3 H), 3.54 (d, J = 3.6
Hz, 1 H), 3.46 (dd, J = 9.6 Hz, 4.8 Hz, 1 H), 3.41 (s, 3 H), 3.37 (dd, J
= 9.6 Hz, 6.0 Hz, 1 H), 2.62−2.55 (m, 1 H), 2.48−2.42 (m, 1 H),
2.18−2.11 (m, 4 H), 1.73−1.67 (m, 1 H), 1.44−1.38 (m, 1 H), 1.40
(s, 3 H), 0.92 (d, J = 6.0 Hz, 3 H), 0.90 (s, 9 H), 0.89 (s, 9 H), 0.88 (d,
J = 6.0 Hz, 3 H), 0.11 (s, 3 H), 0.08 (s, 3 H), 0.033 (s, 3 H), 0.027 (s,
3 H). 13C NMR (100 MHz, CDCl3, ppm): δ 210.4, 110.8, 97.8, 81.5,
70.9, 67.4, 65.5, 64.6, 55.8, 50.5, 47.0, 41.2, 31.8, 26.0, 25.9, 22.6, 20.7,
18.3, 18.0, 16.7, −3.9, −4.7, −5.4, −5.5. MS (EI) m/z: 87 (100), 131
(12), 213 (10), 243 (8), 343 (1). HRMS for C29H60O7Si2Na (M +
Na+): calcd 599.3770, found 599.3762.
Compound 2j: colorless oil, 65% yield (three steps). Rf = 0.70
1
(petroleum/EtOAc = 3:1). [α]23 = −26.0 (c = 10.0, EtOAc). H
D
NMR (400 MHz, CDCl3, ppm): δ 4.75 (d, J = 6.8 Hz, 1 H), 4.59 (d, J
= 6.8 Hz, 1 H), 3.99−3.86 (m, 4 H), 3.67−3.65 (m, 1 H), 3.61 (t, J =
6.0 Hz, 2 H), 3.55 (d, J = 4.0 Hz, 1 H), 3.39 (s, 3 H), 2.55−2.47 (m, 1
H), 2.46−2.34 (m, 2 H), 2.19−2.10 (m, 2 H), 1.65−1.47 (m, 6 H),
1.35 (s, 3 H), 0.92 (d, J = 6.8 Hz, 3 H), 0.90 (s, 9 H), 0.89 (s, 9 H),
0.11 (s, 3 H), 0.09 (s, 3 H), 0.04 (s, 6 H). 13C NMR (100 MHz,
CDCl3, ppm): δ 210.8, 110.6, 96.9, 76.6, 76.1, 64.9, 64.7, 62.9, 56.0,
49.2, 43.1, 39.4, 32.3, 26.0, 25.9, 21.2, 20.8, 20.2, 18.3, 18.2, −4.7, −4.8,
−5.3. MS (EI) m/z: 151 (12), 199 (6), 255 (12), 283 (6), 413 (2),
457 (0.5). HRMS for C29H60O7Si2Na (M + Na+): calcd 599.3770,
found 599.3760.
Compound 2e: colorless oil, 73% yield (three steps). Rf = 0.65
1
(petroleum/EtOAc = 3:1). [α]23 = +21.3 (c = 30.0, EtOAc). H
D
Compound 2k: colorless oil, 54% yield (three steps). Rf = 0.70
NMR (400 MHz, CDCl3, ppm): δ 4.98 (s, 1H), 4.87 (s, 1 H), 4.80 (d,
J = 6.4 Hz, 1 H), 4.67 (d, J = 6.4 Hz, 1 H), 4.04 (d, J = 4.4 Hz, 1 H),
4.01−3.95 (m, 2 H), 3.92−3.88 (m, 3 H), 3.65 (dt, J = 8.0 Hz, 4.0 Hz,
1 H), 3.52 (d, J = 3.6 Hz, 1 H), 3.39 (s, 3 H), 2.44−2.33 (m, 2 H),
2.16−2.02 (m, 4 H), 1.71 (s, 3 H), 1.69−1.67 (m, 1 H), 1.46−1.40
(m, 2 H), 1.38 (s, 3 H), 1.14−1.09 (m, 1 H), 0.91 (d, J = 6.0 Hz, 3 H),
0.90 (s, 9 H), 0.89 (s, 9 H), 0.88 (d, J = 5.2 Hz, 3 H), 0.88 (s, 9H),
0.09 (s, 3 H), 0.08 (s, 3 H), 0.06 (s, 3 H), 0.05 (s, 3 H), 0.04 (s, 3 H),
0.01 (s, 3 H). 13C NMR (100 MHz, CDCl3, ppm): δ 210.1, 144.7,
111.9, 110.7, 97.8, 81.3, 77.5, 73.7, 70.8, 65.4, 64.6, 55.8, 50.6, 50.5,
41.0, 40.0, 26.0, 25.9, 25.8, 25.61, 25.58, 22.52, 21.2, 21.1, 20.7, 18.1,
18.01, 17.96, −3.8, −3.9, −4.7, −4.9, −5.1. MS (EI) m/z: 87 (100),
1
(petroleum/EtOAc = 3:1). [α]26 = +5.0 (c = 2.0, EtOAc). H NMR
D
(400 MHz, CDCl3, ppm): δ 4.76 (d, J = 6.8 Hz, 1 H), 4.60 (d, J = 6.8
Hz, 1 H), 4.00−3.86 (m, 4 H), 3.69−3.65 (m, 1 H), 3.55 (d, J = 4.4
Hz, 1 H), 3.46 (dd, J = 10.0 Hz, 5.2 Hz, 1 H), 3.40−3.36 (m, 1 H),
3.39 (s, 3 H), 2.61−2.52 (m, 2 H), 2.19−2.10 (m, 4 H), 1.64−1.49
(m, 2 H), 1.36 (s, 3 H), 0.93 (d, J = 6.4 Hz, 3 H), 0.91 (s, 9 H), 0.89
(d, J = 4.4 Hz, 3 H), 0.89 (s, 9 H), 0.11 (s, 3 H), 0.09 (s, 3 H), 0.04 (s,
3 H), 0.03 (s, 3 H). 13C NMR (100 MHz, CDCl3, ppm): δ 210.7,
110.7, 96.9, 76.6, 67.4, 64.9, 64.8, 56.0, 49.9, 46.9, 39.4, 31.9, 26.0,
25.9, 21.2, 20.7, 18.3, 18.2, 16.7, −4.6, −4.8, −5.4, −5.5. MS (EI) m/z:
57 (100), 71 (60), 99 (22), 127 (14), 239 (8), 267 (15), 341 (17).
554
dx.doi.org/10.1021/jo402167q | J. Org. Chem. 2014, 79, 546−558