X. Gao, M. Harmata / Tetrahedron 69 (2013) 7675e7682
7681
il. Rf¼0.29 (10% EtOAc/hexanes). 1H NMR (500 MHz, CDCl3)
d
6.26 (d,
ꢂ0.9 (3C), ꢂ5.3 (2C); IR (cmꢂ1) 2953, 2898, 2858, 1749, 1560, 1472,
1463, 1410, 1250, 1161, 1105, 1011, 972, 837, 776, 691; HRMS m/z
calcd for (C27H52O3Si3)Naþ: 531.3116, found: 531.3116.
J¼6.0 Hz, 1H), 6.11 (d, J¼6.0 Hz, 1H), 4.70 (dd, J¼1.5, 4.0 Hz, 1H),
3.64e3.54 (m, 2H), 2.42e2.35 (m, 2H), 2.06e1.90 (m, 4H), 1.85e1.75
(m, 2H), 0.77 (dd, J¼2.5, 14.5 Hz, 1H), 0.72 (dd, J¼2.0, 14.5 Hz, 1H),
0.40e0.29 (m, 2H), 0.05 (s, 9H), 0.04 (s, 9H), 13C NMR (125 MHz,
4.3.26. (2S*,3R*,4S*)-2-(5-Butylfuran-2-yl)-3,4-bis((trimethylsilyl)
CDCl3)
d
209.5, 135.0, 133.9, 90.1, 81.9, 63.4, 57.5, 45.1, 34.4, 34.0, 30.5,
methyl)cyclopentanone (23k). Colorless oil. Rf¼0.50 (10% EtOAc/
27.5, 18.2, 17.7, ꢂ0.7 (6C); IR (cmꢂ1) 2953, 1748, 1445, 1419, 1314, 1249,
1199, 1181, 1137, 1127, 1009, 922, 858, 837, 720, 694; HRMS m/z calcd
for (C20H35ClO2Si2)Naþ: 421.1756, found: 421.1754.
hexanes). 1H NMR (500 MHz, CDCl3)
d
5.99 (d, J¼3.0 Hz,1H), 5.88 (d,
J¼3.0 Hz, 1H), 3.10 (d, J¼9.0 Hz, 1H), 2.59e2.44 (m, 5H), 2.22e2.15
(m, 1H), 1.61e1.54 (m, 2H), 1.38e1.30 (m, 2H), 0.90 (t, J¼7.5 Hz, 3H),
0.82e0.75 (m, 2H), 0.57 (dd, J¼6.0, 15.0 Hz, 1H), 0.35 (dd, J¼12.5,
14.0 Hz, 1H), 0.04 (s, 9H), 0.00 (s, 9H), 13C NMR (125 MHz, CDCl3)
4.3.21. (2S*,3R*,4S*)-2-(Furan-2-yl)-3,4-bis((trimethylsilyl)methyl)
cyclopentanone (23a). Colorless oil. Rf¼0.55 (10% EtOAc/hexanes).
d 215.9,156.1,149.2,108.2,105.3, 54.9, 45.7, 43.3, 34.1, 30.1, 27.7, 22.2,
1H NMR (500 MHz, CDCl3)
d
7.35 (d, J¼1.0 Hz, 1H), 6.32 (dd, J¼2.0,
16.0, 15.5, 13.8, ꢂ0.7 (3C), ꢂ0.9 (3C); IR (cmꢂ1) 2955, 2874, 1749,
1560,1411,1249,1180,1162,1111,1077,1013, 966, 860, 838, 779, 691;
HRMS m/z calcd for (C21H38O2Si2)Naþ: 401.2306, found: 401.2306.
3.0 Hz, 1H), 6.12 (d, J¼3.5 Hz, 1H), 3.17 (d, J¼9.5 Hz, 1H), 2.59e2.43
(m, 3H), 2.25e2.17 (m, 1H), 0.84e0.76 (m, 2H), 0.58 (dd, J¼6.0,
14.5 Hz, 1H), 0.35 (dd, J¼12.5, 14.5 Hz, 1H), 0.05 (s, 9H), 0.00 (s, 9H),
13C NMR (125 MHz, CDCl3)
d
215.5, 151.3, 142.1, 110.3, 107.7, 54.7,
4.3.27. (2S*,3R*,4S*)-2-(5-(3-Chloropropyl)furan-2-yl)-3,4-bis((trime
45.7, 43.4, 34.2, 16.1, 15.5, ꢂ0.7 (3C), ꢂ0.9 (3C); IR (cmꢂ1) 2953,
2899, 1749, 1504, 1411, 1249, 1148, 1010, 860, 838, 730, 691; HRMS
m/z calcd for (C17H30O2Si2)Naþ: 345.1677, found: 345.1675.
thylsilyl)methyl) cyclopentanone (23l). Colorless oil. Rf¼0.43 (10%
EtOAc/hexanes). 1H NMR (500 MHz, CDCl3)
d
6.01 (d, J¼3.0 Hz, 1H),
5.96 (d, J¼2.5 Hz, 1H), 3.53 (t, J¼6.0 Hz, 2H), 3.10 (d, J¼9.0 Hz, 1H),
2.75 (t, J¼7.5 Hz, 2H), 2.56e2.42 (m, 3H), 2.23e2.16 (m, 1H),
2.10e2.03 (m, J¼7.0 Hz, 2H), 0.83e0.75 (m, 2H), 0.56 (dd, J¼6.5,
15.0 Hz, 1H), 0.34 (dd, J¼12.5, 14.0 Hz, 1H), 0.04 (s, 9H), 0.00 (s, 9H),
4.3.22. (2S*,3R*,4S*)-2-(5-Methylfuran-2-yl)-3,4-bis((trimethylsilyl)
methyl)cyclopentanone (23b). Colorless oil. Rf¼0.48 (10% EtOAc/
hexanes). 1H NMR (500 MHz, CDCl3)
d
5.98 (d, J¼3.0 Hz,1H), 5.88 (d,
13C NMR (125 MHz, CDCl3)
d 215.7, 153.9, 149.9, 108.4, 106.4, 54.8,
J¼2.0 Hz, 1H), 3.09 (d, J¼9.5 Hz, 1H), 2.58e2.43 (m, 3H), 2.24 (s, 3H),
2.23e2.16 (m, 1H), 0.82e0.76 (m, 2H), 0.58 (dd, J¼6.0, 15.0 Hz, 1H),
0.34 (dd, J¼12.5, 14.5 Hz, 1H), 0.04 (s, 9H), 0.00 (s, 9H), 13C NMR
45.8, 44.1, 43.3, 34.1, 30.9, 25.2, 16.1, 15.5, ꢂ0.7 (3C), ꢂ0.9 (3C); IR
(cmꢂ1) 2953, 2901, 1748, 1560, 1411, 1249, 1184, 1152, 1111, 1076,
1014, 968, 860, 838, 783, 691; HRMS m/z calcd for (C20H35ClO2Si2)
Naþ: 421.1756, found: 421.1755.
(125 MHz, CDCl3)
d 215.9, 151.7, 149.4, 108.5, 106.2, 54.8, 45.8, 43.3,
34.1,16.1,15.5,13.6, ꢂ0.7 (3C), ꢂ0.9 (3C); IR (cmꢂ1) 2953, 2900,1747,
1567, 1410, 1249, 1022, 860, 838, 780, 734, 691; HRMS m/z calcd for
(C18H32O2Si2)Naþ: 359.1833, found: 359.1832.
4.3.28. (1R*,2S*,3S*,4R*,5R*,6S*,10R*)-1-Benzyl-3,4-bis((trimethylsilyl)
methyl)-9-oxatricyclo [4.2.1.12,5]dec-7-en-10-ol (24i). White solid;
mp¼122e123 ꢀC, Rf¼0.19 (10% EtOAc/hexanes). 1H NMR (500 MHz,
4.3.23. (2S*,3R*,4S*)-2-(5-Ethylfuran-2-yl)-3,4-bis((trimethylsilyl)
CDCl3)
d
7.30e7.25 (m, 2H), 7.23e7.18 (m, 3H), 6.47 (dd, J¼1.5, 6.0 Hz,
methyl)cyclopentanone (23c). Colorless oil. 1H NMR (500 MHz,
1H), 6.42 (d, J¼6.0 Hz, 1H), 4.49e4.46 (m, 1H), 3.97e3.91 (m,
J¼12.5 Hz, 1H), 3.08 (d, J¼14.0 Hz, 1H), 2.92 (d, J¼12.0 Hz, 1H), 2.90
(d, J¼14.0 Hz, 1H), 2.48 (dt, J¼4.5, 9.5 Hz, 1H), 2.33 (ddd, J¼2.5, 9.0,
13.0 Hz, 1H), 1.90 (dd, J¼2.0, 3.5 Hz, 1H), 1.80e1.76 (m, 1H), 0.91 (dd,
J¼4.5, 15.0 Hz, 1H), 0.73 (dd, J¼3.0, 15.0 Hz, 1H), 0.46 (dd, J¼10.0,
15.0 Hz, 1H), 0.40 (dd, J¼13.5, 14.5 Hz, 1H), 0.10 (s, 9H), 0.04 (s, 9H),
CDCl3)
d
6.00 (d, J¼3.0 Hz, 1H), 5.89 (d, J¼3.0 Hz, 1H), 3.10 (d,
J¼9.5 Hz, 1H), 2.59 (q, J¼7.0 Hz, 2H), 2.56e2.44 (m, 3H), 2.23e2.15
(m, 1H), 1.19 (t, J¼7.5 Hz, 3H), 0.82e0.75 (m, 2H), 0.57 (dd, J¼14.5,
6.0 Hz, 1H), 0.34 (dd, J¼14.5, 12.0 Hz, 1H), 0.04 (s, 9H), 0.00 (s, 9H);
13C NMR (125 MHz, CDCl3)
d 215.9, 157.4, 149.2, 108.2, 104.5, 54.9,
45.7, 43.3, 34.1, 21.4, 16.1, 15.5, 12.0, ꢂ0.7, ꢂ0.9; IR (cmꢂ1) 2953,
2900, 1749, 1559, 1411, 1249, 1012, 860, 837, 776, 690; HRMS m/z
calcd for C19H34O2Si2Naþ: 373.1990, found: 373.1985.
13C NMR (125 MHz, CDCl3)
d 138.4,136.5, 136.4, 130.3 (2C), 128.1 (2C),
126.4, 87.4, 81.0, 73.5, 55.8, 49.4, 41.1, 37.5, 19.4, 18.7, ꢂ0.6 (3C), ꢂ0.7
(3C); IR (cmꢂ1) 3609, 3457, 3064, 3029, 2950, 1496, 1454, 1314, 1248,
1182, 1092, 1020, 1001, 837, 740, 697; HRMS m/z calcd for
(C24H38O2Si2)Naþ: 437.2303, found: 437.2308.
4.3.24. (2S*,3R*,4S*)-2-(5-Benzylfuran-2-yl)-3,4-bis((trimethylsilyl)
methyl)cyclopentanone (23i). Colorless oil. Rf¼0.52 (10% EtOAc/
hexanes). 1H NMR (500 MHz, CDCl3)
d
7.31e7.26 (m, 2H), 7.24e7.19
4.3.29. (1R*,2S*,3S*,4R*,5R*,6S*,10R*)-1-(4-((tert-Butyldimethylsilyl)
(m, 3H), 6.03 (d, J¼3.5 Hz, 1H), 5.91 (d, J¼3.0 Hz, 1H), 3.93 (s, 2H),
3.12 (d, J¼9.5 Hz, 1H), 2.56e2.42 (m, 3H), 2.24e2.17 (m, 1H),
0.82e0.75 (m, 2H), 0.58 (dd, J¼6.0, 15.0 Hz, 1H), 0.35 (dd, J¼12.0,
14.0 Hz, 1H), 0.05 (s, 9H), ꢂ0.02 (s, 9H), 13C NMR (125 MHz, CDCl3)
oxy)butyl)-3,4-bis((trimethylsilyl)methyl)-9-oxatricyclo[4.2.1.12,5
]
dec-7-en-10-ol (24j). Colorless oil. Rf¼0.21 (10% EtOAc/hexanes). 1H
NMR (500 MHz, CDCl3)
d
6.59 (d, J¼5.5 Hz, 1H), 6.43 (d, J¼6.0 Hz,
1H), 4.50e4.48 (m, 1H), 3.88 (d, J¼12.0 Hz, 1H), 3.64e3.54 (m, 2H),
2.93 (d, J¼12.0 Hz, 1H), 2.30e2.21 (m, 2H), 1.80e1.77 (m, 1H),
1.77e1.74 (m, 1H), 1.74e1.66 (m, 1H), 1.66e1.58 (m, 1H), 1.58e1.51
(m, 2H), 1.45e1.27 (m, 2H), 0.88 (s, 9H), 0.82 (d, J¼15.0 Hz, 1H), 0.74
(d, J¼15.0 Hz, 1H), 0.37 (dd, J¼11.0, 14.5 Hz, 2H), 0.03 (s, 15H), 0.02
d
215.6, 154.0, 150.1, 138.1, 128.6 (2C), 128.4 (2C), 126.3, 108.5, 107.0,
54.8, 45.8, 43.3, 34.5, 34.0, 16.0, 15.4, ꢂ0.7 (3C), ꢂ0.9 (3C); IR (cmꢂ1
)
3064, 3030, 2952, 2900, 1748, 1604, 1560, 1496, 1454, 1411, 1249,
1157, 1111, 1074, 1014, 967, 860, 837, 782, 703, 693; HRMS m/z calcd
for (C24H36O2Si2)Naþ: 435.2146, found: 435.2142.
(s, 9H), 13C NMR (125 MHz, CDCl3)
d 138.8, 136.7, 87.6, 81.2, 73.5,
63.1, 54.9, 49.4, 37.8, 37.4, 34.3, 33.3, 26.0 (3C), 20.1, 19.5, 18.6, 18.4,
ꢂ0.6 (3C), ꢂ0.7 (3C), ꢂ5.3 (2C); IR (cmꢂ1) 3619, 3474, 2951, 2897,
2858, 1472, 1463, 1248, 1194, 1088, 1007, 836, 775, 751, 697; HRMS
m/z calcd for (C27H54O3Si3)Naþ: 533.3273, found: 533.3272.
4.3.25. (2S*,3R*,4S*)-2-(5-(4-((tert-Butyldimethylsilyl)oxy)butyl)fu-
ran-2-yl)-3,4-bis((trimethylsilyl)methyl)cyclopentanone
(23j). Colorless oil. Rf¼0.33 (5% EtOAc/hexanes). 1H NMR (500 MHz,
CDCl3)
d
5.99 (d, J¼3.0 Hz, 1H), 5.90 (d, J¼3.0 Hz, 1H), 3.61 (t,
J¼6.0 Hz, 2H), 3.09 (d, J¼9.5 Hz, 1H), 2.58 (t, J¼7.5 Hz, 2H),
2.55e2.42 (m, 3H), 2.22e2.15 (m, 1H), 1.69e1.61 (m, 2H), 1.58e1.51
(m, 2H), 0.89 (s, 9H), 0.82e0.75 (m, 2H), 0.57 (dd, J¼6.5, 15.0 Hz,
1H), 0.34 (dd, J¼12.0, 14.0 Hz, 1H), 0.04 (s, 15H), 0.00 (s, 9H), 13C
4.3.30. (1R*,2S*,3S*,4R*,5R*,6S*,10R*)-1-Butyl-3,4-bis((trimethylsilyl)
methyl)-9-oxatricyclo [4.2.1.12,5]dec-7-en-10-ol (24k). Colorless oil.
Rf¼0.21 (10% EtOAc/hexanes). 1H NMR (500 MHz, CDCl3)
d 6.60 (d,
J¼5.0 Hz, 1H), 6.44 (d, J¼5.5 Hz, 1H), 4.51e4.49 (m, 1H), 3.89 (d,
J¼12.0 Hz,1H), 2.94 (d, J¼12.0 Hz,1H), 2.32e2.22 (m, 2H),1.81e1.78
(m, 1H), 1.78e1.75 (m, 1H), 1.75e1.67 (m, 1H), 1.63e1.58 (m, 1H),
NMR (125 MHz, CDCl3) d 215.9, 155.9, 149.3, 108.2, 105.4, 62.9, 54.9,
45.7, 43.3, 34.1, 32.3, 27.8, 26.0 (3C), 24.3, 18.4, 16.0, 15.6, ꢂ0.7 (3C),