Thorsten Bach et al.
FULL PAPERS
128.3 (Ph), 127.6 (Ph), 127.4 (Ph), 85.2 (C-7), 82.6 (C-1), 68.2 (CH2Ph),
63.2 (CH2OCO), 51.5 (C-6), 38.1 (C-4), 25.0 (C-5), 23.2 (C-2), 22.7 ppm
(C-3); IR (ATR): n˜ =3065, 3031, 2964, 2871, 1769, 1717, 1601, 1584, 1453,
1268 cmꢀ1; MS (EI, 70 eV): m/z (%)=378 (1) [M+], 91 (100) [C7H7+];
HRMS (EI): C23H22O5 [M+] calcd. 378.1462, found 378.1454.
(%)=417 (2) [M+-91], 91 (100) [C7H7+]; HRMS (EI): C22H29O6Si [M+
-91] calcd. 417.1728, found 415.1745.
(1R*,3S*,4R*,6R*,7R*)-6-Benzoyoxymethyl-7-benzyloxy-3-(tert-butyldi-
metheylsilyl-oxy)-9-oxatricyclo[4.3.0.04,7]nonan-8-one (rac-27a): Rf =0.2
(Pentane/EtOAc=10:1, CAM); m.p.=112–1158C; 1H NMR (500 MHz,
CDCl3): d=8.00 (d, J=7.8 Hz, 2H, COPh), 7.55 (t, J=7.1 Hz, 1H,
COPh), 7.43 (virt. t, J ffi 7.6 Hz, 2H, COPh), 7.40 (d, J=7.8 Hz, 2H,
CH2Ph), 7.33 (virt. t, J ffi 7.5 Hz, 2H, CH2Ph), 7.29 (t, J=7.3 Hz, 1H,
CH2Ph), 5.22 (d, J=11.8 Hz, 1H, CHHPh), 5.03 (s, 1H, H-1), 4.80 (d, J=
11.8 Hz, 1H, CHHPh), 4.52 (d, J=11.8 Hz, 1H, HH-10), 4.45 (virt. t, J
ffi 5.6 Hz, 1H, H-3), 4.39 (d, J=11.8 Hz, 1H, HH-10), 3.02 (virt. t, J
ffi 6.0 Hz, 1H, H-4), 2.34 (dd, J=10.5, 6.7 Hz, 1H, HH-5), 2.21 (ddd, J=
15.3, 6.2, 2.8 Hz, 1H, HH-2), 2.04 (d, J=15.3 Hz, 1H, HH-2), 1.60 (d, J=
10.5 Hz, 1H, HH-5), 0.92 (s, 9H, SiMe2CMe3), 0.09 (s, 3H, SiMe-
MeCMe3), 0.08 ppm (s, 3H, SiMeMeCMe3); 13C NMR (91 MHz, CDCl3):
d=174.0 (C-3), 166.3 (COPh), 138.4 (Ph), 133.2 (Ph), 129.7 (Ph), 129.6
(Ph), 128.5 (Ph), 128.3 (Ph), 127.6 (Ph), 127.4 (Ph), 82.2 (C-7), 81.3 (C-
1), 69.5 (C-3), 67.7 (CH2Ph), 63.0 (C-10), 52.9 (C-6), 46.7 (C-4), 33.5 (C-
2), 25.6 (SiMe2CMe3), 25.1 (C-5), 17.9 (SiMe2CMe3), ꢀ4.9 (SiMe-
MeCMe3), ꢀ5.0 ppm (SiMeMeCMe3); IR (ATR): n˜ =2953, 2929, 2857,
1772, 1720, 1342, 1272 cmꢀ1; MS (EI, 70 eV): m/z (%)=451 (1) [M+-57],
91 (100) [C7H7+]; HRMS (EI): C25H27O6Si [M+-57] calcd. 415.1571,
found 415.1565.
Intramolecular photocycloaddition reaction of butenolide rac-21a: The
reaction of butenolide rac-21a (28.0 mg, 64.7 mmol) in CH2Cl2 (13 mL)
afforded straight product rac-24a (5.0 mg, 18%) and crossed product rac-
25a (13.4 mg, 48%) after flash chromatography (eluent: pentane/
EtOAc=9:1).
(1R*,4R*,6R*,7S*,9R*)-4-Benzyloxy-9-methoxycarbonyl-7-(tert-butyldi-
methylsilyl-oxy)-2-oxatricyclo[4.2.1.04,9]nonan-3-one (rac-24a): Rf =0.39
(Pentane/EtOAc=8:1, CAM); m.p.=103–1058C; 1H NMR (500 MHz,
CDCl3): d=7.36–7.26 (m, 5H, CH2Ph), 5.33 (d, J=4.7 Hz, 1H, H-1), 4.61
(d, J=11.0 Hz, 1H, CHHPh), 4.55 (d, J=11.0 Hz, 1H, CHHPh), 4.49
(virt. t, J ffi 6.4 Hz, 1H, H-7), 3.72 (s, 3H, CO2Me), 3.25 (ddd, J=10.8,
7.2, 3.1 Hz, 1H, H-6), 2.66 (dd, J=12.5, 3.1 Hz, 1H, HH-5), 2.56 (dd, J=
12.5, 10.8 Hz, 1H, HH-5), 2.28 (d, J=15.0 Hz, 1H, HH-8), 1.96 (ddd, J=
15.0, 5.5, 4.7 Hz, 1H, HH-8), 0.90 (s, 9H, SiMe2CMe3), 0.08 (s, 3H, SiMe-
MeCMe3), 0.04 ppm (s, 3H, SiMeMeCMe3); 13C NMR (91 MHz, CDCl3):
d=174.3 (C-3), 168.9 (CO2Me), 137.1 (Ph), 128.3 (Ph), 127.8 (Ph), 127.6
(Ph), 83.6 (C-1), 80.1 (C-4), 71.7 (C-7), 67.9 (CH2Ph), 63.5 (C-9), 52.7
(CO2Me), 44.8 (C-8), 39.2 (C-6), 26.9 (C-5), 25.7 (SiMe2CMe3), 18.1(Si-
Me2CMe3), ꢀ4.9 (SiMeMeCMe3), ꢀ5.2 ppm (SiMeMeCMe3); IR (ATR):
n˜ =2952, 2927, 2856, 1770, 1719, 1498, 1436 cmꢀ1; MS (EI, 70 eV): m/z
(%)=375 (2.8) [M+-57], 91 (100) [C7H7+]; HRMS (EI): C19H23O6Si [M+
-57] calcd. 375.1258, found 375.1256; C19H23O6Si [M+] calcd. 432.1963,
found 432.1951.
Intramolecular photocycloaddition reaction of butenolide rac-21b: The
reaction of rac-21b (28.0 mg, 64.7 mmol) in CH2Cl2 (13 mL) afford
straight product rac-24b (10.0 mg, 36%) and crossed product rac-25b
(11.0 mg, 39%) after flash chromatography (eluent: pentane/EtOAc=
10:1).
(1R*,3S*,4R*,6R*,7R*)-7-Benzyloxy-6-methoxycarbonyl-3-(tert-butyldi-
metheylsilyl-oxy)-9-oxatricyclo[4.3.0.04,7]nonan-8-one (rac-25a): Rf =0.21
(Pentane/EtOAc=8:1, CAM); m.p.=57–598C; 1H NMR (500 MHz,
CDCl3): d=7.40 (d, J=7.1 Hz, 2H, CH2Ph), 7.34 (virt. t, J ffi 7.2 Hz, 2H,
CH2Ph), 7.28 (t, J=7.3 Hz, 1H, CH2Ph), 5.21 (s, 1H, H-1), 4.82 (d, J=
11.6 Hz, 1H, CHHPh), 4.75 (d, J=11.6 Hz, 1H, CHHPh), 4.41 (virt. t, J
ffi 4.5 Hz, 1H, H-3), 3.72 (s, 3H, CO2Me), 2.89–2.82 (m, 2H, HH-5, H-4),
2.18 (ddd, J=15.3, 6.1, 2.8 Hz, 1H, HH-2), 2.05 (dd, J=15.3, 1.5 Hz, 1H,
HH-2), 1.66–1.60 (m, 1H, HH-5), 0.89 (s, 9H, SiMe2CMe3), 0.07 (s, 3H,
SiMeMeCMe3), 0.05 ppm (s, 3H, SiMeMeCMe3); 13C NMR (91 MHz,
CDCl3): d=171.8 (C-8), 169.8 (CO2Me), 137.8 (Ph), 128.3 (Ph), 127.7
(Ph), 127.5 (Ph), 86.3 (C-7), 80.1 (C-1), 69.0 (C-3), 68.0 (CH2Ph), 55.8
(C-6), 52.4 (CO2Me), 47.6 (C-4), 33.4 (C-2), 25.5 (SiMe2CMe3), 24.4 (C-
5), 17.9 (SiMe2CMe3), ꢀ5.0 (SiMeMeCMe3), ꢀ5.1 ppm (SiMeMeCMe3);
(1R*,4R*,6R*,7R*,9R*)-4-Benzyloxy-9-methoxycarbonyl-7-(tert-butyldi-
methylsilyl-oxy)-2-oxatricyclo[4.2.1.04,9]nonan-3-one (rac-24b): Rf =0.56
(Pentane/EtOAc=10:1, CAM); 1H NMR (360 MHz, CDCl3): d=7.40–
7.26 (m, 5H, CH2Ph), 5.42 (dd, J=5.2, 2.0 Hz, 1H, H-1), 4.60 (d, J=
10.9 Hz, 1H, CHHPh), 4.48 (d, J=10.9 Hz, 1H, CHHPh), 4.29 (ddd, J=
6.8, 5.6, 3.3 Hz, 1H, H-7), 3.73 (s, 3H, CO2Me), 3.01 (virt. dt, Jffi11.0,
3.8 Hz, 1H, H-6), 2.83 (dd, J=13.5, 11.0 Hz, 1H, HH-5), 2.45 (ddd, J=
14.6, 5.6, 2.0 Hz, 1H, HH-8), 2.21 (dd, J=13.5, 4.0 Hz, 1H, HH-5), 2.08
(ddd, J=14.6, 6.8, 5.2 Hz, HH-8), 0.85 (s, 9H, SiMe2CMe3), 0.04 ppm (s,
6H, SiMe2CMe3); 13C NMR (91 MHz, CDCl3): d=174.4 (C-3), 168.7
(CO2Me), 136.8 (Ph), 128.4 (Ph), 127.9 (Ph), 127.5 (Ph), 83.3 (C-1), 79.6
(C-4), 78.3 (C-7), 68.2 (CH2Ph), 61.6 (C-9), 52.7 (C-11), 44.6 (C-8), 42.0
(C-6), 32.9 (C-5), 25.6 (SiMe2CMe3), 17.9 (SiMe2CMe3), ꢀ4.87 (SiMe-
MeCMe3), ꢀ4.92 ppm (SiMeMeCMe3); IR (ATR): n˜ =2952, 2935, 2926,
2856, 1777, 1730, 1435 cmꢀ1; MS (EI, 70 eV): m/z (%)=375 (78) [M+
-57], 91 (100) [C7H7+]; HRMS (EI): C19H23O6Si [M+-57] calcd. 375.1258,
found 375.1256.
IR (ATR): n˜ =2960, 2929, 2888, 2854, 1776, 1740, 1453, 1343, 1259 cmꢀ1
;
MS (EI, 70 eV): m/z (%)=375 (45) [M+-57], 91 (100) [C7H7+]; HRMS
(EI): C19H23O6Si [M+-57] calcd. 375.1258, found 375.1251.
Intramolecular photocycloaddition reaction of butenolide rac-23a: The
reaction of rac-23a (30.0 mg, 59.0 mmol) in CH3CN/acetone (11:1, 12 mL)
afforded straight product rac-26a (7.2 mg, 24%) and crossed product rac-
27a (12.6 mg, 42%) after flash chromatography (eluent: pentane/
EtOAc=10:1!8:1).
(1R*,3R*,4R*,6R*,7R*)-7-Benzyloxy-6-methoxycarbonyl-3-(tert-butyldi-
methylsilyl-oxy)-9-oxatricyclo[4.3.0.04,7]nonan-8-one (rac-25b): Rf =0.36
(Pentane/EtOAc=10:1, CAM); m.p.=78–808C; 1H NMR (500 MHz,
CDCl3): d=7.40 (d, J=7.2 Hz, 2H, CH2Ph), 7.36 (t, J=7.2 Hz, 2H,
CH2Ph), 7.30 (t, J=7.2 Hz, 1H, CH2Ph), 5.19 (virt. t, J ffi 2.4 Hz, 1H, H-
1), 4.76 (d, J=11.0 Hz, 1H, CHHPh), 4.56 (d, J=11.0 Hz, 1H, CHHPh),
4.22 (virt. t, J ffi 7.0 Hz, 1H, H-3), 3.72 (s, 3H, CO2Me), 2.87 (dd, J=10.5,
6.4 Hz, 1H, HH-5), 2.67 (dd, J=6.4, 1.5 Hz, 1H, H-4), 2.44 (ddd, J=14.5,
6.7, 2.0 Hz, 1H, HH-2), 2.07 (d, J=10.5 Hz, 1H, HH-5), 1.85 (ddd, J=
14.5, 7.8, 2.8 Hz, 1H, HH-2), 0.85 (s, 9H, SiMe2CMe3), 0.04 (s, 3H, SiMe-
MeCMe3), 0.03 ppm (s, 3H, SiMeMeCMe3); 13C NMR (91 MHz, CDCl3):
d=171.4 (C-8), 169.7 (CO2Me), 137.0 (Ph), 128.4 (Ph), 128.0 (Ph), 127.7
(Ph), 87.9 (C-7), 79.6 (C-1), 68.7 (CH2Ph), 66.2 (C-3), 54.8 (C-6), 52.5
(CO2Me), 46.9 (C-4), 34.3 (C-2), 25.7 (SiMe2CMe3), 21.7 (C-5), 17.9 (Si-
Me2CMe3), ꢀ4.8 (SiMeMeCMe3), ꢀ4.9 ppm (SiMeMeCMe3); IR (ATR):
n˜ =2952, 2933, 2857, 1776, 1738, 1471, 1234 cmꢀ1; MS (EI, 70 eV): m/z
(%)=375 (6) [M+-57], 91 (100) [C7H7+]; HRMS (EI): C19H23O6Si [M+
-57] calcd. 375.1258, found 375.1252; C23H32O6Si [M+] calcd. 432.1963,
found 432.1952.
(1R*,4R*,6R*,7S*,9R*)-9-Benzoyoxymethyl-4-benzyloxy-7-(tert-butyldi-
methylsilyl-oxy)-2-oxatricyclo[4.2.1.04,9]nonan-3-one (rac-26a): Rf =0.40
(Pentane/EtOAc=10:1, CAM); m.p.=79–818C; 1H NMR (500 MHz,
CDCl3): d=7.99 (d, J=8.2 Hz, 2H, COPh), 7.61 (t, J=7.4 Hz, 1H,
COPh), 7.47 (virt. t, J ffi 7.8 Hz, 2H, COPh), 7.37–7.26 (m, 5H, CH2Ph),
4.94 (d, J=4.4 Hz, 1H, H-1), 4.94 (d, J=11.4 Hz, 1H, CHHPh), 4.73 (d,
J=11.4 Hz, 1H, CHHPh), 4.67 (d, J=11.9 Hz, 1H, HH-10), 4.60 (d, J=
11.9 Hz, 1H, HH-10), 4.55 (virt. t, J ffi 5.9 Hz, 1H, H-7), 2.86 (ddd, J=
10.8, 7.1, 3.2 Hz, 1H, H-6), 2.68 (dd, J=12.7, 3.2 Hz, 1H, HH-5), 2.47
(dd, J=12.7, 10.8 Hz, 1H, HH-5), 2.30 (d, J=14.9 Hz, 1H, HH-8), 2.08
(ddd, J=14.9, 5.9, 4.4 Hz, 1H, HH-8), 0.94 (s, 9H, SiMe2CMe3), 0.11 (s,
3H, SiMeMeCMe3), 0.06 ppm (s, 3H, SiMeMeCMe3); 13C NMR
(91 MHz, CDCl3): d=175.9 (C-3), 166.3 (COPh), 137.6 (Ph), 133.4 (Ph),
129.51 (Ph), 129.49 (Ph), 128.6 (Ph), 128.3 (Ph), 127.7 (Ph), 127.5 (Ph),
84.6 (C-1), 77.5 (C-4), 72.2 (C-7), 67.5 (CH2Ph), 62.3 (C-10), 58.3 (C-9),
44.6 (C-8), 38.7 (C-6), 25.7 (SiMe2CMe3), 25.6 (C-5), 18.1 (SiMe2CMe3),
ꢀ4.8 (SiMeMeCMe3), ꢀ5.1 ppm (SiMeMeCMe3); IR (ATR): n˜ =2957,
2950, 2926, 2855, 1769, 1718, 1602, 1453, 1273 cmꢀ1; MS (EI, 70 eV): m/z
Intramolecular photocycloaddition reaction of butenolide rac-22b: The
reaction of rac-22b (24.0 mg, 59.3 mmol) in CH3CN/acetone (11:1, 12 mL)
was irradiated at l=300 nm for 2 h. The reaction mixture was concen-
trated in vacuo to afford a residue, which was purified by flash chroma-
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Chem. Asian J. 0000, 00, 0 – 0
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