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H. Miyauchi et al. / Tetrahedron 64 (2008) 4108e4116
3
ꢁ
ꢁ
ꢁ
˚
a¼89.953(8) , b¼89.898(3) , g¼82.978(7) , V¼2672.1(2) A ,
(4H, ddd, J¼9.0, 5.6, and 3.6 Hz), 4.12 (2H, ddd, J¼12.0, 5.6,
and 3.6 Hz, CH2), 4.38 (2H, ddd, J¼12.0, 5.6, and 3.6 Hz,
CH2), 4.94 (2H, d, J¼11.6 Hz, OCH2), 4.98 (2H, d,
J¼11.6 Hz, OCH2), 5.44 (2H, s, 3-H), 7.33 (2H, d, J¼8.8 Hz,
Ar-H), 7.43 (1H, t, J¼8.8 Hz, Ar-H), 7.43 (1H, s, Ar-H). IR
(KBr) 1690, 1615 cmꢀ1. LRMS m/z 597 (MHþ). Anal. Calcd
for C32H36O11: C, 64.42; H, 6.08. Found: C, 63.60; H, 6.10.
Compound 3c0: oil. 1H NMR (CDCl3) d 1.34(6H, s, Me), 1.52
(6H, s, Me), 2.31 (2H, d, J¼13.2 Hz), 2.74 (2H, dd, J¼13.2 and
1.6 Hz), 3.42 (2H, d, J¼1.6 Hz), 3.59 (4H, t, J¼4.8 Hz), 4.13
(2H, dt, J¼12.0 and 4.8 Hz, CH2), 4.39 (2H, dt, J¼12.0 and
4.8 Hz, CH2), 4.99 (4H, s, OCH2), 5.43 (2H, s, 3-H), 7.34 (2H,
d, J¼8.8 Hz, Ar-H), 7.42 (1H, t, J¼8.8 Hz, Ar-H), 7.43 (1H, s,
Ar-H). IR (KBr) 1690, 1615 cmꢀ1. HRMS (MHþ) calcd for
C32H37O11: m/z 597.2336; found: m/z 597.2340.
Z¼4, rcalcd¼1.374 g/m3, 2qmax¼55.0ꢁ, T¼113(2) K,
R
(Rw)¼0.2050 (0.5008) for 11,885 reflection data with I>2s(I)
and 721 variables, GOF¼1.095.
1
Compound 3b0: oil. H NMR (CDCl3) d 1.33 (6H, s, Me),
1.55 (6H, s, Me), 2.32 (2H, d, J¼13.2 Hz), 2.70 (2H, dd,
J¼13.2 and 2.4 Hz), 3.48 (2H, d, J¼2.4 Hz), 4.31 (2H, m,
CH2), 4.47 (2H, m, CH2), 4.97 (4H, s, OCH2), 5.44 (2H, s,
3-H), 7.31 (2H, d, J¼7.2 Hz, Ar-H), 7.40 (1H, t, J¼7.2 Hz,
Ar-H), 7.46 (1H, s, Ar-H). IR (KBr) 1710, 1630 cmꢀ1
.
HRMS (FAB, MHþ) calcd for C30H33O10: m/z 553.2074;
found: m/z 553.2142.
1
Compound 4b: mp 127e130 ꢁC. H NMR (CDCl3) d 1.33,
1.52 (each 3H, s, Me), 1.54, 1.96 (each 3H, s, Me), 2.10 (1H,
dd, J¼11.6 and 10.4 Hz), 2.31 (1H, d, J¼13.2 Hz), 2.39 (1H,
dd, J¼11.6 and 10.4 Hz), 2.70 (1H, dd, J¼13.2 and 1.6 Hz),
3.33 (1H, dt, J¼10.4 and 1.6 Hz), 3.58 (1H, d, J¼1.6 Hz),
4.29 (1H, d, J¼11.6 Hz), 4.30e4.36 (2H, m, CH2), 4.36 (1H,
d, J¼11.6 Hz), 4.46 (2H, ddd, J¼12.8, 8.8, and 1.2 Hz), 4.56
(2H, ddd, J¼12.8, 8.8, and 1.2 Hz), 4.76 (1H, s, 5-H), 4.99
(1H, d, J¼12.8 Hz, OCH2), 5.14 (1H, d, J¼12.8 Hz, OCH2),
5.35 (1H, s, 3-H), 7.10 (1H, d, J¼7.2 Hz, Ar-H), 7.16 (1H, d,
J¼7.2 Hz, Ar-H), 7.30 (1H, t, J¼7.2 Hz, Ar-H), 7.53 (1H, s,
Ar-H). IR (KBr) 1760, 1710, 1670, 1620 cmꢀ1. HRMS (FAB,
MHþ) calcd for C30H33O10: m/z 553.2074; found: m/z 553.2077.
4.1.5. 2,20,22,35-Tetramethyl-3,7,15,19,24,27,30,33-
octaoxahexacyclo[33.12,35.19,13.120,22.0.01,6.016,21]-
pentatriaconta-5,9,11,13(36),16-pentaen-4,18,23,34-
tetraone (22-exo,35-exo adduct) (3d) (C2 symmetry)
and (3d0) (Cs symmetry)
A solution of 1 (708 mg, 2.00 mmol) with tri(ethylene
glycol)dimethacrylate (2d) (1145 mg, 4.00 mmol) in acetoni-
trile (200 ml) was irradiated in the presence of benzophenone
(182 mg, 1.00 mmol) for 10 h with a 300 W high-pressure mer-
cury lamp using a UV cut filter under 320 nm under a nitrogen
atmosphere at room temperature. After removal of the solvent,
the oily residue was chromatographed by silica gel (eluent:
ethyl acetate/hexane¼2:1, v/v) to give a mixture of 3d and
3d0 (1:1) (286 mg, 22% yield). Compounds 3d and 3d0 were
separated by fractional recrystallization from acetonitrile.
1
Compound 4b0: oil. H NMR (CDCl3) d 1.45, 1.48 (each
3H, s, Me), 1.56, 1.94 (each 3H, s, Me), 2.09 (1H, dd,
J¼11.6 and 10.4 Hz), 2.34 (1H, d, J¼13.2 Hz), 2.35 (1H,
dd, J¼11.6 and 10.4 Hz), 2.73 (1H, dd, J¼13.2 and 1.6 Hz),
3.33 (1H, dt, J¼10.4 and 1.6 Hz), 3.56 (1H, d, J¼1.6 Hz),
4.29 (1H, d, J¼11.6 Hz), 4.30e4.36 (2H, m, CH2), 4.36
(1H, d, J¼11.6 Hz), 4.38 (2H, m), 4.44 (2H, m), 4.81 (1H,
s, 17-H), 4.92 (1H, d, J¼11.6 Hz, OCH2), 5.03 (1H, d,
J¼11.6 Hz, OCH2), 5.47 (1H, s, 5-H), 7.10 (1H, d, J¼7.2 Hz,
Ar-H), 7.16 (1H, d, J¼7.2 Hz, Ar-H), 7.30 (1H, t, J¼7.2 Hz,
Ar-H), 7.56 (1H, s, Ar-H). IR (NaCl) 1760, 1710, 1680,
1630 cmꢀ1. HRMS (FAB, MHþ) calcd for C30H33O10: m/z
553.2074; found: m/z 553.2077.
1
Compound 3d: mp 187e190 ꢁC. H NMR (CDCl3) d 1.37
(6H, s, Me), 1.53 (6H, s, Me), 2.30 (2H, d, J¼13.6 Hz), 2.73
(2H, dd, J¼13.6 and 2.0 Hz), 3.30 (4H, s), 3.40 (2H, d,
J¼2.0 Hz), 3.58 (4H, t, J¼4.4 Hz), 4.20 (2H, dt, J¼12.4 and
4.4 Hz, CH2), 4.31 (2H, dt, J¼12.4 and 4.4 Hz, CH2), 4.91
(2H, d, J¼11.6 Hz, OCH2), 4.95 (2H, d, J¼11.6 Hz, OCH2),
5.46 (2H, s, 3-H), 7.37 (2H, d, J¼7.6 Hz, Ar-H), 7.38 (1H,
s, Ar-H), 7.43 (1H, t, J¼7.6 Hz, Ar-H). IR (KBr) 1690,
1610 cmꢀ1. LRMS m/z 640 (MHþ). Anal. Calcd for
C34H40O12: C, 63.74; H, 6.29. Found: C, 63.73; H, 6.30.
4.1.4. 2,20,22,32-Tetramethyl-3,7,15,19,24,27,30-
heptaoxahexacyclo[30.12,32.19,13.120,22.0.01,6.016,21]-
dotriaconta-5,9,11,13(33),16-pentaen-4,18,23,31-tetraone
(22-exo,32-exo adduct) (3c) (C2 symmetry) and (3c0)
(Cs symmetry)
1
Compound 3d0: oil. H NMR (CDCl3) d 1.37 (6H, s, Me),
1.54 (6H, s, Me), 2.30 (2H, d, J¼13.6 Hz), 2.78 (2H, d,
J¼13.6 Hz), 3.30 (4H, s), 3.42 (2H, s), 3.59 (4H, m), 4.19
(2H, m, CH2), 4.32 (2H, m, CH2), 4.94 (4H, s, OCH2), 5.47
(2H, s, 3-H), 7.38 (2H, d, J¼7.6 Hz, Ar-H), 7.39 (1H, s,
Ar-H), 7.46 (1H, t, J¼7.6 Hz, Ar-H). IR (KBr) 1690,
A solution of 1 (708 mg, 2.00 mmol) with di(ethylene gly-
col)dimethacrylate (2c) (969 mg, 4.00 mmol) in acetonitrile
(200 ml) was irradiated in the presence of benzophenone
(182 mg, 1.00 mmol) for 8 h with a 300 W high-pressure mer-
cury lamp using a UV cut filter under 320 nm under a nitrogen
atmosphere at room temperature. After removal of the solvent,
the oily residue was chromatographed by silica gel (eluent:
ethyl acetate/hexane¼2:1, v/v) to give a mixture of 3c and
3c0 (1:1) (238 mg, 20% yield). Compounds 3c and 3c0 were
separated by fractional recrystallization from acetonitrile.
1610 cmꢀ1
.
HRMS (MHþ) calcd for C34H41O12: m/z
641.2598; found: m/z 641.2607.
4.1.6. 4,18-Dimethyl-3,7,15,19,24,27,30-
heptaoxahexacyclo[30.19,13.0.01,6.06,31.016,21.016,23]-
dotriaconta-4,9,11,13(33),17-pentaen-2,20-dione
(23-exo,31-exo adduct) (5e-xx) (C2 symmetry) and (5e0-xx)
(Cs symmetry), 4,18-dimethyl-3,7,15,19,24,27,30-
heptaoxahexacyclo[30.19,13.0.01,6.06,31.016,21.016,23]-
dotriaconta-4,9,11,13(33),17-pentaen-2,20-dione
1
Compound 3c: mp 241e244 ꢁC. H NMR (CDCl3) d 1.33
(6H, s, Me), 1.53 (6H, s, Me), 2.31 (2H, d, J¼13.2 Hz), 2.73
(2H, dd, J¼13.2 and 2.0 Hz), 3.42 (2H, d, J¼2.0 Hz), 3.58