T. Shibata et al. / Tetrahedron 58 (2002) 8661–8667
8665
NMR (CDCl3) d (ppm)¼57.4, 87.6, 105.1, 128.0, 130.0,
133.0, 135.5; IR (KBr disk) 2175 cm21; HRMS found m/z
610.2139, calcd for C42H34OSi2: 610.2148.
4.4.10. 4,4-Bis(benzyloxycarbonyl)-1,7-bis[(4-methoxy-
carbonyl)phenyl]hepta-1,6-diyne (3f). Pale yellow solid.
1
Mp 106–1078C. H NMR (CDCl3) d (ppm)¼3.32 (s, 4H),
3.91 (s, 6H), 5.20 (s, 4H), 7.27–7.34 (m, 14H), 7.91–7.95
(m, 4H); 13C NMR (CDCl3) d (ppm)¼23.9, 52.2, 57.1, 67.7,
83.4, 86.9, 127.5, 128.1, 128.4, 128.5, 129.3, 129.4, 131.6,
135.0, 166.5, 168.4; IR (CH2Cl2) 1730, 1741 cm21; HRMS
found m/z 628.2100, calcd for C39H32O8: 628.2097.
4.4.2. 1,8-Bis(triphenylsilylethynyl)naphthalene (1b).
1
Light pink solid. Mp 192.5–193.08C. H NMR (CDCl3)
d (ppm)¼7.08–7.16 (m, 12H), 7.24–7.32 (m, 6H),
7.41–7.54 (m, 14H), 7.86 (dd, 2H, J¼1.4, 8.2 Hz), 7.95
(dd, 2H, J¼1.4, 7.2 Hz); IR (KBr disk) 2137 cm21. Anal.
found C, 86.65; H, 5.21%, calcd for C50H36Si2: C, 86.66; H,
5.24%.
4.4.11. 4,4-Bis(benzyloxycarbonyl)-1,7-dimethylhepta-
1
1,6-diyne (3i). Colorless oil. H NMR (CDCl3) d (ppm)¼
1.67 (t, 6H, J¼2.5 Hz), 2.94 (q, 4H, J¼2.5 Hz), 5.13 (s, 4H),
7.25–7.32 (m, 10H); 13C NMR (CDCl3) d (ppm)¼3.4, 22.9,
57.2, 67.3, 73.1, 79.1, 128.0, 128.2, 128.4, 135.3, 169.0; IR
(neat) 1735 cm21; HRMS found m/z 388.1687, calcd for
C25H24O4: 388.1675.
4.4.3. 2,4-Bis(triphenylsilyl)-7-oxabicyclo[3.3.0]octa-1,4-
dien-3-one (2a). Yellow solid. Mp 211.5–212.08C (dec). 1H
NMR (CDCl3) d (ppm)¼3.69 (s, 4H), 7.31–7.43 (m, 18H),
7.54–7.58 (m, 12H); IR (KBr disk) 1585, 1693 cm21; lmax
(CH3CN) 258 nm (1 5700), 396 nm (1 1400); HRMS found
m/z 638.2079, calcd for C43H34O2Si2: 638.2097.
4.4.12. 4,4-Bis(benzyloxycarbonyl)-1,7-bis(trimethyl-
silyl)hepta-1,6-diyne (3j). Colorless oil. 1H NMR
(CDCl3) d (ppm)¼0.11 (s, 18H), 3.04 (s, 4H), 5.12 (s,
4H), 7.25–7.33 (m, 10H); 13C NMR (CDCl3) d (ppm)¼
20.1, 24.0, 57.2, 67.4, 88.5, 100.9, 127.9, 128.2, 128.5,
135.2, 168.3; IR (neat) 1742, 2176 cm21; HRMS found m/z
504.2148, calcd for C29H36O4Si2: 504.2152.
4.4.4. 1-Oxo-2,5-bis(triphenylsilyl)cyclopenta-1,4-
dieno[3,4-a]acenaphthene (2b). Red solid. Mp .3008C.
1H NMR (CDCl3) d (ppm)¼6.00 (d, 2H, J¼7.2 Hz), 7.04 (d,
1H, J¼7.4 Hz), 7.08 (d, 1H, J¼7.4 Hz), 7.28–7.46 (m,
20H), 7.63–7.67 (m, 12H); IR (KBr disk) 1556, 1672 cm21
.
Anal. found C, 85.22; H, 5.01%, calcd for C51H36OSi2: C,
84.96; H, 5.03%.
4.4.13. 7,7-Bis(benzyloxycarbonyl)-2,4-diphenylbicyclo-
[3.3.0]octa-1,4-dien-3-one (4a). Purple solid. Mp 133.08C
(dec). 1H NMR (CDCl3) d (ppm)¼3.51 (s, 4H), 5.15 (s, 4H),
7.18–7.41 (m, 16H), 7.60–7.64 (m, 4H); IR (CH2Cl2)
1712, 1732 cm21; lmax (CH3CN) 257 nm (1 42000),
497 nm (1 3600); HRMS found m/z 540.1917, calcd for
C36H28O5: 540.1937.
4.4.5. 4,4-Bis(benzyloxycarbonyl)-1,7-diphenylhepta-
1,6-diyne (3a). Colorless oil. 1H NMR (CDCl3) d
(ppm)¼3.31 (s, 4H), 5.19 (s, 4H), 7.24–7.27 (m, 20H);
13C NMR (CDCl3) d (ppm)¼23.8, 57.4, 67.6, 83.8, 83.9,
110.0, 123.0, 128.0, 128.1, 128.3, 128.5, 131.7, 135.2,
168.6; IR (neat) 1739 cm21; HRMS found m/z 512.1978,
calcd for C35H28O4: 512.1988.
4.4.14. 2,4-Diphenyl-7,7-bis(ethoxycarbonyl)bicyclo-
[3.3.0]octa-1,4-dien-3-one (4b). Red purple solid. Mp
1
4.4.6. 1,7-Diphenyl-4,4-bis(ethoxycarbonyl)hepta-1,6-
diyne (3b). Spectral data were accorded with those in the
literature.25
137.08C (dec). H NMR (CDCl3) d (ppm)¼1.28 (t, 6H,
J¼7.1 Hz), 3.52 (s, 4H), 4.24 (q, 4H, J¼7.1 Hz), 7.24–7.44
(m, 6H), 7.65–7.69 (m, 4H); IR (neat) 1727 cm21; lmax
(CH3CN) 258 nm (1 45000), 495 nm (1 4700); HRMS
found m/z 416.1621, calcd for C26H24O5: 416.1624.
4.4.7. 4,4-Bis(tert-butoxycarbonyl)-1,7-diphenylhepta-
1
1,6-diyne (3c). White solid. Mp 1428C. H NMR (CDCl3)
d (ppm)¼1.49 (s, 18H), 3.15 (s, 4H), 7.25–7.40 (m, 10H);
13C NMR (CDCl3) d (ppm)¼23.5, 27.8, 57.8, 81.9, 83.3,
84.7, 123.3, 127.8, 128.1, 131.6, 168.0; IR (CH2Cl2)
; HRMS found m/z 444.2297, calcd for
C29H32O4: 444.2301.
4.4.15. 7,7-Bis(tert-buthoxycarbonyl)-2,4-diphenylbicyclo-
[3.3.0]octa-1,4-dien-3-one (4c). Red purple solid. Mp
1
190.08C (dec). H NMR (CDCl3) d (ppm)¼1.47 (s, 18H),
1731 cm21
3.40 (s, 4H), 7.29–7.42 (m, 6H), 7.65–7.69 (m, 4H); 13C
NMR (CDCl3) d (ppm)¼27.8, 35.8, 63.8, 82.5, 119.5,
127.2, 128.1, 128.5, 131.5, 158.7, 169.7, 201.9; IR (CH2Cl2)
1697, 1717 cm21; lmax (CH3CN) 258 nm (1 34000),
495 nm (1 3200). Anal. found C, 76.18; H, 6.84%, calcd
for C30H32O5: C, 76.25; H, 6.82%.
4.4.8. 4,4-Bis(benzyloxycarbonyl)-1,7-bis(4-methoxy-
phenyl)hepta-1,6-diyne (3d). Colorless oil. 1H NMR
(CDCl3) d (ppm)¼3.30 (s, 4H), 3.74 (s, 6H), 5.17 (s, 4H),
6.74–6.78 (m, 4H), 7.21–7.25 (m, 14H); 13C NMR (CDCl3)
d (ppm)¼23.7, 55.1, 57.4, 67.4, 82.3, 83.7, 113.6, 115.1,
127.9, 128.2, 128.4, 133.0, 135.2, 159.3, 168.7; IR (CH2Cl2)
4.4.16. 7,7-Bis(benzyloxycarbonyl)-2,4-bis(4-methoxy-
phenyl)bicyclo[3.3.0]octa-1,4-dien-3-one (4d). Red purple
1746 cm21
;
C37H32O6: 572.2199.
HRMS found m/z 572.2209, calcd for
solid. Mp 136.08C (dec). H NMR (CDCl3) d (ppm)¼3.46
1
(s, 4H), 3.82 (s, 6H), 5.14 (s, 4H), 6.91 (d, 4H, J¼9.0 Hz),
7.18–7.32 (m, 10H), 7.57 (d, 4H, J¼9.0 Hz); IR (CH2Cl2)
1604, 1716, 1737 cm21; lmax (CH3CN) 265 nm (1 50000),
497 nm (1 4500); HRMS found m/z 600.2133, calcd for
C38H32O7: 600.2148.
4.4.9. 4,4-Bis(benzyloxycarbonyl)-1,7-bis(4-chlorophenyl)-
1
hepta-1,6-diyne (3e). Colorless oil. H NMR (CDCl3) d
C
(ppm)¼3.27 (s, 4H), 5.18 (s, 4H), 7.20–7.27 (m, 18H); 13
NMR (CDCl3) d (ppm)¼23.8, 57.2, 67.6, 82.9, 84.8, 121.3,
128.1, 128.3, 128.4, 128.5, 132.9, 134.0, 135.1, 168.5; IR
(CH2Cl2) 1739 cm21; HRMS found m/z 580.1207, calcd for
C35H26Cl2O4: 580.1208.
4.4.17. 7,7-Bis(benzyloxycarbonyl)-2,4-bis(4-chloro-
phenyl)bicyclo[3.3.0]octa-1,4-dien-3-one (4e). Purple
1
solid. Mp 177.08C (dec). H NMR (CDCl3) d (ppm)¼3.47