S. S. Hussaini et al. / Tetrahedron Letters 48 (2007) 775–778
777
7. Moricnoni, E. J.; Connor, W. F. O.; Kuhn, L. P.;
Keneally, E. A.; Wallenberger, F. T. J. Am. Chem. Soc.
1959, 81, 6472–6477.
ment of diol 6 was studied as before giving compound 7
as a white solid.12 The IR spectrum showed a broad
peak at 3390 cmÀ1 for the OH and absence of carbonyl
1
8. Tandem dianionic oxy-Cope rearrangement/transannular
reaction of 1 (Table 1, entry 1): A solution of 1 (0.169 g,
0.0005 mol) in dry THF (5 ml) was added to a suspension
of t-BuOK (0.560 g, 0.005 mol) in dry THF (5 ml). The
mixture was stirred under N2 at rt for 3 h and quenched
with a satd solution of NH4Cl (10 ml). The product was
extracted into diethyl ether (3 · 10 ml) and the combined
organic phases were washed with water, dried over anhyd
Na2SO4 and evaporated. Purification of the residue by
column chromatography on silica gel, with ethyl acetate/
hexane (0.5:10 ) as eluent afforded the diol 2 as a white
solid (mp 119–120 ꢁC), (0.005 g), 30% yield. Further
elution with ethyl acetate/hexane (2:10) gave a pale yellow
solid 3 (mp 113–114 ꢁC), (0.010 g) 60% yield. Compound
stretching. The H NMR showed a D2O exchangeable
signal at d 6.0 (2H, s) for the OH and at d 7.25 (2H, s)
for the methine protons. The 1H coupled 13C NMR
spectrum showed a doublet at d 115.4 for both C–OH
carbons. The mass spectrum showed a molecular ion
peak at m/z 364.49.
We observed formation of a transannular product in
addition to the usual oxy-Cope product, only in the case
of 1,2-diphenylacenaphthene-1,2-diol 2. The polycyclic
compounds 2, 5 and 7 were isolated as diastereomers.
The best yields of the products were obtained with t-
BuOK as the base and t-BuOH as solvent (method B).
We presume that the higher polarity of the solvent is
the reason for the greater yield of the products via this
method. Further work is being carried out in our labo-
ratory on these lines.
1
2: IR (KBr, cmÀ1) 3501, 1596, 1494, 1446, 1024, 714; H
NMR (400 MHz, CDCl3/TMS) d (ppm) 1.57 (2H, s, D2O
exchangeable), 6.6 (2H, s), 6.8–8.0 (14H, m); 13C NMR
(100 MHz, CDCl3) d (ppm) 134.21, 132.95, 130.70, 129.23,
128.95, 128.59, 128.42, 128.16, 126.39, 125.61, 123.02,
73.87. HRMS: calcd for C24H18O2, (M+): 338.4024.
Found: 338.4020. Anal. Calcd for C24H18O2: C, 85.18;
H, 5.36. Found: C, 85.14; H, 5.41. Compound 3: IR (KBr,
cmÀ1) 3532, 1654, 1577, 1449, 1271, 771, 715; 1H NMR
(400 MHz, CDCl3/TMS) d (ppm) 3.30 (1H, s, D2O
In conclusion our work reports an easy route to the syn-
thesis of functionalized polycyclic compounds from sim-
ple starting materials via a novel diaromatic dianionic
oxy-Cope rearrangement.
3
exchangeable), 3.32 (1H, d, J = 4.10 Hz), 6.6–8.02 (14H,
m); 13C NMR (100 MHz, CDCl3) d (ppm), 198.12, 144.22,
140.78, 137.95, 137.27, 135.66, 135.22, 133.14, 132.82,
132.26, 130.73, 130.33, 129.26, 128.88, 128.62, 128.42,
127.51, 127.09, 126.71, 125.92, 125.20, 123.32, 98.97,
74.14. HRMS: calcd for C24H16O2, (M+): 336.3868.
Found: 336.3872 (10%). Anal. Calcd for C24H16O2: C,
85.69; H, 4.79. Found: C, 85.61; H, 4.82.
Acknowledgements
We thank the management of the New College, Chen-
nai, for providing the necessary facilities. Our sincere
thanks are also due to SPIC Science Foundation, Chen-
nai and to SAIF, IIT, Chennai, for recording the high
resolution spectra.
9. Santora, V. J.; Moore, H. W. J. Am. Chem. Soc. 1995, 117,
8486–8490; Rao, C. S. S.; Kumar, G.; Rajagopalan, K.;
Swaminathan, S. Tetrahedron 1982, 38, 2195–2202; Sathya-
moorthi, G.; Thangaraj, K.; Srinivasan, P. C.; Swami-
nathan, S. Tetrahedron Lett. 1989, 30, 4427–4430.
10. Dianionic oxy-Cope rearrangement of 4 (Table 1, entry 5):
A solution of 4 (0.200 g, 0.0005 mol) in dry t-BuOH
(10 ml) was added to a suspension of t-BuOK (0.560 g,
0.005 mol) in dry t-BuOH (10 ml).The mixture was
refluxed under N2 for 4 h and then quenched with a satd
solution of NH4Cl (10 ml). The product was extracted into
diethyl ether (3 · 10). The ether layer was washed with
water, dried over anhyd Na2SO4 and evaporated. Purifi-
cation of the residue by column chromatography on silica
gel, with ethyl acetate/hexane (1:10) as eluent afforded the
diol 5 as a white solid (mp 118–120 ꢁC), (0.074 g) 62%
yield. IR (KBr, cmÀ1) 3435 (br), 2958, 1607, 1251, 824; 1H
NMR (400 MHz, CDCl3/TMS) d (ppm) 1.61 (2H, br s,
D2O exchangeable), 3.82 (3H, s), 3.84 (3H, s), 6.55 (2H, s)
6.85–7.8 (12H, m); 13C NMR (100 MHz, CDCl3) d (ppm)
132.1, 132.0, 130.20, 127.70, 127.66, 126.71, 125.58, 124.0,
122.0, 113.96, 113.41, 73.0, 55.29, 55.32. HRMS: calcd for
C26H22O4, (M+): 398.4536. Found: 398.4539. Anal. Calcd
for C26H22O4: C, 78.37; H, 5.56. Found: C, 78.31; H, 5.60.
11. Hussaini, S. S.; Sriraman, V.; Huq, C. A. M. A. J. Indian
Chem. Soc 2004, 81, 249–250.
Supplementary data
Supplementary data associated with this article can
References and notes
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12. Dianionic oxy-Cope rearrangement of 6 (Table 1, entry
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