8610 J . Org. Chem., Vol. 66, No. 25, 2001
Datta et al.
the solution was refluxed under nitrogen atmosphere for
several hours (see Table 1). The reaction mixture was cooled
to room temperature, quenched with 5% aqueous sodium
bicarbonate solution (10 mL), and extracted with CH2Cl2. The
combined organic extracts were washed with brine, dried with
magnesium sulfate, and concentrated in vacuo. The crude
product was purified by silica gel column chromatography
using EtOAc in hexanes to produce pure 1,2-dihydronaphtha-
lene derivatives.
J ) 10.8 Hz), 3.06 (m, 2H), 3.13 (m, 1H), 3.96 (m, 2H), 4.08
(m, 1H, J ) 11.0 Hz), 4.14 (m, 2H), 5.85 (m (AB), 2H), 5.92 (s,
2H), 6.22 (s, 1H), 6.54 (d, 1H, J ) 1.6 Hz), 6.56 (s, 1H), 6.60
(dd, 1H, J ) 1.7, 7.8 Hz), 6.71 (d, 1H, J ) 7.8 Hz); 13C NMR
(CDCl3) δ 13.9, 14.1, 32.4, 43.4, 49.2, 51.5, 60.4, 60.9, 100.8,
100.9, 107.7, 107.9, 109.0, 109.1, 122.6, 127.2, 131.0, 136.8,
146.2, 146.3, 146.6, 147.9, 173.5, 173.9; mass spectrum m/z
(relative intensity) 440 (M+, 32), 366 (47), 263 (26), 235 (21),
220 (12), 135 (22); HRMS calcd for C24H24O8 440.1471 found
440.1473.
The 1H NMR, 13C NMR, and mass spectral properties of
trans-1,2-dihydro-naphthalene-2,3-dicarboxylate derivatives
6a p , 6bq, 6cr , 6et, 6br , 6cr , 6a r , and 6cp were identical to
those previously reported.9,10
Diet h yl
r -1-(3,4-Dim et h oxyp h en yl)-6,7-d im et h oxy-
1,2,3,4-tetr ah ydr on aph th alen e-t-2,c-3-dicar boxylate (8cr ).
Dihydronaphthalene diester (6cr ) (0.15 g, 0.3 mmol) was
stirred with Pd/C (0.023 g, 0.2 mmol) under hydrogen atmo-
sphere for 18 h, as described above, to afford a colorless oil
(0.14 g, 92%). The product was used in the next step without
further purification. 1H NMR (CDCl3) δ 0.96 (t, 3H, J ) 7.1
Hz), 1.24 (t, 3H, J ) 7.1 Hz), 3.00 (t, J ) 10.8 Hz), 3.06-3.24
(m, 3H), 3.57 (s, 3H), 3.79 (s, 3H), 3.84 (s, 3H), 3.86 (s, 3H),
3.92 (m, 2H), 4.12 (m, 2H), 4.14 (d, 1H of C1, J ) 10.7 Hz),
6.22 (s, 1H), 6.59 (d, 2H, J ) 2.2 Hz), 6.68 (dd, 1H, J ) 2.1,
8.2 Hz), 6.78 (d, 1H, J ) 8.2 Hz); 13C NMR (CDCl3) δ 13.9,
14.1, 31.9, 43.4, 49.0, 51.5, 55.8, 55.9, 60.3, 60.9, 110.7, 110.9,
111.9, 112.1, 121.7, 126.2, 129.9, 135.4, 147.5, 147.7, 148.0,
149.0, 173.7, 174.1; mass spectrum m/z (relative intensity) 472
(M+, 50), 398 (42), 325 (100), 269 (22), 236 (20), 151 (29); HRMS
calcd for C26H32O8 472.2097 found 472.2086.
Dieth yl 7-Meth oxy-r -1-(4-m eth oxyp h en yl)-tr a n s-1,2-d i-
h yd r on a p h th a len e-t-2,3-d ica r boxyla te (6d s). The crude
product was purified by column chromatography using 15-
20% EtOAc in hexanes to give a light yellow oil. 1H NMR
(CDCl3) δ 1.13 (t, 3H, J ) 7.1 Hz), 1.29 (t, 3H, J ) 7.1 Hz),
3.74 (s, 3H), 3.76 (s, 3H), 3.98 (d, 1H, J ) 3.4 Hz), 4.07 (m,
2H,), 4.21 (m, 2H), 4.61 (d, 1H, J ) 3.4 Hz), 6.64 (d, 1H, J )
2.5 Hz), 6.75 (d, 2H, J ) 8.7 Hz), 6.79 (dd, 1H, J ) 2.5, 8.3
Hz), 6.97 (d, 2H, J ) 8.7 Hz), 7.28 (d, 1H, J ) 8.4 Hz), 7.67 (s,
1H); 13C NMR (CDCl3) δ 14.0, 14.2, 46.0, 47.3, 55.17, 55.24,
60.6. 61.0, 112.8, 113.9 (2C), 114.8, 122.8, 124.7, 128.7 (2C),
130.6, 134.4, 137.1, 139.3, 158.4, 161.4, 166.7, 172.5; mass
spectrum m/z (relative intensity) 410 (M+, 9), 336 (100), 308
(10), 291 (49), 264 (63), 250 (14), 227 (19), 189 (11), 149 (19),
135 (26), 121 (22); HRMS calcd for 410.1729 C24H26O6 found
410.1741.
Diet h yl 6,7,8-Tr im et h oxyn a p h t h a len e-2,3-d ica r b ox-
yla te (7p ). The crude product was purified by column chro-
matography using 30% EtOAc in hexanes to give a colorless
oil, which solidified on standing, mp 50.0-52.0 °C (from
hexanes/ether). 1H NMR (CDCl3) δ 1.39 (t, 3H, J ) 7.1 Hz),
1.39 (t, 3H, J ) 7.1 Hz), 3.98 (s, 6H), 4.06 (s, 3H), 4.38 (q, 2H,
J ) 7.1 Hz), 4.40 (q, 2H, J ) 7.1 Hz), 6.99 (s, 1H), 8.04 (s, 1H),
8.44 (s, 1H); 13C NMR (CDCl3) δ 14.1, 14.2, 56.0 (CH3), 61.2,
61.4, 61.5, 61.6, 102.8, 124.2, 124.5, 126.6, 128.2, 129.0, 131.0,
142.5, 148,4, 155.2, 167.9, 168.0; mass spectrum m/z (relative
intensity) 362 (M+, 100), 347 (32), 319 (16), 289 (37), 245 (9),
231 (12), 202 (9); HRMS calcd for C19H22O7 362.1365 found
362.1347.
Dieth yl 6,7-Meth ylen ed ioxyn a p h th a len e-2,3-d ica r box-
yla te (7q). The crude product was purified by column chro-
matography using 35% EtOAc in hexanes to give a colorless
viscous oil, which solidified on standing at 4 °C, mp 107.0-
109.0 °C (from hexanes/ether). 1H NMR (CDCl3) δ 1.39 (t, 6H,
J ) 7.1 Hz), 4.39 (q, 4H, J ) 7.1 Hz), 6.01(s, 2H), 7.15 (s, 2H),
8.02 (s, 2H);13C NMR (CDCl3) δ 14.2 (2C), 61.5 (2C), 101.7,
104.4 (2C), 127.6 (2C), 128.7 (2C), 131.0 (2C), 149.7 (2C), 167.9
(2C); mass spectrum m/z (relative intensity) 316 (M+, 42), 271
(6), 243 (100), 149 (31); HRMS calcd for C17H16O6 316.0946
found 316.0934.
Dieth yl 6,7-Dim eth oxyn a p h th a len e-2,3-d ica r boxyla te
(7r ). The crude product was purified by column chromatog-
raphy using 30% EtOAc in hexanes to give a colorless viscous
oil, which solidified on standing at 4 °C, mp 123.0-125.0 °C
(from hexanes/EtOAc). 1H NMR (CDCl3) δ 1.38 (t, 6H, J ) 7.1
Hz), 3.99 (s, 6H), 4.39 (q, 4H, J ) 7.1 Hz), 7.15 (s, 2H), 8.07 (s,
2H);13C NMR (CDCl3) δ 14.2 (2C), 56.0 (2C), 61.5 (2C), 106.7
(2C), 127.3 (2C), 128.2 (2C), 129.5 (2C), 151.4 (2C), 168.0 (2C);
mass spectrum m/z (relative intensity) 332 (M+, 43), 287 (17),
259 (100), 214 (17), 186 (22), 115 (9); HRMS calcd for C18H20O6
332.1259 found 332.1261.
r -1-(3,4-Met h ylen ed ioxyp h en yl)-6,7-m et h ylen ed ioxy-
1,2,3,4-t et r a h yd r on a p h t h a len e-t-2,c-3-d i(h yd r oxym et h -
yl) (9bq). Aryltetralin diester 8bq (0.020 g, 0.05 mmol) was
dissolved in THF (3 mL) and added to a slurry of lithium
aluminum hydride (LAH) (0.024 g, 0.6 mmol) and dry THF (2
mL) at room temperature. The reaction was stirred under N2
for 0.5 h at room temperature and then worked up using
Fieser’s method.38 In succession, 0.06 mL of water, 0.06 mL of
15% aqueous NaOH, and 0.18 mL of water were added to
quench the reaction. The solution was diluted with EtOAc (15
mL), dried with MgSO4, filtered through Celite, and evapo-
1
rated to give an oil (0.016 g, 100%). H NMR (CDCl3) δ 1.71-
1.83 (m, 1H), 1.93-2.03 (m, 1H), 2.55 (br s, 2H) 2.68 (m, 2H),
3.48 (dd, 1H, J ) 5.2, 11.3 Hz), 3.72 (m, 2H), 3.78 (m, 2H),
5.83 (m (AB), 2H), 5.92 (s, 2H), 6.20 (s, 1H), 6.54 (d, 1H, J )
1.8 Hz), 6.55 (s, 1H), 6.64 (dd, 1H, J ) 1.7, 7.8 Hz), 6.74 (d,
1H, J ) 7.8 Hz); 13C NMR (CDCl3) δ 33.6, 39.8, 48.2, 48.3,
62.7, 66.3, 100.6, 100.9, 107.8, 108.0, 109.1, 109.6, 122.8, 129.2,
132.8, 139.1, 145.7, 145.8, 146.2, 148.0; mass spectrum m/z
(relative intensity) 356 (M+, 100), 338 (32), 307 (73), 280 (54),
267 (50), 238 (52), 210 (27), 185 (26), 173 (50), 152 (41), 135
(89), 115 (29), 76 (19); HRMS calcd for C20H20O6 356.1259
found 356.1262.
r -1-(3,4-Dim eth oxyp h en yl)-6,7-d im eth oxy-1,2,3,4-tetr a -
h yd r on a p h th a len e-t-2,c-3-d i(h yd r oxym eth yl) (9cr ). Aryl-
tetralin diester 8cr (0.14 g, 0.3 mmol) was reduced with LAH
(0.066 g, 1.7 mmol) in THF as described above to yield a
colorless amorphous solid (0.10 g, 92%). This compound had
1H NMR, 13C NMR, and mass spectral properties identical to
those reported previously.39
(()-Ca ga ya n in (1). Aryltetralin diol 9bq (0.016 g, 0.05
mmol) was taken up in dry CH2Cl2 (4 mL), and diisopropyl-
ethylamine (0.018 g, 0.1 mmol) added. The flask was purged
with N2 and cooled to -10 °C in a salt/ice water bath. Triflic
anhydride (0.039 g, 0.1 mmol) in CH2Cl2 (0.5 mL) was added
dropwise to the cooled reaction mixture. The reaction mixture
was stirred under N2 for 1.5 h, and water (3 mL) was added
to quench the reaction. The solution was diluted with CH2Cl2
(5 mL) and washed with saturated aqueous NaHCO3 (2 × 10
mL). The organic fraction was dried with MgSO4, filtered, and
evaporated. The crude product was dissolved in THF (2 mL)
and added to a slurry of LAH (0.018 g, 0.5 mmol) in THF (2
mL) at -10 °C. The reaction mixture was stirred under N2 at
room temperature for 45 min and worked up by Fieser’s
Diet h yl r -1-(3,4-Met h ylen ed ioxyp h en yl)-6,7-m et h yl-
en ed ioxy-1,2,3,4-t et r a h yd r on a p h t h a len e-t-2,c-3-d ica r -
boxyla te (8bq). Dihydronaphthalene diester (6bq) (0.032 g,
0.07 mmol) was dissolved in anhydrous EtOH (15 mL), and
Pd/C (0.015 g, 0.1 mmol) was added. The reaction flask was
flushed and evacuated with H2 several times; then the mixture
was stirred at room temperature for 27 h under H2. The
reaction mixture was filtered through Celite and concentrated
to give a light yellow oil (0.020 g, 64%). The product was used
in the next step with no further purification. 1H NMR (CDCl3)
δ 1.01 (t, 3H, J ) 7.1 Hz), 1.25 (t, 3H, J ) 7.1 Hz), 2.97 (t, 1H,
(38) Fieser, L. F.; Fieser, M. In Reagents for Organic Synthesis; J ohn
Wiley and Sons: New York, 1967; Vol. I, p 584.
(39) Charlton, J . L.; Alauddin, M. M. J . Org. Chem. 1986, 18, 3490.