64 J . Org. Chem., Vol. 66, No. 1, 2001
Arisawa et al.
107.5, 78.4, 56.2, 55.8, 38.4, 35.7, 31.1, 17.7; HRMS (EI) calcd
for C16H18O4 (M+) 274.1205, found 274.1205.
6.77 (1H, dd, J ) 8.1, 2.9 Hz), 3.83 (3H, s), 3.76 (3H, s), 3.57
(1H, t, J ) 7.0 Hz), 2.87-2.80 (2H, m), 2.24 (3H, s), 2.15-2.05
(2H, m); 13C NMR (75.0 MHz, CDCl3) δ 202.5, 169.7, 163.1,
145.6, 139.5, 133.5, 131.6, 131.4, 116.8, 116.6, 115.5, 109.8,
3′,4′-Dih yd r o-6′,7′-d im et h oxysp ir o[cycloh exa n e-1,1′-
2′H-n a p h th a len e]-2,6-d ion e (8). Prepared from 7 (87.0 mg,
0.300 mmol), PIFA (129 mg, 0.300 mmol), and CF3CH2OH
(6.00 + 6.00 mL) (60.0 mg, 70%, column chromatography, SiO2;
n-hexane/EtOAc ) 1:1): colorless crystal; mp 139-140 °C
(EtOAc); IR (KBr) 2940, 1725, 1695, 1520 cm-1; 1H NMR (500
MHz, CDCl3) δ 6.60 (1H, s), 5.98 (1H, s), 3.84 (3H, s), 3.75
(3H, s), 2.99-2.92 (2H, m), 2.74-2.69 (4H, m), 2.30-2.22 (1H,
m), 2.18-2.16 (2H, m), 2.03-1.93 (1H, m), 1.78-1.73 (2H, m);
13C NMR (75.0 MHz, CDCl3) δ 209.7, 148.5, 147.1, 130.9, 124.1,
113.0, 111.5, 71.3, 56.0, 55.6, 38.0, 34.4, 28.8, 18.9, 17.7; HRMS
(EI) calcd for C17H20O4 (M+) 288.1361, found 288.1351. Anal.
Calcd for C17H20O4: C, 70.81; H, 6.99. Found: C, 70.69; H,
6.90.
58.2, 55.6, 52.6, 36.4, 29.3, 28.6; HRMS (FAB) calcd for C20H22
-
IO4 (M+ - CF3COO-) 453.0563, found 453.0571.
Iod on iu m Sa lt 13c. Compound 13c was obtained in 69%
(161 mg) as a pale yellow oil by the reaction of compound 12c
(0.4 mmol, 106 mg) with PIFA (0.44 mmol, 190 mg) in (CF3)2-
CHOH (1.5 mL): IR (KBr) 3500(br), 3000, 2950, 1740, 1710,
1
1680, 1560 cm-1; H NMR (300 MHz, CDCl3) δ 7.99 (1H, d, J
) 8.8 Hz), 7.87 (2H, d, J ) 7.9 Hz), 7.47-7.43 (1H, m), 7.37-
7.31 (2H, m), 6.91 (1H, d, J ) 3.0 Hz), 6.78-6.74 (1H, dd, J )
8.5, 2.7 Hz), 4.25-4.17 (2H, q, J ) 7.0 Hz), 3.82 (3H, s), 3.54
(1H, t, J ) 7.0 Hz), 2.89-2.82 (2H, m), 2.24 (3H, s), 2.15-2.04
(2H, m), 1.28 (3H, t, J ) 7.0 Hz); 13C NMR (75.0 MHz, CDCl3)
δ 202.6, 169.2, 162.9, 145.5, 139.4, 133.2, 131.4, 130.9, 118.5,
116.7, 115.4, 111.6, 61.7, 58.5, 55.6, 36.4, 29.3, 28.5, 14.1;
HRMS (EI) calcd for C21H24IO4 (M+ - CF3COO-) 467.0719,
found 467.0722.
6′-Meth oxysp ir o[in d a n -2,1′-in d a n ]-1,3-d ion e (10). Pre-
pared from 5 (24.0 mg, 0.0860 mmol), PIFA (37.0 mg, 0.0860
mmol), and CF3CH2OH (2.00 + 2.00 mL) (8.00 mg, 33%,
preparative thin-layer chromatography, SiO2; CH2Cl2/MeOH
) 100:1): yellow crystal; mp 164-165 °C (EtOAc); IR (KBr)
Iod on iu m Sa lt 13d . Compound 13d was obtained in 73%
(225 mg) yield as a pale yellow oil by the reaction of compound
12d (0.53 mmol, 140 mg) with PIFA (0.64 mmol, 274 mg) in
(CF3)2CHOH (1.5 mL): IR (KBr) 2900, 1740, 1710, 1680, 1580,
1560, 1470, 1440 cm-1; 1H NMR (300 MHz, CDCl3) δ 8.00 (1H,
d, J ) 8.8 Hz), 7.82 (2H, d, J ) 7.6 Hz), 7.50 (1H, t, J ) 7.3
Hz), 7.38 (2H, t, J ) 7.3 Hz), 6.90 (1H, d, J ) 2.7 Hz), 6.78-
6.74 (1H, dd, J ) 8.8, 3.0 Hz), 3.83 (3H, s), 3.72 (3H, s), 3.44
(1H, t, J ) 7.0 Hz), 2.82 (2H, t, J ) 7.6 Hz), 2.21 (3H, s), 1.85-
1.83 (2H, m), 1.62-1.52 (2H, m); 13C NMR (75.0 MHz, CDCl3)
δ 202.8, 169.9, 163.2, 146.1, 139.5, 133.3, 131.7, 131.3, 116.8,
116.2, 115.1, 109.2, 58.9, 55.6, 52.4, 38.5, 29.1, 28.0, 27.3;
HRMS (EI) calcd for C21H24IO4 (M+ - CF3COO-) 467.0719,
found 467.0710.
1745, 1705, 1595, 1490 cm-1 1H NMR (270 MHz, CDCl3) δ
;
8.08-8.04 (2H, m), 7.92-7.88 (2H, m), 6.87 (1H, d, J ) 2.5
Hz), 6.61 (1H, dd, J ) 8.4, 2.5 Hz), 6.52 (1H, d, J ) 8.4 Hz),
3.76 (3H, s), 3.28 (2H, t, J ) 7.4 Hz), 2.56 (2H, t, J ) 7.4 Hz);
13C NMR (67.5 MHz, CDCl3) δ 201.7, 160.2, 147.3, 142.5, 135.8,
123.8, 123.3, 113.1, 110.4, 55.4, 33.2, 32.2; HRMS (EI) calcd
for C18H14O3 (M+) 278.0943, found 278.0943. Anal. Calcd for
C
18H14O3: C, 77.68; H, 5.07. Found: C, 77.90; H, 5.14.
Gen er a l P r oced u r e for th e Syn th esis of Dica r bon yl
Com p ou n d s 12. A slurry of 2-(3-methoxyphenyl)-1-iodoethane
or 3-(3methoxyphenyl)-1-iodopropane (1.00 equiv), dicarbonyl
compound (0.900 or 1.00 equiv) and potassium carbonate (2.50
equiv) in dry acetone (10.0 mL for 1 mmol of starting material)
was refluxed (bath temperature 70 °C), and the progress of
the reaction was monitored by TLC. When TLC indicated the
disappearance of starting material the reaction was stopped.
The reaction mixture was then cooled to room temperature,
quenched with water, and extracted with EtOAc. The organic
layer was washed with brine, dried over anhydrous Na2SO4,
filtered, and concentrated. Purification by column chromatog-
raphy over silica gel (n-hexane/EtOAc ) 4:1) afforded the
corresponding products 12.
Gen er a l P r oced u r e for th e Rea ction of Dica r bon yl
Com p ou n d s 12 w ith P IF A. To a solution of the dicarbonyl
compound 12 (1 equiv) in (CF3)2CHOH at room temperature
under N2 atmosphere was added slowly PIFA (1.1 equiv) over
a period of 10 to 15 min. The reaction mixture was then stirred
at room temperature until TLC indicated the absence of
starting material (approximately 10 min). The solvent evapo-
rated, and product was purified by column chromatography
over silica (CH2Cl2/MeOH ) 10:1) to give the diaryliodonium
salts 13.
Iod on iu m Sa lt 13e. Compound 13e was obtained in a yield
of 96% (178 mg) by the reaction of compound 12e (0.64 mmol,
178 mg) with PIFA (0.7 mmol, 302 mg) in (CF3)2CHOH (2.5
mL) as a pale yellow viscous liquid: IR (KBr) 2900, 1710, 1680,
1
1580, 1560 cm-1; H NMR (300 MHz, CDCl3) δ 7.99 (1H, d, J
) 8.5 Hz), 7.80 (2H, d, J ) 7.3 Hz), 7.53-7.50 (1H, m), 7.41-
7.36 (2H, m), 6.90 (1H, d, J ) 2.7 Hz), 6.79-6.75 (1H, dd, J )
11.9, 3.0 Hz), 4.19 (2H, q, J ) 7.3 Hz), 3.83 (3H, s), 3.42 (1H,
t, J ) 7.0 Hz), 2.82 (2H, t, J ) 7.6 Hz), 2.21 (3H, s), 1.88-1.82
(2H, m), 1.60-1.54 (2H, m), 1.26 (3H, t, J ) 7.3 Hz); 13C NMR
(75.0 MHz, CDCl3) δ 202.9, 169.4, 163.2, 146.1, 139.5, 133.3,
131.7, 131.4, 116.8, 116.3, 115.1, 109.2, 61.5, 59.1, 55.6, 38.5,
29.1, 28.0, 27.3, 14.0; HRMS (EI) calcd for C22H26IO4 (M+
-
CF3COO-) 481.0876, found 481.0876.
Gen er a l P r oced u r e for th e Ba se-In d u ced Cycliza tion
of th e Dia r yliod on iu m Sa lts 13. To a flame-dried two-
necked flask, cooled under nitrogen atmosphere, were added
KOtBu (1.2 equiv) and dry THF (1.00 mL for 1.00 mmol scale).
A solution of the iodonium salt (1 equiv) in THF (2.00 mL for
1 mmol scale) was then added dropwise through a cannula
over a period of 15 min. The reaction mixture was then stirred
at room temperature for 30 min, after which time TLC
indicated the disappearance of starting material. The solvent
was evaporated, and the residue was purified by column
chromatography over silica (n-hexane/EtOAc ) 4:1) to afford
the cyclized products 14.
Iod on iu m Sa lt 13a . Iodonium salt 13a was obtained in
64% (146 mg) yield by the reaction of 12a (0.39 mmol, 105
mg) with PIFA (0.43 mmol, 186 mg) in (CF3)2CHOH (1.00
mL): pale yellow oil; IR (KBr) 3500, 2950, 1730, 1680, 1590,
1
1570 cm-1; H NMR (300 MHz, CDCl3) δ 7.95 (1H, d, J ) 8.5
Hz), 7.81 (2H, dd, J ) 8.2, 1.0 Hz), 7.43-7.38 (1H, m), 7.38-
7.25 (2H, m), 6.83 (1H, d, J ) 3.0 Hz), 6.70 (1H, dd, J ) 8.8,
3.0 Hz), 3.73 (3H, s), 3.66 (6H, s), 3.37 (1H, t, J ) 7.3 Hz),
2.83-2.78 (2H, m), 2.09-2.01 (2H, m); 13C NMR (75.0 MHz,
CDCl3) δ 169.1, 162.9, 145.2, 139.5, 133.5, 131.4, 131.1, 116.8,
116.6, 115.2, 109.9, 55.5, 52.6, 50.5, 36.1, 29.3; HRMS (FAB)
calcd for C20H22IO5 (M+ - CF3COO-) 469.0512, found 469.0537;
HRMS (FAB) calcd for C2F3O2 (CF3COO-) 112.9850, found
112.9877. Anal. Calcd for C22H22F3IO7: C, 45.38; H, 3.81.
Found: C, 45.40; H, 4.09.
1,1-Dim eth oxyca r bon yl-5-m eth oxyin d a n e (14a ). The
cyclized product 14a was obtained in 65% (32 mg) yield by
the reaction of iodonium salt 13a (0.19 mmol, 108 mg) with
KOtBu (0.22 mmol, 25 mg) as a colorless oil: IR (KBr) 2900,
1740, 1600, 1580, 1500 cm-1 1H NMR (300 MHz, CDCl3) δ
;
7.45 (1H, d, J ) 8.5 Hz), 6.81-6.75 (2H, m), 3.80 (3H, s), 3.74
(6H, s), 3.00 (2H, t, J ) 7.0 Hz), 2.70 (2H, t, J ) 7.0 Hz); 13C
NMR (75.0 MHz, CDCl3) δ 171.4, 160.3, 146.0, 131.1, 127.3,
113.0, 109.4, 64.7, 55.3, 52.8, 34.6, 31.0; HRMS (EI) calcd for
Iod on iu m Sa lt 13b. Iodonium salt 13b was obtained as a
pale yellow viscous liquid by the reaction of 12b (0.8 mmol,
200 mg) with PIFA (0.88 mmol, 379 mg) in (CF3)2CHOH (1.5
mL) in 84% (382 mg) yield: pale yellow viscous liquid; IR (KBr)
C
14H16O5 (M+) 264.0998, found 264.1033.
1-Acetyl-1-m eth oxyca r bon yl-5-m eth oxyin d a n e (14b).
Compound 14b was obtained as a colorless oil in 75% (56 mg)
yield by the reaction of iodonium salt 13b (0.3 mmol, 172 mg)
with KOtBu (0.36 mmol, 41 mg): IR (KBr) 2900, 1740, 1710,
2950, 1750, 1720, 1570 cm-1 1H NMR (300 MHz, CDCl3) δ
;
8.00 (1H, d, J ) 9.1 Hz), 7.85 (2H, d, J ) 7.3 Hz), 7.50 (1H, t,
J ) 7.7 Hz), 7.37 (2H, t, J ) 8.1 Hz), 6.91 (1H, d, J ) 2.9 Hz),
1
1600, 1500 cm-1; H NMR (300 MHz, CDCl3) δ 7.38(1H, d, J