A. S. K. Hashmi et al.
FULL PAPER
added to quench the reaction, and the resulting mixture was stirred for
d 10.9 (q), 22.7 (q), ±±.1 (d), 48.2 (t), 12±.6 (d), 124.4 (d), 125.0 (s), 1±6.1
0
.5 h. After removing most of the CH
column chromatography on silica gel (10% CH
give 7b (410 mg, 77%). IR (neat): nÄ ±262, 1681 cm
±00 MHz, CDCl
2
Cl
2
, the residue was purified by
(s), 154.5 (s), 156.5 (s), 210.8 (s); MS: m/z (%): 176 [M 3 (69), 161 (100);
2
Cl /petroleum ether) to
2
HRMS: m/z: calcd for C11
H
11
O
2
: 176.08±7 [M 3, found: 176.08±7.
À1
1
;
H
NMR
): d 1.27 (d, ±H, J 7.0 Hz), 2.24 (s, ±H), 2.70 (dd,
H, J 16.±, 8.1 Hz), ±.00 (dd, 1H, J 16.±, 6.0 Hz), ±.2± (s, 1H), ±.45 (m,
2
,2,8-Trimethyl-4,5-dihydro-2H-cyclopenta[de]chromene (11a): A solution
(
1
1
±
of indanone 8a (162 mg, 1.00 mmol) in dry THF (4 mL) was added
dropwise to a solution of 2-methyl-1-propenylmagnesium bromide (0.5m in
THF, 20.0 mL, 10.0 mmol) at 08C, and the resulting solution was stirred for
1
±
H), 5.8± (dd, 1H, J 2.9, 1.2 Hz), 5.87 (d, 1H, J ±.0 Hz); C NMR
(
75.5 MHz, CDCl
±
): d 1±.9 (q), 19.1 (q), 29.5 (d), 51.5 (t), 79.1 (s), 81.8 (d),
1.5 h. After quenching the reaction with ice, the mixture was filtered
1
05.2 (d), 106.2 (d), 151.1 (s), 156.6 (s), 186.2 (s); MS: m/z (%): 176 [M 3
through a silica gel pad, which was then thoroughly washed with diethyl
ether. The phases of the filtrate were separated, and the aqueous phase was
extracted with diethyl ether. The combined organic portions were then
(
12 2
±1), 109 (100); elemental analysis (%) calcd for C11H O : C 74.98, H 6.86;
found: C 74.62, H 6.92.
7
-Hydroxy-6-methylindan-1-one (8a), 2-methyl-7,8-dihydro-6H-cyclohep-
washed with brine and dried over MgSO
the residue was purified by column chromatography on silica gel (2%
CH Cl /petroleum ether) to give 11a (128 mg, 64%). IR (CDCl
): nÄ ±010,
1660, 1249, 1025 cm ; H NMR (500 MHz, CD
4
. After removal of the solvents,
ta[b]furan-6-one (9a) and 6-hydroxy-7-methylindan-1-one (10a): AuCl
±
(
46.8 mg, 154 mmol) in CH
±
CN (1 mL) was added to a solution of ketone 7a
CN (25 mL) at room temperature, and the
2
2
±
À1
1
(
500 mg, ±.08 mmol) in CH
±
±
CN): d 1.42 (s, 6H), 2.11
resulting deep red solution was stirred for 2 h. The reaction mixture was
then evaporated under reduced pressure to remove all the solvent. Column
(s, ±H), 2.71 ± 2.75 (dt, 2H, J 2.0 Hz, 6.7 Hz), 2.97 (t, 2H, J 6.7 Hz), 5.2±
(t, 1H, J 2.0 Hz), 6.66 (d, 1H, J 7.6 Hz), 6.91 (d, 1H, J 7.5 Hz);
1
±
chromatography on silica gel (20 ± 40% CH
0.4 in 10% EtOAc/petroleum ether) (225 mg, 45%) and 9a (R
in 10% EtOAc/petroleum ether; 45.0 mg, 9%); further elution with 40%
2
Cl
2
/petroleum ether) gave 8a
C NMR (75.5 MHz, CDCl
±
): d 1±.0 (q), 27.7 (t), 28.2 (q, 2C), 29.9 (t),
(
R
f
f
0.±
79.2 (s), 115.8 (d), 117.2 (d), 120.± (s), 125.9 (s), 1±1.4 (d), 1±7.1 (s), 140.9 (s),
148.4 (s); MS: m/z (%): 200 [M 3 (2±), 185 (100); elemental analysis (%)
EtOAc/petroleum ether afforded 10a (R
ether) (±5.8 mg, 7%). 8a: M.p. 79 ± 808C; IR (CDCl
f
0.1 in 10% EtOAc/petroleum
calcd for C14
H16O: C 8±.96, H 8.05; found: C 8±.91, H 8.±±.
À1
±
): nÄ ±±20, 1675 cm
;
2
,2,5,8-Tetramethyl-4,5-dihydro-2H-cyclopenta[de]chromene (11b): A sol-
1
H NMR (±00 MHz, CDCl
±
): d 2.2± (s, ±H), 2.70 (t, 2H, J 5.6 Hz), ±.06
ution of the indanone 8b (±±9 mg, 1.92 mmol) in dry THF (10 mL) was
added dropwise to a solution of 2-methyl-1-propenylmagnesium bromide
(
1
1
t, 2H, J 5.6 Hz), 6.84 (d, 1H, J 7.5 Hz), 7.±2 (d, 1H, J 7.5 Hz), 9.2± (s,
H); 1±C NMR (75.5 MHz, CDCl
): d 14.1 (q), 25.4 (t), ±6.2 (t), 116.8 (d),
±
(
0.5m in THF; 40.0 mL, 20.0 mmol) at 08C. The resulting solution was
22.2 (s), 122.7 (s), 1±8.8 (d), 152.6 (s), 155.5 (s), 210.± (s); MS: m/z (%): 162
stirred for 2 h and then quenched with a saturated aqueous NH Cl solution.
The layers were separated, and the aqueous phase was extracted with
diethyl ether. The combined organic portions were then washed with brine
and dried over MgSO
dissolved in CH Cl (100 mL) and stirred with silica gel (50 g) for 1 h. The
mixture was then filtered, and the filtrate was concentrated, purified by
4
[
M 3 (100); elemental analysis (%) calcd for C10
H
10
O
2
: C 74.06, H 6.21;
À1
1
found: C 74.07, H 6.2±. 9a: IR (CDCl
±
): nÄ 1640, 1570 cm
; H NMR
(
±00 MHz, CDCl
±
): d 2.26 (s, ±H), 2.80 ± 2.86 (m, 2H), 2.91 ± 2.97 (m,
4
. After removal of the solvents, the residue was
2
H), 5.97 (s, 1H), 5.99 (d, 1H, J 12.1 Hz), 6.82 (d, 1H, J 12.1 Hz);
2
2
1
±
C NMR (75.5 MHz, CDCl
±
): d 1±.6 (q), 21.± (t), ±9.± (t), 108.0 (d), 119.0
(
s), 127.4 (d), 1±4.9 (d), 150.7 (s), 156.5 (s), 200.5 (s); MS: m/z (%): 162 [M 3
column chromatography on silica gel (2.5% CH
2
Cl
2
/petroleum ether) to
(
100); HRMS: m/z: calcd for C10
H
10
O
2
: 162.0681 [M 3; found: 164.0681.
À1
give 11b (±96 mg, 96%). IR (neat): nÄ ±0±7, 1666, 1259, 1081 cm
;
À1
1
1
CD
1
CD
0a: M.p. 169 ± 1708C; IR (KBr): nÄ 1660 cm
;
H NMR (±00 MHz,
1
H NMR (500 MHz, CDCl
±
): d 1.29 (d, ±H, J 7.1 Hz), 1.4± (s, ±H), 1.47
±
CN): d 2.46 (s, ±H), 2.59 (m, 2H), 2.96 (t, 2H, J 5.8 Hz), 6.97 (s,
(
1
2
(
(
s, ±H), 2.16 (s, ±H), 2.29 (ddd, 1H, J 17.0, 4.7, 2.2 Hz), 2.98 (ddd, 1H, J
1
±
H), 7.06 (d, 1H, J 8.2 Hz), 7.17 (d, 1H, J 8.2 Hz); C NMR (75.5 MHz,
7.0 Hz, 8.0, 1.9 Hz), ±.±8 (dq, 1H, J 5.1, 7.2 Hz,), 5.1± (dd, 1H, J 2.0 Hz,
CN): d 9.1 (q), 2±.9 (t), ±7.2 (t), 121.4 (d), 122.9 (s), 124.2 (d), 1±5.1
1±
±
.1 Hz), 6.6± (d, 1H, J 7.5 Hz), 6.9± (d, 1H, J 7.5 Hz); C NMR
(
s), 147.7 (s), 15±.8 (s), 208.0 (s); MS: m/z (%): 162 [M 3 (100); elemental
75.5 MHz, CDCl
±
): d 14.6 (q), 21.7 (q), 29.7 (q), ±0.0 (q), ±8.4 (t), ±8.8
analysis (%) calcd for C10
-Hydroxy-3,6-dimethylindan-1-one (8b), 2,8-dimethyl-7,8-dihydro-6H-cy-
clohepta[b]furan-6-one (9b), and 6-hydroxy-3,7-dimethylindan-1-one
10b): A solution of AuCl (200 mg, 2.9% in CD CN, 19.1 mmol) was
added to a solution of ketone 7b (47.6 mg, 270 mmol) in CD CN at room
10 2
H O : C 74.06, H 6.21; found: C 7±.97, H 6.26.
d), 79.9 (s), 115.2 (d), 118.0 (d), 121.7 (s), 126.0 (s), 1±2.2 (d), 1±6.7 (s),
1
46.± (s), 149.1 (s); MS: m/z (%): 214 [M 3 (21), 199 (100); elemental
7
analysis (%) calcd for C15H18O: C 84.07, H 8.47; found: C 84.19, H 8.54.
(
±
±
5-Methyl-3-(2-methylprop-1-enyl)indan-4-ol (12a): A solution of chro-
mene 11a (40.1 mg, 200 mmol) in dry diethyl ether (2 mL) was added to a
suspension of LAH (90.1 mg, 2.±7 mmol) in dry diethyl ether (8 mL) at
room temperature. The mixture was irradiated in a quartz flask with stirring
for 6 h with a Heraeus TQ 150 mercury lamp. The reaction mixture was
then poured onto crushed ice and acidified with dilute HCl until the
hydroxides just dissolved. The water layer was extracted with diethyl ether,
and the combined organic portions were washed with a saturated solution
of Na CO and brine and dried over MgSO . After removal of the solvent,
±
temperature, and the resulting deep red solution was shaken occasionally
1
over 2 h until the H NMR spectrum showed completion of the reaction.
Then the reaction mixture was evaporated and the residue was purified by
column chromatography on silica gel (5% EtOAc/petroleum ether) to give
À1
1
8
b (±5.6 mg, 75%). IR (neat): nÄ ±±21, 1671 cm
;
H NMR (500 MHz,
CDCl
±
): d 1.±7 (d, ±H, J 7.1 Hz), 2.2± (s, ±H), 2.29 (dd, 1H, J 19.1,
±
.2 Hz), 2.95 (dd, 1H, J 19.1, 7.5 Hz), ±.±6 ± ±.42 (m, 1H), 6.86 (d, 1H, J
1±
2
±
4
7
.6 Hz), 7.±4 (d, 1H, J 7.5 Hz), 9.21 (s, 1H); C NMR (126 MHz, CDCl
±
):
the residue was purified by column chromatography on silica gel (2%
EtOAc/petroleum ether) to give 12a (±6.8 mg, 91%). M.p. 24.5 ± 25.58C;
d 14.6 (q), 21.6 (q), ±±.1 (d), 45.7 (t), 115.9 (d), 122.0 (s), 12±.2 (s), 1±9.±
À1 1
(
d), 155.5 (s), 158.1 (s), 210.0 (s); MS: m/z (%): 176 [M 3 (100), 161 (92);
IR (neat): nÄ ±468, 290±, 1580, 1197, 1010, 780 cm ; H NMR (500 MHz,
elemental analysis (%) calcd for C11
H 6.86.
H
12
O
2
: C 75.0±, H 6.97; found: C 74.98,
CDCl ): d 1.7± ± 1.81 (m, 1H), 1.84 (s, ±H), 1.89 (s, ±H), 2.21 (s, ±H),
±
2.28 ± 2.±± (m, 1H), 2.80 ± 2.9± (m, 2H), 4.09 (dt, 1H, J 7.9, J 9.6 Hz),
1
2
5
.1± (d, 1H, J 9.4 Hz), 5.8± (s, 1H), 6.71 (d, 1H, J 7.4 Hz), 6.96 (d, 1H,
When ketone 7b (887 mg, 5.0± mmol) was treated with AuCl
5± mmol) in CH CN at 08C for 2 h, purification by column chromatog-
raphy on silica gel (5% EtOAc/petroleum ether) gave 8b (R
0.2, 470 mg,
±%) and 9b (R
0.1, 17.4 mg, 2%); further elution with 50% EtOAc/
petroleum ether afforded 10b (R
0.2 in 10% EtOAc/petroleum ether)
27.7 mg, ±%). 9b: IR (CDCl
): nÄ 1651, 1575 cm ; H NMR (500 MHz,
CDCl
): d 1.24 (d, ±H, J 7.± Hz), 2.27 (s, ±H), 2.75 (dd, 1H, J 15.1 Hz,
.4 Hz), 2.89 (dd, 1H, J 15.1 Hz, ±.2 Hz), ±.1± ± ±.19 (m, 1H), 5.96 (s, 1H),
±
(107 mg,
1±
J 7.4 Hz); C NMR (126 MHz, CDCl
±
): d 15.2 (q), 18.2 (q), 25.9 (q),
±
±
±
1
1.9 (t), ±4.1 (t), 42.2 (d), 116.1 (d), 122.2 (s), 127.6 (d), 129.6 (s), 129.9 (d),
±5.7 (s), 14±.2 (s), 151.7 (s); MS: m/z (%): 202 [M 3 (56), 187 (55), 147
f
5
f
(
100); HRMS: m/z: calcd for C14
H
18O: 202.1±58 [M 3, found: 202.1±57.
f
À1
1
(
±
1,5-Dimethyl-3-(2-methylprop-1-enyl)indan-4-ol (epi-jungianol; 12) and
1,5-dimethyl-3-(2-methylpropylidene)indan-4-ol (13): A solution of chro-
mene 11b (282 mg, 1.±2 mmol) in dry diethyl ether (5 mL) was added to a
suspension of LAH (467 mg, 12.± mmol) in dry diethyl ether (25 mL) at
room temperature. The mixture was irradiated in a quartz flask with stirring
for 6 h with a Heraeus TQ 150 mercury lamp. The reaction mixture was
then poured onto crushed ice and acidified with dilute HCl until the
hydroxides just dissolved. The water layer was extracted with diethyl ether,
and the combined organic portions were washed with a saturated solution
±
8
5
1
±
.99 (d, 1H, J 11.9 Hz), 6.82 (d, 1H, J 11.9 Hz); C NMR (126 MHz,
CDCl
1
±
): d 1±.6 (q), 17.0 (q), 28.7 (d), 47.0 (t), 108.± (d), 117.7 (s), 127.5 (d),
±4.8 (d), 150.5 (s), 160.± (s), 200.± (s); MS: m/z (%): 176 [M 3 (100), 161
(
11 2
87); HRMS: m/z: calcd for C11H O : 176.08±7 [M 3, found: 176.08±7.
À1
1
1
CD
0b: M.p. 1±8 ± 1±98C; IR (neat): nÄ ±±14, 1677 cm ; H NMR (500 MHz,
±
OD): d 1.50 (d, ±H, J 7.1 Hz), 2.±9 (dd, 1H, J 18.9 Hz, ±.± Hz),
2
1
.6± (s, ±H), ±.06 (dd, 1H, J 18.9 Hz, 7.4 Hz), ±.4± ± ±.49 (m, 1H), 7.25 (d,
of Na
2 ± 4
CO and brine and dried over MgSO . After removal of the solvent,
1
±
H, J 8.2 Hz), 7.±7 (d, 1H, J 8.2 Hz); C NMR (126 MHz, CD
±
OD):
the residue was purified by preparative TLC (4% EtOAc/petroleum ether)
4344
¹ 200± Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
Chem. Eur. J. 2003, 9, 4±±9 ± 4±45