818
Vol. 62, No. 8
(500MHz, CDCl3) δ: 2.07 (1H, dt, J=8.6, 13Hz), 2.45 (1H, ed with CH2Cl2 (10mL). The organic layer was washed with
ddd, J=3.5, 8.0, 13Hz), 2.85 (1H, dt, J=8.0, 16Hz), 3.03 (1H, brine and dried over Na2SO4. The solvent was evaporated and
ddd, J=3.5, 8.6, 16Hz), 3.30 (1H, brs), 3.65 (2H, d, J=12Hz), the residue was purified by column chromatography (hexane–
3.74 (1H, d, J=12Hz), 7.25 (1H, t, J=7.5Hz), 7.26 (1H, d, AcOEt=9:1) to give the fluoroester 2 (0.14g, 0.71mmol, 83%)
J=7.5Hz), 7.29 (1H, t, J=7.5Hz), 7.40 (1H, d, J=7.5Hz); as a yellow oil; the structure of 2 was confirmed by compar-
13C-NMR (125MHz, CDCl3) δ: 29.2, 36.8, 67.7, 83.7, 123.4, ing its NMR data with those obtained previously.1)
124.9, 126.6, 128.5, 143.3, 144.5; MS m/z: 164 (M+), 133 ([M−
CH2OH]+), 115 (indenyl cation); HR-MS Calcd for C10H12O2 solution of 4-methyl-1-indanone (9) (1.0g, 6.8mmol) and
(M+): 164.0837, Found: 164.0810.
Ph3PMeBr (4.9g, 13.7mmol) in dry THF (50mL) was added
4-Methyl-1-methylene-2,3-dihydro-1H-indene (10) To a
1-Hydroxy-2,3-dihydro-1H-indene-1-carboxylic Acid (6) tert-BuOK (1.5g, 13.4mmol) in dry THF (50mL) over a period
A suspension of the diol 5 (0.55g, 3.4mmol), 5% Pt/C (0.31g), of 1h under nitrogen atmosphere at room temperature. After
NaHCO3 (0.63g, 7.5mmol) in H2O (5mL) was stirred at 70°C. being stirred at room temperature for 2h, half amount of THF
Oxygen gas was introduced into the reaction mixture for 48h. was evaporated. To the residue was added H2O (100mL) and
The mixture was filtered through a celite pad. The filtrate was the aqueous layer was extracted with Et2O (80mL×3). The
washed with AcOEt to remove non-acidic compound. The organic layer was washed with brine and dried over Na2SO4.
aqueous layer was acidified with 2mol/L H2SO4 to pH 2. Then The solvent was evaporated and the residue was purified by
the acidic solution was extracted with AcOEt (10mL×3). The column chromatography (hexane) to give the exo-methylene
organic layer was washed with brine and dried over Na2SO4. compound 10 (0.84g, 5.8mmol, 85%) as a colorless oil; IR
1
The solvent was evaporated and the residue was purified by (neat) 2915 (CH) cm−1; H-NMR (500MHz, CDCl3) δ: 2.26
column chromatography (hexane–AcOEt=3:7) to give the (3H, s), 2.79–2.82 (2H, m), 2.87–2.89 (2H, m), 5.01 (1H, d,
hydroxycarboxylic acid 6 (0.50g, 8.4mmol, 83%) as a color- J=1.8Hz), 5.42 (1H, d, J=2.3Hz), 7.03 (1H, d, J=7.5Hz), 7.12
less oil; IR (neat) 3415 (OH), 2946 (CH), 1709 (C=O) cm−1; (1H, t, J=7.5Hz), 7.33 (1H, d, J=7.4Hz); 13C-NMR (125MHz,
1H-NMR (500MHz, CDCl3) δ: 2.30 (1H, m), 2.76 (1H, m), CDCl3) δ: 18.7, 28.8, 30.9, 102.3, 117.9, 126.7, 128.9, 134.6,
3.12 (2H, m), 7.23 (1H, m), 7.31 (3H, m); 13C-NMR (125MHz, 140.8, 145.7, 150.9; MS m/z: 144 (M+), 115 (indenyl cation);
CDCl3) δ: 30.3, 38.6, 83.7, 123.0, 125.1, 126.9, 129.3, 142.7, HR-MS Calcd for C11H12 (M+): 144.0939, Found: 144.0949.
144.0, 179.5; MS m/z: 178 (M+), 133 ([M−COOH]+), 115
(indenyl cation); HR-MS Calcd for C10H10O3 (M+): 178.0630, (11) To a mixture of exo-methylene compound 10 (1.02g,
Found: 178.0602. 7.1mmol) and NMO (1.33g, 11.4mmol) in CH3CN–ace-
4-Methyl-1-(hydroxymethyl)-2,3-dihydro-1H-inden-1-ol
Fluorination of the Hydroxycarboxylic Acid 6 by DAST tone–H2O (1:1:1, 10mL) was added Os IC-I (1.30g, OsO4
To a solution of hydroxycarboxylic acid 6 (0.11g, 0.62mmol) 0.36mmol) at room temperature. After being stirred at room
in dry CH2Cl2 (10mL), DAST (0.20g 1.24mmol) in dry temperature for 5h, Os IC-I was removed by filtration. The
CH2Cl2 (10mL) was added slowly at −78°C under nitrogen Os IC-I was washed with H2O (10mL×3) and then AcOEt
atmosphere. The reaction mixture was warmed to room tem- (10 mL×3). The washed solvents were added to the filtrate.
perature and stirred for 4.5h. To the reaction mixture, H2O The mixed solution was extracted with AcOEt (30mL×3).
(2mL) was added carefully. The solution was extracted with The organic layer was washed with brine and dried over
CH2Cl2 (5 mL×2). The organic layer was washed with brine Na2SO4. The solvent was evaporated and the residue was
and dried over Na2SO4. The solvent was evaporated and the purified by column chromatography (hexane–AcOEt=2:3)
residue was purified by column chromatography (hexane– to give the diol 11 (1.22g, 6.8mmol, 96%) as a colorless oil;
1
AcOEt=9:1) to give the product 3 (30mg, 0.23mmol, 37%) IR (neat) 3422 (OH), 2915 (CH) cm−1; H-NMR (500MHz,
as a colorless power. The structure of the product 3 was CDCl3) δ: 2.03–2.09 (1H, m), 2.27 (3H, s), 2.45 (1H, ddd,
confirmed by comparing its NMR data with those of commer- J=4.0, 8.6, 13Hz), 2.73 (1H, ddd, J=8.0, 8.0, 16Hz,), 2.95
cially available 1-indanone.
(1H, ddd, J=4.0, 9.2, 16Hz), 3.63 (1H, d, J=11Hz), 3.73 (1H,
Methyl 1-Hydroxy-2,3-dihydro-1H-indene-1-carboxylate d, J=11Hz), 7.10 (1H, d, J=7.5Hz), 7.17 (1H, t, J=7.5Hz),
(7) To a solution of the acid 6 (0.21g, 1.2mmol) in MeOH 7.23 (1H, d, J=7.5Hz); 13C-NMR (125MHz, CDCl3) δ: 18.6,
(7mL) was added H3BO3 (22mg, 0.35mmol) at room tempera- 27.8, 36.5, 68.0, 84.0, 120.7, 127.0, 129.3, 134.3, 142.1, 144.3;
ture. After being stirred at room temperature for 66h, satu- MS m/z: 178 (M+), 147 ([M−CH2OH]+), 115 (indenyl cation);
rated aqueous NaHCO3 solution (5mL) and H2O (10mL) were HR-MS Calcd for C11H14O2 (M+): 178.0994, Found: 178.0969.
added to the reaction mixture. The solution was extracted with
4-Methyl-1-hydroxy-2,3-dihydro-1H-indene-1-carboxylic
AcOEt (20mL×3). The organic layer was washed with brine Acid (12) A suspension of the diol 11 (1.13g, 6.3mmol),
and dried over Na2SO4. The solvent was evaporated and the 5% Pt/C (0.65g), NaHCO3 (1.25g, 14.9mmol) in H2O–acetone
residue was purified by column chromatography (hexane– (5:1, 27mL) was stirred at 70–80°C. Oxygen gas was intro-
AcOEt=7:3) to give the ester 7 (0.16g, 0.86mmol, 73%) as a duced into the reaction mixture for 53h. The mixture was
colorless oil; the structure of 7 was confirmed by comparing filtered through a celite pad. The filtrate was extracted with
its NMR data with those obtained previously.1)
AcOEt to remove non-acidic compound. The aqueous layer
Methyl 1-Fluoroindan-1-carboxylate (2) (FICA Me Ester) was acidified using 2mol/L H2SO4 to pH 2. Then the acidic
To a solution of the ester 7 (0.16g, 0.86mmol) in dry CH2Cl2 solution was extracted with AcOEt (30mL×3). The organic
(4mL) was added slowly Deoxo-fluor (0.57g, 2.57mmol) in layer was washed with brine and dried over Na2SO4. The sol-
dry CH2Cl2 (8mL) at room temperature under nitrogen atmo- vent was evaporated and the residue was purified by column
sphere. After being stirred at room temperature for 40min, chromatography (hexane–AcOEt=3:7) to give the hydroxy-
saturated aqueous NaHCO3 solution (6mL) and H2O (6mL) carboxylic acid 12 (0.84g, 4.4mmol, 69%) as a colorless oil;
1
were added to the reaction mixture. The solution was extract- IR (neat) 3362 (OH), 2934 (CH), 1712 (C=O) cm−1; H-NMR