1494
Vol. 56, No. 10
m), 7.42(1H, t, Jꢁ8.0 Hz), 7.42 (1H, d, Jꢁ8.5 Hz), 7.25 (2H, d, Jꢁ8.5 Hz), (1H, d, Jꢁ8.5 Hz), 7.22 (1H, t, Jꢁ7.5 Hz), 7.03 (2H, d, Jꢁ7.5 Hz), 2.26 (3H,
6.80 (2H, d, Jꢁ8.5 Hz), 5.96 (1H, s), 0.97 (9H, s), 0.18 (6H, s).
s), 2.13 (3H, s); HR-FAB-MS m/z: 318.0682 (Calcd for C17H15ClO4: (M)ꢂ,
4-(tert-Butyldimethylsilyloxy)-a-(9ꢀ-anthracenyl)benzyl Alcohol (19) 318.0659).
Prepared from 10 and 9-bromoanthracene by typical procedure B (34%):
Ethyl 4-{1ꢀ-Acetoxy-1ꢀ-[(4ꢁ-acetoxyphenyl)methyl]benzoate (3i) Pre-
Yellow oil; 1H-NMR (500 MHz, CDCl3) d: 8.47 (1H, s), 8.37 (2H, d, Jꢁ pared from ethyl 11i by typical procedure D (48%): Colorless viscous oil;
8.5 Hz), 8.02 (2H, d, Jꢁ8.5 Hz), 7.44 (2H, t, Jꢁ8.5 Hz), 7.40 (2H, t, Jꢁ 1H-NMR (300 MHz, CDCl3) d: 8.02 (2H, d, Jꢁ8.4 Hz), 7.41 (2H, d, Jꢁ
8.5 Hz), 7.35 (1H, s), 7.22 (2H, d, Jꢁ8.5 Hz), 6.74 (2H, d, Jꢁ8.5 Hz), 0.96
8.4 Hz), 7.33 (2H, d, Jꢁ8.4 Hz), 7.06 (2H, d, Jꢁ8.4 Hz), 6.90 (1H, s), 4.37
(2H, q, Jꢁ6.9 Hz), 2.28 (3H, s), 2.17 (3H, s), 1.38 (3H, t, Jꢁ6.9 Hz); HR-
(9H, s), 0.16 (6H, s).
4-(tert-Butyldimethylsilyloxy)-a-(4ꢀ-trimethylsilylphenyl)benzyl Alco- FAB-MS m/z: 356.1288 (Calcd for C20H20O6: (M)ꢂ, 356.1260).
hol (11l) To a solution of magnesium (200 mg, 7.5 mmol) activated with
iodine (5.0 mg) in Et2O was added dropwise 10 (342 mg, 1.50 mmol) at
room temperature. This solution was added dropwise to a solution of 1 (236
mg, 1.0 mmol) in dry THF (3.0 ml) at ꢄ78 °C. The mixture was stirred for
4-Acetoxy-a-(3ꢀ-methoxyphenyl)benzyl Acetate (4a) Prepared from
12a by typical procedure D (48%): Colorless oil; 1H-NMR (300 MHz,
CDCl3) d: 7.34 (2H, d, Jꢁ8.4 Hz), 7.28—7.23 (1H, m), 7.05 (2H, d, Jꢁ
8.4 Hz), 6.92—6.80 (4H, m), 3.78 (3H, s), 2.28 (3H, s), 2.15 (3H, s); HR-
1.5 h at ꢄ78 °C, brine was added and the whole was extracted with ethyl FAB-MS m/z: 314.1162 (Calcd for C18H18O5: (M)ꢂ, 314.1154).
acetate. The organic layer was dried over MgSO4, and concentrated. The
4-Acetoxy-a-(3ꢀ-methylphenyl)benzyl Acetate (4b) Prepared from
residue was purified by column chromatography (ethyl acetate : hexaneꢁ 12b by typical procedure D (59%): Colorless oil; 1H-NMR (300 MHz,
1
1 : 10) to give 11l (198 mg, 52%) as a pale yellow oil: H-NMR (500 MHz,
CDCl3) d: 7.34 (2H, d, Jꢁ8.4 Hz), 7.22—7.20 (1H, m), 7.14—7.03 (5H, m),
CDCl3) d: 7.49 (2H, d, Jꢁ8.0 Hz), 7.35 (2H, d, Jꢁ8.0 Hz), 7.22 (2H, d, Jꢁ 6.84 (1H, s), 2.33 (3H, s), 2.28 (3H, s), 2.15 (3H, s); HR-FAB-MS m/z:
8.5 Hz), 6.79 (2H, d, Jꢁ8.5 Hz), 5.78 (1H, d, Jꢁ3.5 Hz), 2.12 (1H, d, Jꢁ 298.1231 (Calcd for C18H18O4: (M)ꢂ, 298.1205).
3.5 Hz) 0.97 (9H, s), 0.25 (9H, s). 0.18 (6H, s); HR-FAB-MS m/z: 356.1455
4-Acetoxy-a-(3ꢀ-fluorophenyl)benzyl Acetate (4c) Prepared from 12c
by typical procedure D (38%): Colorless oil; 1H-NMR (300 MHz, CDCl3) d:
(Calcd for C20H24O4Si: (M)ꢂ, 356.1444).
4-Acetoxy-a-(4ꢀ-methoxyphenyl)benzyl Acetate (3a) [Typical Proce- 7.35—7.26 (3H, m), 7.11—7.04 (4H, m), 7.01—6.95 (1H, m), 6.85 (1H, s),
dure D] To a solution of 11a (192 mg, 0.58 mmol) in dry THF (5.0 ml)
was added TBAF (1.0 M in THF, 0.5 ml, 0.500 mmol) at 0 °C. The reaction
mixture was stirred for 1 h at the same temperature, then concentrated under
2.29 (3H, s), 2.16 (3H, s); HR-FAB-MS m/z: 302.0982 (Calcd for
C17H15FO4: (M)ꢂ, 302.0954).
4-Acetoxy-a-(3ꢀ-chlorophenyl)benzyl Acetate (4d) Prepared from 12d
reduced pressure. The residue was taken up in pyridine (4.0 ml) and acetic by typical procedure D (87%): Colorless oil; 1H-NMR (300 MHz, CDCl3) d:
anhydride (500 ml, 1.47 mmol) was added to the solution at room tempera- 7.34—7.31 (3H, m), 7.27—7.26 (2H, m), 7.21—7.19 (1H, m), 7.07 (2H, d,
ture. The mixture was stirred for 3 h at room temperature, NH4Cl aq. was Jꢁ8.7 Hz), 6.82 (1H, s), 2.28 (3H, s), 2.16 (3H, s); HR-FAB-MS m/z:
added and the whole was extracted with ethyl acetate. The organic layer was 318.0694 (Calcd for C17H15ClO4: (M)ꢂ, 318.0659).
dried with MgSO4, and concentrated. The residue was purified by column
4-Acetoxy-a-(3ꢀ-trifluoromethylphenyl)benzyl Acetate (4e) Prepared
1
chromatography (ethyl acetate/hexaneꢁ1/4) to give 3a (27.0 mg, 51%) as a
from 12e by typical procedure D (33%): Colorless oil; H-NMR (300 MHz,
1
colorless oil: H-NMR (500 MHz, CDCl3) d: 7.27 (2H, d, Jꢁ8.0 Hz), 7.25
CDCl3) d: 7.62 (1H, s), 7.57—7.43 (3H, m), 7.34 (2H, d, Jꢁ8.7 Hz), 7.08
(2H, d, Jꢁ8.7 Hz), 6.91 (1H, s), 2.29 (3H, s), 2.18 (3H, s); HR-FAB-MS
m/z: 352.0954 (Calcd for C18H15F3O4: (M)ꢂ, 352.0922).
(2H, t, Jꢁ8.5 Hz), 7.01 (2H, d, Jꢁ8.0 Hz), 6.96 (2H, t, Jꢁ8.5 Hz), 6.80 (1H,
s), 2.22 (3H, s), 2.09 (3H, s); HR-FAB-MS m/z: 302.0989 (Calcd for
C17H16FO4: (M)ꢂ, 302.0954).
4-Acetoxy-a-(3ꢀ-cyanophenyl)benzyl Acetate (4f) Prepared from 12f
4-Acetoxy-a-(4ꢀ-methylphenyl)benzyl Acetate (3b) Prepared from by typical procedure D (74%): Colorless oil; 1H-NMR (300 MHz, CDCl3) d:
11b by typical procedure D (21%): Colorless oil; 1H-NMR (500 MHz,
7.66 (1H, s), 7.60—7.53 (2H, m), 7.47—7.42 (1H, m), 7.32 (2H, d, Jꢁ
CDCl3) d: 7.46 (2H, d, Jꢁ8.0 Hz), 7.56 (2H, d, Jꢁ7.5 Hz), 7.48 (2H, d, Jꢁ 8.4 Hz), 7.09 (2H, d, Jꢁ8.4 Hz), 6.86 (1H, s), 2.30 (3H, s), 2.18 (3H, s); HR-
7.5 Hz), 7.39 (2H, d, Jꢁ8.0 Hz), 7.19 (1H, s), 2.67 (3H, s), 2.63 (3H, s), 2.37 FAB-MS m/z: 309.1017 (Calcd for C18H15NO4: (M)ꢂ, 309.1001).
(3H, s); HR-FAB-MS m/z: 298.1169 (Calcd for C18H18O4: (M)ꢂ, 298.1205).
Ethyl 3-{1ꢀ-Acetoxy-1ꢀ-[(4ꢁ-acetoxyphenyl)methyl]benzoate (4g) Pre-
4-Acetoxy-a-(4ꢀ-methylsulfanylphenyl)benzyl Acetate (3c) Prepared pared from 12g by typical procedure D (48%): Colorless oil; 1H-NMR
from 11c by typical procedure D (87%): Yellow oil; 1H-NMR (500 MHz,
(300 MHz, CDCl3) d: 8.04 (1H, s), 7.97 (1H, d, Jꢁ7.2 Hz), 7.52—7.50 (1H,
CDCl3) d: 7.32 (2H, d, Jꢁ8.5 Hz), 7.25 (2H, d, Jꢁ8.5 Hz), 7.21 (2H, d, Jꢁ m), 7.41 (1H, t, Jꢁ7.5 Hz), 7.34 (2H, d, Jꢁ8.4 Hz), 7.06 (2H, d, Jꢁ8.4 Hz),
8.5 Hz), 7.05 (2H, d, Jꢁ8.5 Hz), 6.84 (1H, s), 2.47 (3H, s), 2.29 (3H, s), 2.15 6.90 (1H, s), 4.37 (2H, q, Jꢁ7.2 Hz), 2.28 (3H, s), 2.14 (3H, s), 1.39 (3H, t,
(3H, s); FAB-MS m/z: 330.0891 (Calcd for C18H18O4S: (M)ꢂ, 330.0926).
Jꢁ7.2 Hz); HR-FAB-MS m/z: 356.1253 (Calcd for C20H20O6: (M)ꢂ,
4-Acetoxy-a-(4ꢀ-fluorophenyl)benzyl Acetate (3d) Prepared from 11d 356.1260).
by typical procedure D (81%): Colorless oil; 1H-NMR (500 MHz, CDCl3) d:
7. 27 (2H, d, Jꢁ8.0 Hz), 7.25 (2H, dd, Jꢁ8.5, 5.5 Hz [with H-F coupling]),
7.01 (2H, d, Jꢁ8.0 Hz), 6.96 (2H, dd, Jꢁ8.5, 8.5 Hz [with H-F coupling]),
6.80 (1H, s), 2.22 (3H, s), 2.09 (3H, s); HR-FAB-MS m/z: 302.0989 (Calcd
for C17H16O4F: (M)ꢂ, 302.0954).
4-Acetoxy-a-(4ꢀ-trimethylsilylphenyl)benzyl Acetate (3l) Prepared
1
from 11l by typical procedure D (71%): Colorless oil; H-NMR (500 MHz,
CDCl3) d: 7.49 (2H, d, Jꢁ8.0 Hz), 7.35 (2H, d, Jꢁ8.0 Hz), 7.31 (2H, d, Jꢁ
8.0 Hz), 7.05 (2H, d, Jꢁ8.0 Hz), 6.86 (1H, s), 2.29 (3H, s), 2.15 (3H, s), 0.25
(9H, s); FAB-MS m/z: 356.1455 (Calcd for C20H24O4Si: (M)ꢂ, 356.1444).
4-Acetoxy-a-(3ꢀ,5ꢀ-diphenylphenyl)benzyl Acetate (4h) Prepared
4-Acetoxy-a-(4ꢀ-chlorophenyl)benzyl Acetate (3e) Prepared from 11e
by typical procedure D (79%): Colorless oil; 1H-NMR (500 MHz, CDCl3) d: from 12h by typical procedure D (75%): Colorless oil; 1H-NMR (500 MHz,
7.31 (4H, d, Jꢁ8.5 Hz), 7.26 (2H, d, Jꢁ8.5 Hz), 7.06 (2H, d, Jꢁ8.5 Hz),
6.84 (1H, s), 2.29 (3H, s), 2.15 (3H, s,); HR-FAB-MS m/z: 318.0609 (Calcd
for C17H15ClO4: (M)ꢂ, 318.0659).
CDCl3) d: 7.74 (1H, s), 7.62 (4H, d, Jꢁ7.0 Hz), 7.55 (2H, s), 7.46 (4H, t, Jꢁ
7.0 Hz), 7.44 (2H, d, Jꢁ7.5 Hz), 7.38 (2H, t, Jꢁ7.0 Hz), 7.09 (2H, d, Jꢁ
7.5 Hz), 7.02 (1H, s), 2.29 (3H, s), 2.02 (3H, s); HR-FAB-MS m/z: 436.1672
4-Acetoxy-a-(4ꢀ-trifluoromethylphenyl)benzyl Acetate (3f) Prepared (Calcd for C29H24O4: (M)ꢂ, 436.1675).
1
from 11f by typical procedure D (94%): Colorless oil; H-NMR (500 MHz,
4-Acetoxy-a-(4ꢀ-phenyl)benzyl Acetate (3m) Prepared from 12m by
CDCl3) d: 7.60 (2H, d, Jꢁ8.0 Hz), 7.46 (2H, d, Jꢁ8.0 Hz), 7.33 (2H, d, Jꢁ typical procedure D (97%): Colorless oil; 1H-NMR (500 MHz, CDCl3) d:
8.0 Hz), 7.07 (2H, d, Jꢁ8.0 Hz), 6.90 (1H, s), 2.29 (3H, s), 2.17 (3H, s); HR-
7.56 (4H, d, Jꢁ7.5 Hz), 7.45—7.38 (6H, m), 7.35 (2H, t, Jꢁ7.5 Hz), 7.08
(2H, d, Jꢁ8.0 Hz), 6.93 (1H, s), 2.30 (3H, s), 2.17 (3H, s); HR-FAB-MS
FAB-MS m/z: 352.0895 (Calcd for C18H15F3O4: (M)ꢂ, 352.0922).
4-Acetoxy-a-(4ꢀ-cyanophenyl)benzyl Acetate (3g) Prepared from 11g m/z: 360.1402 (Calcd for C23H20O4: (M)ꢂ, 360.1362).
by typical procedure D (39%): Colorless oil; 1H-NMR (500 MHz, CDCl3) d:
7.64 (2H, d, Jꢁ8.5 Hz), 7.45 (2H, d, Jꢁ8.5 Hz), 7.31 (2H, d, Jꢁ8.5 Hz),
7.08 (2H, d, Jꢁ8.5 Hz), 6.87 (1H, s), 2.29 (3H, s), 2.17 (3H, s); HR-FAB-
MS m/z: 3091036 (Calcd for C18H15NO4: (M)ꢂ, 309.1001).
4-Acetoxy-a-(1ꢀ-naphthyl)benzyl Acetate (6) Prepared from 17 by
typical procedure D (99%): Colorless oil; 1H-NMR (500 MHz, CDCl3) d:
7.96 (4H, d, Jꢁ8.0 Hz), 7.87—7.84 (2H, m), 7.61 (1H, s), 7.58 (2H, d, Jꢁ
8.0 Hz), 7.50—7.40 (3H, m), 7.36 (2H, d, Jꢁ8.5 Hz), 7.04 (2H, d, Jꢁ
4-Acetoxy-a-(4ꢀ-acetoxyphenyl)benzyl Acetate (3h) Prepared from 8.5 Hz), 2.28 (3H, s), 2.18 (3H, s). HR-FAB-MS: m/z 334.1208 (Calcd for
11h by typical procedure D (82%): Colorless oil; 1H-NMR (500 MHz,
CDCl3) d: 7.32 (2H, d, Jꢁ8.5 Hz), 7.24 (2H, d, Jꢁ8.5 Hz), 7.21 (2H, d, Jꢁ
C21H18O4: (M)ꢂ, 3334.1205).
4-Acetoxy-a-(2ꢀ-naphthyl)benzyl Acetate (7) Prepared from 18 by
8.5 Hz), 7.05 (2H, d, Jꢁ8.5 Hz), 6.84 (1H, s), 2.47 (3H, s), 2.29 (3H, s), 2.14 typical procedure D (95%): Colorless oil; 1H-NMR (500 MHz, CDCl3) d:
(3H, s); HR-FAB-MS m/z: 342.1103 (Calcd for C19H18O6: (M)ꢂ, 342.1103).
7.84—7.80 (4H, m), 7.51—7.46 (2H, m), 7.40—7.38 (3H, m), 7.06 (2H, d,
4-Acetoxy-a-(2ꢀ-chlorophenyl)benzyl Acetate (5a) Prepared from 13a Jꢁ7.5 Hz), 7.05 (1H, s), 2.29 (3H, s), 2.19 (3H, s); HR-FAB-MS m/z:
by typical procedure D (94%): Colorless oil; 1H-NMR (500 MHz, CDCl3) d: 334.1202 (Calcd for C21H18O4: (M)ꢂ, 334.1205).
7.47 (1H, d, Jꢁ7.5 Hz), 7.35 (2H, d, Jꢁ8.5 Hz), 7.27 (1H, t, Jꢁ7.5 Hz), 7.23
4-Acetoxy-a-(9ꢀ-anthracenyl)benzyl Acetate (8) Prepared from 19 by