1378
A. Ladépêche et al.
PAPER
After workup, the products were purified by flash chromatography
(CH2Cl2–cyclohexane or EtOAc–cyclohexane).
13C NMR (100 MHz, CDCl3): d = 142.5, 131.1, 129.2, 128.4, 128.2,
125.6, 78.7, 56.5, 43.7, 35.2, 31.4, 21.2, 16.2, 14.2.
MS (CI): m/z (%) = 233 (6, [M + H]+), 201 (29), 159 (6), 149 (100),
131 (14), 127 (4), 117 (76), 109 (2), 105 (7), 91 (34).
HRMS ([M – H]+): m/z calcd for C16H24O: 231.174891; found:
231.174778.
1-(3-Methoxy-4-cyclohexen-1-ylbutyl)benzene (2)
Compound 1 (556 mg, 3.1 mmol) and methylenecyclohexane (0.37
mL, 3.1 mmol) with FeCl3 (25 mg, 0.15 mmol) in CH2Cl2 (30 mL)
gave 6 after flash chromatography (cyclohexane–CH2Cl2, 60:40);
yield: 716 mg (95%); colorless oil.
1H NMR (400 MHz, CDCl3): d = 7.16–7.31 (m, 5 H), 5.46 (br s, 1
H), 3.35 (s, 3 H), 3.29 (m, 1 H), 2.76 (m, 1 H), 2.62 (m, 1 H), 2.26
(dd, 1 H, J = 6, 14 Hz), 2.05 (dd, 1 H, J = 6.8, 14 Hz), 1.89–1.99 (m,
4 H), 1.69–1.80 (m, 2 H), 1.51–1.63 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 142.5, 134.7, 128.4, 128.3, 125.6,
123.7, 78.7, 56.6, 42.3, 35.3, 31.5, 28.8, 25.3, 23.0, 22.4.
MS (CI): m/z (%) = 245 (1, [M + H]+), 213 (11), 149 (47), 139 (2),
131 (19), 121 (59), 117 (84), 109 (6), 105 (14), 91 (100).
Anal. Calcd for C16H24O: C, 82.70; H, 10.41. Found: C, 82.42; H,
10.58.
1-(3-Methoxy-5-methyldec-5-enyl)benzene (10)
Compound 1 (556 mg, 3.1 mmol) and 2-methylhept-1-ene (0.49
mL, 3.1 mmol) with FeCl3 (25 mg, 0.15 mmol) in CH2Cl2 (30 mL)
gave 10 after flash chromatography (cyclohexane–CH2Cl2, 60:40);
yield: 711 mg (88%); colorless oil.
1H NMR (400 MHz, CDCl3): d = 7.16–7.30 (m, 5 H), 5.21 (t, 1 H,
J = 7.2 Hz), 3.37 (s, 3 H), 3.29 (m, 1 H), 2.78 (m, 1 H), 2.63 (m, 1
H), 2.34 (dd, 1 H, J = 6, 13.2 Hz), 2.18 (dd, 1 H, J = 7.2, 13.2 Hz),
1.99 (m, 2 H), 1.72–1.81 (m, 2 H), 1.68 (s, 3 H), 1.29 (m, 4 H), 0.87
(t, 3 H, J = 6.4 Hz).
HRMS ([M – H]+): m/z calcd for C17H24O: 243.174891; found:
243.174416.
1-(3-Methoxy-4-cyclopenten-1-ylbutyl)benzene (7)
Compound 1 (556 mg, 3.1 mmol) and methylenecyclopentane (0.32
mL, 3.1 mmol) with FeCl3 (25 mg, 0.15 mmol) in CH2Cl2 (30 mL)
gave 7 after flash chromatography (cyclohexane–CH2Cl2, 60:40);
yield: 674 mg (94%); colorless oil.
1H NMR (400 MHz, CDCl3): d = 7.16–7.30 (m, 5 H), 5.40 (br s, 1
H), 3.36 (s, 3 H), 3.34 (m, 1 H), 2.75 (m, 1 H), 2.63 (m, 1 H), 2.40
(dd, 1 H, J = 5.6, 14.4 Hz), 2.20–2.32 (m, 5 H), 1.85 (m, 2 H), 1.76
(m, 2 H).
13C NMR (100 MHz, CDCl3): d = 142.5, 131.6, 128.4, 128.3, 127.7,
125.6, 78.8, 56.5, 43.8, 35.3, 31.9, 31.4, 27.6, 22.3, 16.4, 14.0.
MS (CI): m/z (%) = 261 (1, [M + H]+), 229 (20), 173 (5), 159 (6),
155 (2), 149 (100), 131 (15), 117 (63), 105 (5), 91 (25).
HRMS ([M – H]+): m/z calcd for C18H28O: 259.206191; found:
259.207902.
1-(3-Ethoxy-4-cyclohexen-1-ylbutyl)benzene (11)
Compound 3 (642 mg, 3.1 mmol) and methylenecyclohexane (0.37
mL, 3.1 mmol) with FeCl3 (25 mg, 0.15 mmol) in CH2Cl2 (30 mL)
yielded 11 after flash chromatography (cyclohexane–CH2Cl2,
60:40); yield: 752 mg (94%); colorless oil.
13C NMR (100 MHz, CDCl3): d = 142.4, 141.1, 128.4, 128.2, 126.0,
125.7, 78.8, 56.4, 35.4, 35.2, 32.4, 31.5, 23.5.
MS (CI): m/z (%) = 231 (3, [M + H]+), 199 (29), 157 (3), 149 (70),
131 (11), 125 (2), 121 (74), 117 (100), 105 (10), 95 (9), 91 (74).
HRMS ([M – H]+): m/z calcd for C16H22O: 229.159240; found:
229.159175.
1H NMR (400 MHz, CDCl3): d = 7.16–7.30 (m, 5 H), 5.45 (br s),
3.54 (m, 1 H), 3.45 (m, 1 H), 3.36 (m, 1 H), 2.79 (m, 1 H), 2.62 (m,
1 H), 2.24 (dd, 1 H, J = 6, 13.6 Hz), 2.06 (dd, 1 H, J = 6.8, 13.6 Hz),
1.90–1.98 (m, 4 H), 1.67–1.81 (m, 2 H), 1.50–1.63 (m, 4 H), 1.20 (t,
3 H, J = 7.2 Hz).
1-(3-Methoxy-5-ethylhept-5-enyl)benzene (8)
Compound 1 (556 mg, 3.1 mmol) and 2-ethylbut-1-ene (0.38 mL,
3.1 mmol) with FeCl3 (25 mg, 0.15 mmol) in CH2Cl2 (30 mL) af-
forded 8 after flash chromatography (cyclohexane–CH2Cl2, 60:40);
yield: 650 mg (90%); colorless oil.
1H NMR (400 MHz, CDCl3): d = 7.16–7.30 (m, 5 H), 5.21 (q, 1 H,
J = 6.8 Hz), 3.38 (s, 3 H), 3.28 (m, 1 H), 2.77 (m, 1 H), 2.62 (m, 1
H), 2.35 (dd, 1 H, J = 5.6, 13.2 Hz), 2.06 (dd, 1 H, J = 6, 13.2 Hz),
2.00 (m, 2 H), 1.66–1.87 (m, 2 H), 1.59 (q, 2 H, J = 7.2 Hz), 1.06
(d, 3 H, J = 6.8 Hz), 0.95 (t, 3 H, J = 7.2 Hz).
13C NMR (100 MHz, CDCl3): d = 142.6, 134.8, 128.4, 128.3, 125.6,
123.7, 77.2, 64.3, 43.1, 35.8, 31.7, 28.8, 25.3, 23.0, 22.4, 15.7.
MS (CI): m/z (%) = 259 (2, [M + H]+), 213 (13), 163 (100), 123
(35), 117 (68), 109 (15), 91 (18), 81 (6).
HRMS ([M – H]+): m/z calcd for C18H26O: 257.190541; found:
257.191323.
Anal. Calcd for C18H26O: C, 83.67; H, 10.14. Found: C, 83.40; H,
10.30.
13C NMR (100 MHz, CDCl3): d = 142.6, 138.6, 128.4, 128.3, 125.6,
119.5, 79.0, 56.5, 40.7, 35.4, 31.5, 22.9, 13.1, 12.7.
1-(1-Methoxy-2-cyclohexen-1-ylethyl)benzene (12)
Compound 4 (472 mg, 3.1 mmol) and methylenecyclohexane (0.37
mL, 3.1 mmol) with FeCl3 (25 mg, 0.15 mmol) in CH2Cl2 (30 mL)
yielded 12 after flash chromatography (cyclohexane–CH2Cl2,
60:40); yield: 442 mg (66%); colorless oil.
MS (CI): m/z (%) = 233 (3, [M + H]+), 201 (29), 149 (97), 131 (17),
117 (100), 105 (12), 91 (70).
HRMS ([M – H]+): m/z calcd for C16H24O: 231.174891; found:
231.174237.
1H NMR (400 MHz, CDCl3): d = 7.20–7.35 (m, 5 H), 5.38 (br s, 1
H), 4.24 (dd, 1 H, J = 5.6, 8 Hz), 3.21 (s, 3 H), 2.46 (dd, 1 H, J = 8,
14 Hz), 2.20 (dd, 1 H, J = 5.6, 14 Hz), 1.84–2.00 (m, 4 H), 1.48–
1.61 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 142.4, 134.3, 128.2, 127.4, 126.6,
123.6, 82.7, 56.7, 46.9, 28.7, 25.3, 22.9, 22.3.
1-(3-Methoxy-5-methyloct-5-enyl)benzene (9)
Compound 1 (556 mg, 3.1 mmol) and 2-methylpent-1-ene (0.38
mL, 3.1 mmol) with FeCl3 (25 mg, 0.15 mmol) in CH2Cl2 (30 mL)
gave 9 after flash chromatography (cyclohexane–CH2Cl2, 60:40);
yield: 585 mg (81%); colorless oil.
MS (CI): m/z (%) = 217 (12, [M + H]+), 185 (19), 157 (16), 143
(46), 129 (47), 121 (60), 105 (19), 95 (39), 91 (100), 77 (18), 67
(22).
HRMS ([M – H]+): m/z calcd for C15H20O: 215.143590; found:
215.143002.
1H NMR (400 MHz, CDCl3): d = 7.19–7.32 (m, 5 H), 5.24 (t, 1 H,
J = 6.4 Hz), 3.40 (s, 3 H), 3.32 (m, 1 H), 2.81 (m, 1 H), 2.67 (m, 1
H), 2.37 (dd, 1 H, J = 6, 13.6 Hz), 2.20 (dd, 1 H, J = 6.8, 13.6 Hz),
2.05 (m, 2 H), 1.74–1.82 (m, 2 H), 1.72 (s, 3 H), 0.96 (t, 3 H, J = 7.6
Hz).
Synthesis 2004, No. 9, 1375–1380 © Thieme Stuttgart · New York