Job/Unit: O20350
/KAP1
Date: 05-06-12 15:44:12
Pages: 9
B. Guo, C. Fu, S. Ma
FULL PAPER
141.0, 140.1, 128.4, 128.3, 125.9, 124.9, 66.9, 33.7, 30.8, 27.8, 22.9,
8.9 Hz, 1 H, one proton of ArCH2), 2.08–1.91 (m, 2 H, CH2), 1.91–
1.78 (m, 1 H, CH), 1.60 (d, J = 3.0 Hz, 1 H, OH), 0.97–0.88 (m, 6
H, 2 CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 149.9, 138.4,
129.4, 128.4, 126.5, 110.7, 75.4, 42.7, 42.2, 26.5, 22.8, 22.4 ppm. IR
14.0 ppm. IR (neat): ν = 3327, 3085, 3062, 3027, 2956, 2931, 2860,
˜
1604, 1494, 1453, 1378, 1221, 1159, 1103, 1058, 1030, 1000 cm–1.
MS (EI, 70 eV): m/z (%) = 204 (18.17) [M]+, 173 (91.91) [M –
CH2OH]+, 117 (100). HRMS: calcd for C14H20O [M]+ 204.1514; (neat): ν = 3420, 3086, 3063, 3028, 2954, 2924, 2868, 1647, 1599,
˜
found 204.1513.
1496, 1454, 1384, 1366, 1168, 1099, 1077, 1050, 1031 cm–1. MS (EI,
70 eV): m/z (%) = 204 (1.24) [M]+, 92 (100). HRMS: calcd for
C14H20O [M]+ 204.1514; found 204.1511.
2,3-Dibutylhept-2-en-1-ol (3o): The reaction of K2CO3 (187.0 mg,
1.35 mmol), Pd(OAc)2 (3.4 mg, 0.015 mmol), 2a (46.3 mg,
0.45 mmol), 1o (75.0 mg, 0.3 mmol), toluene (2 mL), and LB-
Phos·HBF4 (6.8 mg, 0.015 mmol) at 110 °C for 4 h afforded 3o
(36.7 mg, 54%) after purification by chromatography [petroleum
ether (30–60 °C)/ethyl acetate = 30:1] as a liquid. 1H NMR
(300 MHz, CDCl3): δ = 4.10 (s, 2 H, CH2-O), 2.18–1.93 (m, 6 H,
3 CH2), 1.46–1.23 (m, 12 H, 6 CH2), 1.18 (br. s, 1 H), 1.02–0.83
(m, 9 H, 3 CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 139.1,
132.9, 61.7, 32.1, 31.7, 31.6, 31.4, 31.2, 29.9, 23.05, 22.98, 22.9,
3-Cyclopropyl-1-phenylbut-3-en-2-ol (3s): The reaction of K2CO3
(186.2 mg, 1.35 mmol), Pd(OAc)2 (3.4 mg, 0.015 mmol), 2b
(39.1 mg, 0.45 mmol), 1a (68.3 mg, 0.3 mmol), toluene (2 mL), and
LB-Phos·HBF4 (6.8 mg, 0.015 mmol) at 110 °C for 22.5 h afforded
3s (48.4 mg, 86%) after purification by chromatography (n-hexane/
ethyl acetate = 30:1) as a liquid. 1H NMR (300 MHz, CDCl3): δ =
7.39–7.17 (m, 5 H, ArH), 4.87 (s, 1 H, one proton of =CH2), 4.62
(s, 1 H, one proton of =CH2), 4.37 (dd, J = 8.4, 3.9 Hz, 1 H, CH-
O), 3.05 (dd, J = 13.8, 4.5 Hz, 1 H, one proton in ArCH2), 2.83
(dd, J = 13.5, 8.7 Hz, 1 H, one proton in ArCH2), 1.84 (s, 1 H,
OH), 1.45–1.33 (m, 1 H, CH), 0.82–0.67 (m, 2 H, CH2), 0.58–0.43
(m, 2 H, CH2) ppm. 13C NMR (75 MHz, CDCl3): δ = 152.7, 138.4,
14.0 ppm. IR (neat): ν = 3322, 2957, 2929, 2872, 2860, 1466, 1378,
˜
1150, 1105, 1084, 1022 cm–1. MS (EI, 70 eV): m/z (%) = 226 (16.99)
[M]+, 208 (14.61) [M – H2O]+, 169 (100). HRMS: calcd for
C15H30O [M]+ 226.2297; found 226.2293.
129.4, 128.3, 126.4, 106.0, 42.8, 12.1, 7.1 ppm. IR (neat): ν = 3420,
˜
(Z)-2-Butyl-3-phenylnon-2-en-1-ol (3p): The reaction of K2CO3
(186.5 mg, 1.35 mmol), Pd(OAc)2 (3.4 mg, 0.015 mmol), 2a
(46.2 mg, 0.45 mmol), 1p (89.4 mg, 0.3 mmol), toluene (2 mL), and
LB-Phos·HBF4 (6.8 mg, 0.015 mmol) at 110 °C for 13.7 h afforded
3p (49.8 mg, 60%) after purification by chromatography [petroleum
ether (30–60 °C)/ethyl acetate = 30:1] as a liquid. 1H NMR
(300 MHz, CDCl3): δ = 7.40–7.18 (m, 3 H, ArH), 7.17–7.00 (m, 2
H, ArH), 3.87 (s, 2 H, CH2-O), 2.40–2.21 (m, 4 H, 2 CH2), 1.55–
1.30 (m, 4 H, 2 CH2), 1.30–1.05 (m, 9 H), 0.96 (t, J = 7.2 Hz, 3 H,
CH3), 0.84 (t, J = 6.8 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz,
CDCl3): δ = 142.5, 140.5, 135.1, 128.5, 128.0, 126.3, 62.9, 34.1,
3083, 3060, 3028, 3000, 2922, 2852, 1644, 1602, 1496, 1454, 1423,
1391, 1269, 1081, 1043, 1020 cm–1. MS (EI, 70 eV): m/z (%) = 188
(3.05) [M]+, 92 (100). HRMS: calcd for C13H16O [M]+ 188.1201;
found 188.1204.
3-Methylene-1-phenyloctan-2-ol (3t): The reaction of K2CO3
(185.5 mg, 1.35 mmol), Pd(OAc)2 (3.4 mg, 0.015 mmol), 2d
(52.8 mg, 0.45 mmol), 1a (67.6 mg, 0.3 mmol), toluene (2 mL), and
LB-Phos·HBF4 (6.8 mg, 0.015 mmol) at 110 °C for 3 h afforded 3t
(51.7 mg, 80%) after purification by chromatography (petroleum
ether/ethyl acetate = 30:1) as a liquid. 1H NMR (300 MHz,
CDCl3): δ = 7.36–7.26 (m, 2 H, ArH), 7.26–7.16 (m, 3 H, ArH),
5.04 (s, 1 H, one proton of =CH2), 4.87 (d, J = 0.9 Hz, 1 H, one
proton of =CH2), 4.26 (dd, J = 8.9, 3.8 Hz, 1 H, CH-O), 2.93 (dd,
J = 13.8, 4.2 Hz, 1 H, one proton in ArCH2), 2.73 (dd, J = 13.8,
8.7 Hz, 1 H, one proton in ArCH2), 2.21–1.98 (m, 2 H, CH2), 1.69
(s, 1 H, OH), 1.56–1.40 (m, 2 H, CH2), 1.40–1.26 (m, 4 H, 2 CH2),
0.91 (t, J = 6.8 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3):
δ = 151.4, 138.4, 129.3, 128.4, 126.4, 109.4, 75.8, 42.7, 31.9, 31.7,
31.7, 31.3, 29.4, 29.3, 28.0, 23.0, 22.6, 14.1, 14.0 ppm. IR (neat): ν
˜
= 3322, 3075, 3056, 3015, 2926, 2858, 1596, 1491, 1466, 1444, 1378,
1233, 1185, 1099, 1069, 1028 cm–1. MS (EI, 70 eV): m/z (%) = 274
(45.49) [M]+, 217 (57.61) [M – C4H9]+, 91 (100). HRMS: calcd for
C19H30O [M]+ 274.2297; found 274.2294.
3-(Diphenylmethylene)heptan-2-ol (3q): The reaction of K2CO3
(186.4 mg, 1.35 mmol), Pd(OAc)2 (3.4 mg, 0.015 mmol), 2a
(46.1 mg, 0.45 mmol), 1q (90.7 mg, 0.3 mmol), toluene (2 mL), and
LB-Phos·HBF4 (6.8 mg, 0.015 mmol) at 110 °C for 7.5 h afforded
3q (47.1 mg, 56%) after purification by chromatography [petroleum
ether (30–60 °C)/ethyl acetate = 30:1] as a liquid. 1H NMR
(300 MHz, CDCl3): δ = 7.35–7.22 (m, 4 H, ArH), 7.22–7.10 (m, 6
H, ArH), 4.65 (q, J = 6.5 Hz, 1 H, CH-O), 2.28–2.09 (m, 2 H,
CH2), 1.50–1.22 (m, 6 H, OH, CH2, CH3), 1.22–1.07 (m, 2 H,
CH2), 0.72 (t, J = 7.4 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz,
CDCl3): δ = 142.6, 142.3, 141.4, 140.2, 128.9, 128.8, 128.2, 128.1,
27.6, 22.5, 14.0 ppm. IR (neat): ν = 3417, 3085, 3063, 3028, 2955,
˜
2928, 2859, 1646, 1603, 1496, 1455, 1378, 1078, 1031 cm–1. MS (EI,
70 eV): m/z (%) = 218 (1.18) [M]+, 92 (100). HRMS: calcd for
C15H22O [M]+ 218.1671; found 218.1672.
3-Methylene-1-phenylnonan-2-ol (3u): The reaction of K2CO3
(186.2 mg, 1.35 mmol), Pd(OAc)2 (3.4 mg, 0.015 mmol), 2e
(58.7 mg, 0.45 mmol), 1a (68.2 mg, 0.3 mmol), toluene (2 mL), and
LB-Phos·HBF4 (6.8 mg, 0.015 mmol) at 110 °C for 2.3 h afforded
3u (58.3 mg, 84%) after purification by chromatography (petroleum
ether/ethyl acetate = 30:1) as a liquid. 1H NMR (300 MHz,
CDCl3): δ = 7.38–7.28 (m, 2 H, ArH), 7.28–7.17 (m, 3 H, ArH),
5.05 (s, 1 H, one proton of =CH2), 4.88 (d, J = 1.2 Hz, 1 H, one
proton of =CH2), 4.27 (dd, J = 8.7, 3.9 Hz, 1 H, CH-O), 2.93 (dd,
J = 13.7, 4.1 Hz, 1 H, one proton of ArCH2), 2.73 (dd, J = 13.7,
8.9 Hz, 1 H, one proton of ArCH2), 2.22–1.97 (m, 2 H, CH2), 1.65
(s, 1 H, OH), 1.57–1.42 (m, 2 H, CH2), 1.42–1.22 (m, 6 H, 3 CH2),
0.90 (t, J = 6.5 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3):
δ = 151.4, 138.5, 129.3, 128.4, 126.5, 109.4, 75.9, 42.7, 32.0, 31.7,
126.5, 126.4, 68.5, 32.8, 27.2, 23.1, 22.0, 13.7 ppm. IR (neat): ν =
˜
3389, 3077, 3055, 3020, 2957, 2930, 2871, 1597, 1490, 1463, 1443,
1367, 1285, 1100, 1073, 1053, 1031, 1002 cm–1. MS (EI, 70 eV): m/z
(%) = 280 (1.87) [M]+, 223 (79.04) [M – C4H9]+, 167 (100). HRMS:
calcd for C20H24O [M]+ 280.1827; found 280.1830.
5-Methyl-3-methylene-1-phenylheptan-2-ol (3r): The reaction of
K2CO3 (186.7 mg, 1.35 mmol), Pd(OAc)2 (3.4 mg, 0.015 mmol), 2b
(46.0 mg, 0.45 mmol), 1a (68.7 mg, 0.3 mmol), toluene (2 mL), and
LB-Phos·HBF4 (6.8 mg, 0.015 mmol) at 110 °C for 17 h afforded
3r (25.2 mg, 41%) after purification by chromatography [petroleum
ether (30–60 °C)/ethyl acetate = 30:1] as a liquid. 1H NMR
(300 MHz, CDCl3): δ = 7.37–7.28 (m, 2 H, ArH), 7.28–7.18 (m, 3
H, ArH), 5.12 (s, 1 H, one proton of =CH2), 4.87 (d, J = 0.9 Hz,
1 H, one proton of =CH2), 4.29–4.19 (m, 1 H, CH-O), 2.95 (dd, J
= 13.8, 6.9 Hz, 1 H, one proton of ArCH2), 2.71 (dd, J = 13.8,
29.2, 27.9, 22.6, 14.1 ppm. IR (neat): ν = 3407, 3085, 3063, 3028,
˜
2956, 2927, 2857, 1647, 1603, 1496, 1454, 1378, 1108, 1078, 1049,
1031 cm–1. MS (EI, 70 eV): m/z (%) = 232 (0.75) [M]+, 92 (100).
HRMS: calcd for C16H24O [M]+ 232.1827; found 232.1834.
3-Methylene-1-phenyltridecan-2-ol (3v): The reaction of K2CO3
(186.6 mg, 1.35 mmol), Pd(OAc)2 (3.4 mg, 0.015 mmol), 2f
6
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