2674
V. Pace et al. / Tetrahedron 67 (2011) 2670e2675
137.8, 160.4. IR (NaCl) cmꢁ1 1622, 3081, 1598, 1562, 919. Anal. Calcd
for C15H19 N: C, 84.86; H, 8.98; N, 6.57. Found: C, 84.71; H, 8.69; N,
6.69.
d (ppm): 13.7, 15.8, 18.1, 32.1, 34.4, 43.8, 74.2, 128.3, 132.1. IR (NaCl)
cmꢁ1: 3444, 2957, 2357, 2339, 2247, 1694, 1682, 1652, 1557, 1454,
912, 731. Anal. Calcd for C9H16O: C, 77.09; H, 11.50. Found: C, 77.24;
H, 11.35.
4.3. General procedure for LiBr mediated 1,2-addition of
different organolithiums in 2-MeTHF to
compounds
a
,
b-unsaturated
4.3.8. 1-n-Pentylcyclohex-2-enol (9). 1H NMR (250 MHz, CDCl3)
d
(ppm): 0.88 (t, J¼7.0 Hz, 3H), 1.18e1.39 (m, 6H), 1.48e1.68 (m,
6H), 1.88e2.06 (m, 2H), 5.56 (d, J¼9.8 Hz, 1H), 5.75 (m, 1H). 13C
In a typical experiment a mixture of
a,
b-unsaturated compound
NMR (62.5 MHz, CDCl3) d (ppm): 14.5, 19.5, 23.6, 25.6, 30.5, 32.8,
(2.00 mmol, 1.0 equiv) and LiBr (3.00 mmol, 1.5 equiv) in freshly
distilled 2-MeTHF (5 mL) was cooled at 0 ꢀC. Organolithium re-
agents (3.00 mmol,1.5 equiv) were then added drop-wise. After 2 h,
reactions were quenched with saturated ammonium chloride
aqueous solution (5 mL). After extraction with ethyl acetate
(2ꢂ10 mL), desiccation over sodium sulfate, filtration, and solvent
removal under reduced pressure, whenever necessary, the crude
products were purified by liquid chromatography.
35.8, 42.7, 70.1, 130.1, 133.3. IR (NaCl) cmꢁ1: 3443, 3018, 2957,
1454. Anal. Calcd for C11H20O: C, 78.51; H, 11.98. Found: C, 78.70;
H, 12.17.
4.3.9. 2-Methyl-4-phenylbut-3-en-2-ol (12a). 1H NMR (250 MHz,
CDCl3)
d
(ppm): 1.47 (s, 6H), 2.02 (br s, 1H), 6.39 (d, J¼16.1 Hz, 1H),
6.64 (d, J¼16.1 Hz, 1H), 7.22e7.26 (m, 1H), 7.31e7.37 (m, 2H), 7.39
(m, 2H). 13C NMR (62.5 MHz, CDCl3)
d
(ppm): 28.8 (ꢂ2), 70.0, 125.9,
127.4, 128.6, 128.9, 131.0, 135.8, 136.5. IR (NaCl) cmꢁ1: 3390, 3082,
1636. Anal. Calcd for C11H14O: C, 81.44; H, 8.70. Found: C, 81.20H,
8.99.
4.3.1. 1-Methylcyclohex-2-enol (2). 1H NMR (250 MHz, CDCl3)
d
(ppm): 1.29 (s, 3H), 1.59e1.91 (m, 7H), 5.63 (d, J¼3.7, 4.1, 10.2 Hz,
1H), 5.70e5.74 (m, 1H, ]CH). 13C NMR (62.5 MHz, CDCl3)
d (ppm):
19.7, 25.2, 29.4, 37.6, 67.7, 129.3, 133.9. IR (NaCl) cmꢁ1 3370, 1655.
Anal. Calcd for C7H12O: C, 74.95; H, 10.78. Found: C, 74.76; H, 10.99.
4.3.10. 3-Methyl-1-phenylhept-1-en-3-ol (12b). 1H NMR (250 MHz,
CDCl3)
d
(ppm): 0.95 (t, J¼7.2 Hz, 3H), 1.36e1.40 (m, 4H), 1.43 (s,
3H), 1.64 (m, 2H), 1.96 (br s, 1H), 6.33 (d, J¼16.1 Hz, 1H), 6.63 (d,
4.3.2. 1-n-Butylcyclohex-2-en-1-ol (3). 1H NMR (250 MHz, CDCl3)
J¼16.1 Hz, 1H), 7.24e7.46 (m, 5H). 13C NMR (62.5 MHz, CDCl3)
d
(ppm): 0.88 (t, J¼7.2 Hz, 3H),1.26e1.38 (m, 4H),1.44e1.55 (m, 3H),
d (ppm): 13.1, 22.1, 25.2, 27.1, 41.6, 72.2, 125.3, 125.4, 125.8, 126.3,
1.60e1.70 (m, 4H), 1.90e2.01 (m, 1H), 2.01e2.10 (m, 1H), 5.59e5.65
(m, 1H), 5.88 (ddd, J¼3.1, 4.1, 10.2 Hz, 1H). 13C NMR (62.5 MHz,
126.4, 127.4, 135.8, 136.0. IR (NaCl) cmꢁ1: 3399, 3078, 1666, 1491,
1456, 936. Anal. Calcd for C14H20O: C, 82.30; H, 9.87. Found: C,
82.56; H, 10.05.
CDCl3)
d (ppm): 13.7, 23.7, 24.8, 35.1, 42.1, 70.4, 130.2, 132.5. IR
(NaCl) cmꢁ1: 3365, 1660. Anal. Calcd for C10H18O: C, 78.87; H, 11.76.
Found: C, 79.05; H, 11.93.
4.3.11. 4-Phenylbut-3-en-2-ol (13a). 1H NMR (250 MHz, CDCl3)
d
(ppm): 1.39 (d, J¼6.5 Hz, 3H), 1.65 (s, 1H), 3.78 (s, 3H), 4.32 (br s,
4.3.3. 1-sec-Butylcyclohex-2-enol (4). 1H NMR (250 MHz, CDCl3)
1H), 6.11 (dd, J¼6.5, 16.3 Hz, 1H), 6.54 (d, J¼16.3 Hz, 1H), 6.86e7.36
d
(ppm): 0.89 (t, J¼7.0 Hz, 3H), 0.95 (d, J¼6.8 Hz, 3H), 1.49 (m, 2H),
(m, 4H). 13C NMR (62.5 MHz, CDCl3)
d (ppm): 23.9, 55.7, 69.5, 114.3,
1.56e1.68 (m, 4H), 1.70 (m, 1H), 1.89e1.95 (m, 1H), 2.03e2.12 (m,
1H), 3.05 (br s,1H), 5.56 (ddt, J¼1.5, 2.6, 8.9 Hz,1H), 5.81 (ddt, J¼2.2,
127.9, 129.1, 129.6, 132.0, 159.5. IR (NaCl) cmꢁ1: 3389, 3074, 1660,
1484, 1442, 921. Anal. Calcd for C14H14O2: C, 74.13; H, 7.92. Found: C,
73.90; H, 8.11.
4.6, 9.1 Hz, 1H). 13C NMR (62.5 MHz, CDCl3)
d (ppm): 16.2, 17.9, 18.4,
25.1, 25.6, 30.3, 36.8, 70.6, 131.0, 133.1. IR (NaCl) cmꢁ1: 3451, 1466,
1435. Anal. Calcd for C10H18O: C, 78.87; H, 11.76. Found: C, 79.58; H,
11.51.
4.3.12. 1-Phenylhept-1-en-3-ol (13b). 1H NMR (250 MHz, CDCl3)
d
(ppm): 0.81 (t, J¼7.5 Hz, 3H), 1.26e1.38 (m, 4H),1.46e1.53 (m, 1H),
2.07 (br s, 1H), 3.73 (s, 3H), 4.21e4.26 (m, 1H), 6.21 (dd, J¼6.5,
4.3.4. 1-tert-Butylcyclohexen-2-enol (5). 1H NMR (250 MHz, CDCl3)
16.2 Hz, 1H), 6.55 (d, J¼16.2 Hz, 1H), 6.73e7.18 (m, 4H). 13C NMR
d
(ppm): 0.82 (s, 9H),1.33e2.41 (m, 7H), 5.78 (d, J¼10.3 Hz,1H), 5.86
(62.5 MHz, CDCl3) d (ppm): 13.0, 21.6, 26.6, 36.1, 54.2, 72.2, 112.9
(ddd, J¼1.9, J¼10.3, 1H). 13C NMR (62.5 MHz, CDCl3)
d
(ppm): 18.9,
(ꢂ2), 126.6 (ꢂ2), 128.0, 130.1, 131.0, 153.3. IR (NaCl) cmꢁ1: 3391,
3062, 1612, 1434, 1422, 1324, 931, 716. Anal. Calcd for C14H20O2: C,
76.33; H, 9.15. Found: C, 76.12; H, 9.36.
25.1, 30.9, 36.8, 72.8, 129.5, 130.9. IR (NaCl) cmꢁ1: 3459, 2962. Anal.
Calcd for C10H18O: C, 77.88; H, 11.74. Found: C, 77.56; H, 11.50.
4.3.5. 1-Phenylcyclohex-2-enol (6). 1H NMR (250 MHz, CDCl3)
4.3.13. Hept-1-en-3-ol (13c). 1H NMR (250 MHz, CDCl3)
d (ppm):
d
(ppm): 1.59 (m, 1H), 1.75 (m, 1H), 1.83 (dd, J¼12.6, 3.0 Hz, 1H),
0.82 (t, J¼6.9 Hz, 3H,), 1.11e1.32 (m, 6H), 1.91 (br s, 1H), 3.97 (dd,
J¼5.1, 7.2 Hz, 1H), 5.06 (dd, J¼10.1, 17.2 Hz, 1H), 5.12 (dd, J¼10.3,
17.2 Hz, 1H), 5.85 (ddd, J¼6.5, 10.3, 17.0 Hz). 13C NMR (62.5 MHz,
1.98e2.20 (m, 4H), 5.72 (d, J¼10.0 Hz, 1H), 6.02 (ddd, J¼3.8, 4.0,
10.0 Hz, 1H), 7.18 (t, J¼1.1, 7.2 Hz, 1H), 7.35 (t, J¼7.9 Hz, 2H), 7.44 (d,
J¼7.9 Hz, 2H). 13C NMR (62.5 MHz, CDCl3)
d
(ppm): 71.9, 124.9,
CDCl3) d (ppm): 14.4, 23.0, 27.9, 37.1, 73.6, 114.9, 141.7. IR (NaCl)
126.6, 128.2, 130.0, 131.8, 147.5. IR (NaCl) cmꢁ1: 3449, 2968, 1462.
Anal. Calcd for C12H14O: C, 82.72; H, 8.10. Found: C, 82.49; H, 8.31.
cmꢁ1: 3378, 3085, 1645. Anal. Calcd for C7H14O: C, 73.63; H, 12.36.
Found: C, 73.89; H, 12.03.
4.3.6. 1-Ethylcyclohex-2-enol (7). 1H NMR (250 MHz, CDCl3)
4.3.14. 2-Methylhept-1-en-3-ol (13d). 1H NMR (250 MHz, CDCl3)
d
(ppm): 0.85 (t, J¼7.5 Hz, 3H), 1.48 (d, J¼7.5 Hz, 2H), 1.61e2.23 (m,
d
(ppm): 0.86 (t, J¼7.0 Hz, 3H,),1.13e1.31 (m, 4H),1.46e1.52 (m, 2H),
7H), 5.59 (d, J¼10.0 Hz, 1H), 5.66 (ddd, J¼2.5, 4.1, 10.0 Hz, 1H). 13C
1.74 (s, 3H), 3.99 (dd, J¼5.0, 7.5 Hz, 1H), 4.75 (d, J¼2.5 Hz), 4.86 (d,
NMR (62.5 MHz, CDCl3)
d
(ppm): 18.1, 19.9, 24.6, 32.1, 33.8, 74.2,
J¼2.6 Hz). 13C NMR (62.5 MHz, CDCl3)
d (ppm): 13.0, 16.4, 21.6, 26.7,
128.4, 131.9. IR (NaCl) cmꢁ1: 3443, 3019, 2959, 2359, 2339, 2249,
1694, 1682, 1652, 1455, 1258, 1177, 1113. Anal. Calcd for C8H14O: C,
76.14; H, 11.18. Found: C, 76.36; H, 10.99.
33.6, 75.0, 109.9, 146.6. IR (NaCl) cmꢁ1: 3386, 3081, 1641, 899. Anal.
Calcd for C8H16O: C, 74.94; H, 12.58. Found: C, 74.70; H, 12.42.
4.3.15. N-(4-Phenylbut-3-en-2-yl)aniline (17a). 1H NMR (250 MHz,
CDCl3)
J¼5.4, 16.0 Hz, 1H), 6.61 (d, J¼16.0 Hz, 1H), 6.66e6.70 (m, 2H),
6.70e6.75 (m, 1H), 7.17e7.22 (m, 2H), 7.22e7.28 (m, 1H), 7.32 (dd,
4.3.7. 1-n-Propylcyclohex-2-enol (8). 1H NMR (250 MHz, CDCl3)
d
(ppm): 1.41 (t, J¼7.1 Hz, 3H), 4.12e4.22 (m, 1H), 6.21 (dd,
d
(ppm): 0.86 (d, J¼7.5 Hz, 3H), 1.20e2.11 (m, 10H), 3.15 (br s, 1H),
5.56 (d, J¼10.0 Hz, 1H), 5.73 (m, 1H). 13C NMR (62.5 MHz, CDCl3)