NJC
Paper
4
5
1
.28 (br dd, J = 2.1, 8.1 Hz, 1H), 5.20 (br dd, J = 1.8, 17.2 Hz, 1H), 29.2, 30.3, 30.4, 39.9, 42.7, 43.8, 80.2, 115.0, 143.1; high-
.23 (br dd, J = 1.8, 10.3 Hz, 1H), 5.72 (ddd, J = 9.5, 10.3, 17.2 Hz, resolution MS, calcd for C15 28O: 224.2140, found m/z (relative
H), 7.13–7.53 (m, 5H); C NMR (100 MHz, CDCl , anti-isomer) d intensity): 224.2079 (M , 24), 223 (100).
H
13
+
3
3
0.0, 31.0, 44.1, 49.4, 77.4, 118.2, 127.4, 127.6, 128.2, 141.9, 142.3;
2,2-Dimethyl-4-vinyldecan-5-ol (1e) (a mixture of 1,2-anti :
1
H NMR (400 MHz, CDCl , syn-isomer) d 0.81 (s, 9H), 1.16 (dd, J = syn = 1 : 1 ratio). IR (neat) 3362 (w), 2934 (s), 2862 (s), 1638 (w)
3
À1
1
9
5
1
.5, 13.9 Hz, 1H), 1.47 (dd, J = 2.2, 13.9 Hz, 1H), 2.14 (br d, J = cm ; (one isomer): H NMR (400 MHz, CDCl
.3 Hz, 1H), 2.54 (br dq, J = 2.2, 9.5 Hz, 1H), 4.58 (br t, J = 5.3 Hz, 0.87 (t, J = 5.6 Hz, 3H), 0.89 (s, 9H), 1.21–1.39 (ddm, J = 4.6,
H), 5.08 (br d, J = 10.8, 1H), 5.09 (br dd, J = 16.9 Hz, 1H), 5.62 (ddd, 7.8 Hz, 10H), 2.28 (dq, J = 4.1, 8.3 Hz, 1H), 3.33–3.40 (m, 1H),
3
, anti-isomer) d
13
J = 9.0, 10.8, 16.9 Hz, 1H), 7.13–7.53 (m, 5H); C NMR (100 MHz, 5.08 (dd, J = 1.7, 18.5 Hz, 1H), 5.13 (dd, J = 1.7, 10.0, Hz, 1H),
CDCl
1
3
3
, syn-isomer) d 30.1, 31.0, 42.9, 47.8, 77.4, 116.6, 126.8, 127.2, 5.69 (ddd, J = 8.3, 10.0, 18.5 Hz, 1H); C NMR (400 MHz, CDCl
3
,
1
2
27.9, 141.4, 142.4; high-resolution MS, calcd for C H O: one isomer) d 14.0, 22.6, 26.0, 30.1, 31.1, 33.2, 44.1, 75.7, 116.4,
15 22
+
1
18.1671. Found m/z (relative intensity) 218.1692 (M , 100), 201 141.5; (minor isomer): H NMR (400 MHz, CDCl , other isomer)
3
(88), 147 (34), 146 (32).
d 0.90 (s, 9H), 0.94 (t, J = 7.2 Hz, 3H), 2.12–2.18 (dddm, J = 0.7,
1
-(4-Methoxyphenyl)-4,4-dimethyl-2-vinylpentan-1-ol (1b) (a mixture 4.6, 8.8 Hz, 1H), 5.09 (dd, J = 0.7, 15.9 Hz, 1H), 5.09 (d, J =
1
3
of 1,2-anti :syn = 6:1 ratio). IR (neat) 3452 (m), 2866 (m), 1612 (m), 11.5 Hz, 1H), 5.68 (ddd, J = 8.8, 11.5, 15.9 Hz, 1H); C NMR
À1
1
1
514 (s), 1248 (s), 1038 (s), 833 (s) cm ; H NMR (400 MHz, CDCl
anti-isomer) d 0.76 (s, 9H), 1.17 (dd, J = 3.0, 14.0 Hz, 1H), 1.23 (dd, J = 44.9, 46.8, 74.9, 116.9, 141.2; high-resolution MS, calcd for
.6, 14.0 Hz, 1H), 2.27 (d, J = 1.7 Hz, 1H), 2.42 (ddm, J = 3.0, 8.6 Hz, 24O: 212.214, found m/z (relative intensity): 212.2099
H), 3.80 (s, 3H), 4.22 (dd, J = 1.7, 8.1 Hz, 1H), 5.20 (dd, J = 1.8, 17.1 Hz, (M , 46), 197 (100).
H), 5.23 (dd, J = 1.8, 10.2 Hz, 1H), 5.72 (ddd, J = 9.3, 10.2, 17.1 Hz, 1H), 2,5,5-Trimethyl-3-vinylhexan-2-ol (1f). IR (neat) 3435 (w),
.86 (d, J = 8.5 Hz, 2H), 7.24 (d, J = 8.5 Hz, 2H); C NMR (400 MHz, 2959 (m), 2868 (w), 2345 (w), 1720 (w), 1466 (w), 1020 (m),
CDCl
28.3, 134.2, 142.1, 158.9; H NMR (400 MHz, CDCl
.83 (s, 9H), 2.51–2.53 (m, 1H), 3.80 (s, 3H), 4.53 (t, J = 5.1 Hz, 1H), 5.05 1.6, 13.9 Hz, 1H), 1.75 (s, 1H), 2.12 (br td, J = 1.0, 9.5 Hz, 1H),
dd, J = 1.9, 9.1 Hz, 1H), 5.07 (dd, J = 1.9, 16.8 Hz, 1H), 5.62 (ddd, 5.12 (ddd, J = 1.0, 2.0, 17.3 Hz, 1H), 5.15 (dd, J = 2.0, 10.2 Hz,
3
,
3
(400 MHz, CDCl , other isomer) d 25.6, 30.2, 31.2, 31.9, 34.4,
8
1
1
6
12
C H
+
13
À1
1
3
, anti-isomer) d 30.0, 31.0, 44.1, 49.5, 55.2, 76.4, 113.4, 118.0, 802 (m) cm ; H NMR (400 MHz, CDCl
3
) d 0.90 (s, 9H), 1.10
1
1
0
(
3
, syn-isomer) d (s, 3H), 1.18 (s, 3H), 1.24 (dd, J = 9.5, 13.9 Hz, 1H), 1.45 (dd, J =
1
3
13
J = 9.1, 10.5, 16.8 Hz, 1H); C NMR (400 MHz, CDCl
3
) d 30.1, 1H), 5.67 (ddd, J = 9.5, 10.2, 17.3 Hz, 1H); C NMR (400 MHz,
4
3.2, 47.8, 113.2, 116.5, 127.8, 134.4, 141.2; high-resolution MS, CDCl ) d 26.4, 26.9, 30.2, 31.1, 43.6, 52.3, 71.9, 117.9, 141.9;
3
calcd for C H ClO: 248.1776, found m/z (relative intensity): high-resolution MS, calcd for C H O: 170.1671, found m/z
1
5
21
11 22
+
+
+
2
48.1767 (M , 75), 215 (100).
(relative intensity): 171 (M + 1, 76), 170.1578 (M , 59), 169 (89).
1-(4-Chlorophenyl)-4,4-dimethyl-2-vinylpentan-1-ol (1c) (a mixture
2,4,4-Trimethyl-1-phenyl-2-vinylpentan-1-ol (2a) (a mixture
of 1,2-anti :syn = 9:1 ratio). IR (neat) 3433 (m), 2909 (s), 1638 (w), of 1,2-anti : syn = 10 : 1 ratio). IR (neat) 3462 (br m), 3030 (m),
À1 1
À1
1
1
(
2
7
1
(
3
090 (s), 831 (s) cm ; H NMR (400 MHz, CDCl
s, 9H), 1.16 (dd, J = 2.4, 13.9 Hz, 1H), 1.25 (dd, J = 9.0, 13.9 Hz, 1H), (400 MHz, CDCl
.32 (br s, 1H), 2.39 (dddd, J = 2.4, 7.8, 9.0, 9.3 Hz, 1H), 4.57 (d, J = (d, J = 13.8 Hz, 1H), 1.55 (d, J = 13.8 Hz, 1H), 2.14 (d, J = 1.7 Hz,
.8 Hz, 1H), 5.17 (dd, J = 1.3, 17.2 Hz, 1H), 5.18 (dd, J = 1.3, 10.2 Hz, 1H), 4.24 (d, J = 1.7 Hz, 1H), 5.12 (dd, J = 1.2, 17.6 Hz, 1H), 5.26
H), 5.70 (ddd, J = 9.3, 10.2, 17.2 Hz, 1H), 7.25 (d, J = 8.7 Hz, 2H), 7.30 (dd, J = 1.2, 10.9 Hz, 1H), 5.98 (dd, J = 10.9, 17.6 Hz, 1H),
3
, anti-isomer) d 0.76 2953 (s), 1634 (w), 1454 (s), 1022 (s), 910 (s) cm ; H NMR
3
, anti-isomer) d 0.90 (s, 9H), 1.10 (s, 3H), 1.24
13
13
d, J = 8.7 Hz, 2H); C NMR (400 MHz, CDCl , anti-isomer) d 30.0, 7.20–7.34 (m, 5H); C NMR (400 MHz, CDCl , anti-isomer) d
3
3
1
1.0, 44.0, 49.4, 76.2, 118.5, 128.1, 128.6, 133.1, 140.6, 141.3; H NMR 17.2, 29.7, 31.9, 46.9, 50.7, 80.7, 114.8, 126.2, 127.2, 128.3,
1
(400 MHz, CDCl
3 3
, syn-isomer) d 0.81 (s, 9H), 2.50–2.52 (m, 1H), 4.27 139.9, 145.9; H NMR (400 MHz, CDCl , syn-isomer) d 0.76
(
1
t, J = 4.6 Hz, 1H), 5.08 (dm, J = 17.2 Hz, 1H), 5.10 (dm, J = 10.4 Hz, (s, 9H), 1.23 (s, 3H), 1.23 (d, J = 4.3 Hz, 1H), 1.41 (d, J = 4.3 Hz,
13
H), 5.60 (ddd, J = 9.3, 10.4, 17.2 Hz, 1H); C NMR (400 MHz, CDCl
3
,
1H), 2.04 (d, J = 6.0 Hz, 1H), 4.27 (d, J = 6.0 Hz, 1H), 5.01 (dd,
syn-isomer) d 30.1, 42.8, 47.7, 116.9, 140.7, 140.8; high-resolution MS, J = 1.3, 17.6 Hz, 1H), 5.15 (dd, J = 1.3, 11.8 Hz, 1H), 5.97 (dd,
1
3
calcd for C H ClO: 252.1281, found m/z (relative intensity): J = 11.8, 17.6 Hz, 1H); C NMR (400 MHz, CDCl , syn-isomer) d
15
+
21
3
252.1295 (M , 68), 219 (100).
19.9, 30.7, 32.2, 46.1, 50.1, 82.3, 113.9, 126.9, 127.3, 127.9,
1
-Cyclohexyl-4,4-dimethyl-2-vinylpentan-1-ol (1d) (a mixture 141.3, 144.7; high-resolution MS, calcd for C H O: 232.1827,
16 24
+
of 1,2-anti : syn = 9 : 1 ratio). IR (neat) 3368 (br m), 3071 (s), 2853 found m/z (relative intensity): 232.1823 (M , 2), 199 (100).
s), 1636 (w) cm ; H NMR (400 MHz, CDCl
À1
1
(
3
, anti-isomer) d
4,4-Dimethyl-1-phenyl-2-(prop-1-en-2-yl)pentan-1-ol (3a) (a
0
.90 (s, 9H), 0.96–1.30 (m, 5H), 1.32–1.42 (m, 3H), 1.64–1.76 mixture of 1,2-anti : syn = 9 : 1 ratio). IR (neat) 3470 (m), 3030
À1
(
(
m, 4H), 1.81–1.86 (m, 1H), 2.37 (dq, J = 5.2, 9.2 Hz, 1H), 3.07 (w), 2866 (m), 1641 (w), 1196 (m), 1022 (m), 889 (m) cm ;
t, J = 5.2 Hz, 1H), 5.08 (ddd, J = 0.7, 1.9, 17.3 Hz, 1H), 5.14 (dd,
1
3
H NMR (400 MHz, CDCl , anti-isomer) d 0.71 (s, 9H), 0.97 (dd,
J = 1.9, 10.4 Hz, 1H), 5.73 (ddd, J = 9.2, 10.4, 17.3 Hz, 1H); J = 2.0, 14.1 Hz, 1H), 1.39 (dd, J = 9.6, 14.1 Hz, 1H), 1.78 (dd, J =
1
3
C NMR (400 MHz, CDCl , anti-isomer) d 26.1, 26.3, 26.5, 27.8, 0.7, 1.5 Hz, 3H), 2.35 (br s, 1H), 2.52 (dt, J = 2.0, 9.6 Hz, 1H), 4.27
3
1
3
0.0, 30.1, 31.3, 40.3, 42.9, 45.5, 79.1, 116.7, 140.8; H NMR (d, J = 9.6 Hz, 1H), 5.04 (dd, J = 0.7, 1.8 Hz, 1H), 5.07 (dd, J = 1.5,
1
3
(400 MHz, CDCl
3 3
, syn-isomer) d 0.86 (s, 9H), 3.13 (m, 1H), 5.02 1.8, Hz, 1H), 7.33 (d, J = 4.4 Hz, 5H); C NMR (400 MHz, CDCl ,
(
1
dm, J = 1.0 Hz, 1H), 5.07 (dm, J = 1.0 Hz, 1H), 5.75 (dd, J = 8.5, anti-isomer) d 18.9, 29.5, 31.0, 41.2, 52.6, 75.5, 116.1, 127.4,
7.6 Hz, 1H); C NMR (400 MHz, CDCl , syn-isomer) d 27.2, 127.5, 128.0, 142.5, 146.9; H NMR (400 MHz, CDCl , syn-
3 3
1
3
1
334 | New J. Chem., 2014, 38, 330--337
This journal is ©The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014