698 Letters in Organic Chemistry, 2011, Vol. 8, No. 10
Marques et al.
with a DB-5 (30 m x 0.25 mm x 0.25 μm) capillary column
NMR (CDCl3) 55.3; 74.9; 113.9 114.7; 127.7; 134.9; 140.4;
159.1. IR (film) (cm-1) 3445, 2931, 2837, 1613, 1446, 960.
MS m/z (relative intensity) 164 (M+, 100%), 147 (62%), 121
(52%), 109 (62%), 77 (35%).
where the carrier gas was also helium with a pressure of 25
1
psi. H and 13C NMR spectra were acquired in CDCl3 on a
Bruker AVANCE 400 NMR spectrometer, operating at 9.4
1
Tesla, observing H and 13C at 400.13 and 100.61 MHz,
1-(4-chlorophenyl)prop-2-en-1-ol (1d)
respectively, equipped with a 5 mm multinuclear direct
detection probe. All 1H and 13C NMR chemical shifts (ꢀ) are
given in ppm related to TMS signal at 0,00 ppm as internal
reference, and the coupling constants (J) in Hz. IR spectra
were obtained on a Bomem MB-100 spectrometer. The
optical rotation values were measured on a Rudolph
Research Altopol III polarimeter and the recorded data
referred to the Na-line value with the aid of a 1 dm cell. The
Novozyme 435: Immobilized lipase from Candida antartica
was provided by Novo Nordisk (Brazil). The vinyl acetate,
aromatic and aliphatic aldehydes and the solution of
vinylmagnesium chloride in THF were purchased from the
Aldrich Company.
1
Yield 92%: H NMR (CDCl3) 5.14 (ddd 6.1, 1.4 and 1.3
Hz, 1H); 5.19 (ddd 10.3, 1.4 and 1.3 Hz, 1H); 5.31 (ddd
17.1, 1.4 and 1.4 Hz, 1H); 5.97 (ddd 17.1, 10.3 and 6.1 Hz,
1H); 7.28 (d 8.6 Hz, 2 H); 7.31 (d 8.6 Hz, 2H). 13C NMR
(CDCl3) 74.6; 115.6; 127.7; 128.6; 133.4; 139.9; 140.9. IR
(film) (cm-1) 3357, 3081, 2853, 1646, 1489, 1449, 984. MS
m/z (relative intensity) 168 (M+, 100%), 153 (21%), 151
(75%), 141 (6%), 139 (8%), 133 (56%), 131 (3%), 116
(12%), 105 (16%), 103 (36%).
5-methylhex-1-en-3-ol (1e)
1
Yield 85%: H NMR (CDCl3) 0.927 (d 6.7 Hz, 3H);
0.933 (d 6.6 Hz, 3H); 1.32 (ddd 13.5, 7.8 and 5.6 Hz, 1H);
1.47 (ddd 13.5, 8.1 and 6.4 Hz, 1H); 1.75 (dqqd 7.8, 6.7, 6.6
and 6.4 Hz, 1H); 4.17 (ddddd 8.1, 5.6, 6.3, 1.3 and 1.2 Hz,
1H); 5.09 (ddd 10.4, 1.5 and 1.2 Hz, 1H); 5.22 (ddd 17.2, 1.5
and 1.3 Hz, 1H); 5.86 (ddd 17.2, 10.4 and 6.3 Hz, 1H). 13C
NMR (CDCl3) 22.4; 23.1; 24.5, 46.2; 71.5; 114.3; 141.7. IR
(film) (cm-1) 3332, 2850, 1645, 1487, 1450, 989, 920. MS
m/z (relative intensity) 72 (21%), 57 (100%), 43 (66%).
Allylic Alcohols 1a-g (Racemic)
A solution of the appropriate aldehyde (5 mmol) in ethyl
ether (10 mL) was added to a 250 mL round-bottomed flask
under
argon
atmosphere
at
-15oC
containing
vinylmagnesium chloride in THF (3.25mL, 5.25 mmol) and
ethyl ether (30 mL). The reaction mixture was stirred for 90
minutes at -15oC. After, the reaction was quenched by the
addition of water (30 mL), the phases were separated and the
aqueous layer was extracted with ethyl ether (3 x 30 mL).
The combined organic phases were dried over anhydrous
sodium sulfate and then filtered. The organic solvent was
evaporated under reduced pressure and the residue purified
oct-1-en-3-ol (1f)
1
Yield 79%: H NMR (CDCl3) 0.88 (m, 3H); 1.26 (m,
2H); 1.27 (m, 2H); 1.29 (m, 2H); 1.59 (m, 2H); 4.10 (m,
1H); 5.10 (ddd 10.4, 1.4 and 1.2 Hz, 1H); 5.22 (ddd 17.2, 1.4
and 1.3 Hz, 1H); 5.87 (ddd 17.2, 10.4 and 6.2 Hz, 1H). 13C
NMR (CDCl3) 14.0; 25.4; 29.3; 31.8; 37.1; 73.2; 114.4;
141.1. IR (film) (cm-1) 3565, 3080, 2930, 2851, 1644, 1470,
997, 992. MS m/z (relative intensity) 111 (12%), 97 (23%),
85 (100%), 71 (92%), 57 (90%), 43 (59%).
by
silica
gel
column
chromatography
using
dichloromethane/ethyl ether (95:5 v/v) as eluent.
1-phenylprop-2-en-1-ol (1a)
1
Yield 87%: H NMR (CDCl3) 5.14 (ddd 6.1, 1.5 and 1.3
Hz, 1H); 5.16 (ddd 10.3, 1.4 and 1.3 Hz, 1H); 5.31 (ddd
17.1, 1.5 and 1.4 Hz, 1H); 6.01 (ddd 17.1, 10.3 and 6.1 Hz,
1H); 7.26 (m, 1H); 7.33 (m, 2H); 7.34 (m, 2H). 13C NMR
(CDCl3) 75.3; 115.1; 126.3; 127.7; 128.5; 140.2; 142.6. IR
(film) (cm-1) 3357, 3081, 3034, 1646, 1489, 1449, 984. MS
m/z (relative intensity) 134 (M+, 10%), 117 (100%), 105
(14%), 77 (4%), 57 (2%).
non-1-en-3-ol (1g)
1
Yield 80%: H NMR (CDCl3) 0.89 (m, 3H); 1.28 (m,
2H); 1.29 (m, 2H); 1.31 (m, 2H); 1.32 (m, 2H); 1.53 (m,
2H); 4.09 (ddddd 6.5, 6.3, 5.6, 1.3 and 1.2 Hz, 1H); 5.09
(ddd 10.4, 1.5 and 1.2 Hz, 1H); 5.21 (ddd 17.2, 1.5 and 1.3
Hz, 1H); 5.86 (ddd 17.2, 10.4 and 6.3 Hz, 1H). 13C NMR
(CDCl3) 14.1; 22.6; 25.3; 29.3; 31.8; 37.1; 73.3; 114.5;
141.4. IR (film) (cm-1) 3563, 3081, 2930, 2852, 1644, 1470,
997, 992. MS m/z (relative intensity) 124 (1%), 85 (15%), 72
(18%), 57 (100%), 43 (25%).
1-(3-methoxyphenyl)prop-2-en-1-ol (1b)
Yield 91%: 1H NMR (CDCl3) 3.75 (s, 3H); 5.09(ddd 6.0,
1.4 and 1.3 Hz, 1H); 5.14 (ddd 10.3, 1.4 and 1.3 Hz, 1H);
5.29 (ddd 17.1, 1.4 and 1.4 Hz, 1H); 5.98 (ddd 17.1, 10.3 and
6.0 Hz, 1H); 6.79 (ddd 8.2, 2.6 and 1.0 Hz, 1 H); 6.89 (ddd
2.6, 0.5 and 0.3 Hz, 1 H); 6.90 (ddd 7.6, 1.0 and 0.5 Hz, 1
H); 7.23 (ddd 8.2, 7.6 and 0.3 Hz, 1 H). 13C NMR (CDCl3)
55.2; 75.1; 111.7; 113.3; 115.0; 118.7; 129.5; 140.2; 144.4;
159.7. IR (film) (cm-1) 3444, 2931, 2837, 1615, 1447, 960.
MS m/z (relative intensity) (M+, 65%); 147 (100%); 120
(12%); 107 (15%).
Racemic Allylic Acetates 2a-g (Racemic)
The racemic acetates were prepared as described in the
literature, by treating the appropriate alcohol with excess of
acetic anhydride in pyridine. [10]
1-phenylallyl acetate (2a)
1
Yield 74%: H NMR (CDCl3) 2.10 (s, 3H); 5.24 (ddd
10.4, 1.3 and 1.2 Hz, 1H); 5.29 (ddd 17.2, 1.4 and 1.3 Hz,
1H); 6.00 (ddd 17.2, 10.4 and 6.0 Hz, 1H); 6.26 (ddd 6.0, 1.4
and 1.2 Hz, 1H); 7.31 (m, 1H); 7.35 (m, 4H). 13C NMR
(CDCl3) 21.2; 76.2; 116.9; 127.1; 128.2; 128.6; 136.3; 138.9;
170.0. IR (film) (cm-1) 3091, 2931, 2837, 1741, 1583, 1440,
1-(4-methoxyphenyl)prop-2-en-1-ol (1c)
Yield 89%: 1H NMR (CDCl3) 3.78 (s, 3H); 5.11 (ddd 5.9,
1.4 and 1.3 Hz, 1H); 5.16 (ddd 10.4, 1.4 and 1.3 Hz, 1H);
5.30 (ddd 17.1, 1.4 and 1.4 Hz, 1H); 6.02 (ddd 17.1, 10.4 and
5.9 Hz, 1H); 6.86 (d 8.7 Hz, 2H); 7.26 (d 8.7 Hz, 2H). 13C