Allylic Alcohols
FULL PAPER
(E)-3-(4-Bromophenyl)prop-2-en-1-ol:[38] 74%. 1H NMR (300 MHz,
CDCl3): d=7.45 (d, J=8.5 Hz, 2H), 7.25 (d, J=8.5 Hz, 2H), 6.60 (d, J=
16.0 Hz, 1H; CH=CH), 6.35 (m, CH=CHCH2, 1H), 4.35 (d, J=5.1 Hz,
2H; CH2OH), 3.00 ppm (br. s, 1H; OH); 13C NMR (75 MHz, CDCl3):
d=136.1, 132.1 (2C), 129.7, 128.4 (2C), 123.1, 121.8, 63.9 ppm.
6.4 Hz, 2H; CH2Cl); 13C NMR (50 MHz, CDCl3): d=147.5, 140.8, 130.8,
127.4 (2C), 123.4, 123.0 (2C), 45.8 ppm.
(E)-1-(3-Chloroprop-1-enyl)-4-chlorobenzene:[41] 1H NMR (300 MHz,
CDCl3): d=7.41–7.28 (m, 4H), 6.60 (d, J=16.5 Hz, 1H; CH=CHCH2),
6.31 (m, 1H; CH=CHCH2), 4.26 ppm (dd, J=7.1 Hz, J=1.0 Hz, 2H;
CH2Cl); 13C NMR (50 MHz, CDCl3): d=134.8, 132.3, 131.5, 128.2 (2C),
127.6 (2C), 124.8, 45.3 ppm.
(E)-3-(2,4,6-Trimethylphenyl)prop-2-en-1-ol:[34]
87%.
1H NMR
(200 MHz, CDCl3): d= 6.90 (s, 2H), 6.65 (d, J=16.2 Hz, 1H; CH=
CHCH2), 5.95 (m, 1H; CH=CHCH2), 4.40 (d, J=6.0 Hz, 2H; CH2OH),
3.40 (br. s, 1H; OH), 2.30 ppm (s, 9H; 3 CH3); 13C NMR (50 MHz,
CDCl3): d=137.0, 136.0 (2C), 134.0, 130.0, 129.0 (2C), 124.0, 65.0, 26.0,
21.0 ppm (2C).
(E)-1-(3-Chloroprop-1-enyl)-4-bromobenzene:
1H NMR
(300 MHz,
CDCl3): d=7.45 (d, J=8.5 Hz, 2H), 7.25 (d, J=8.5 Hz, 2H), 6.65 (d, J=
15.7 Hz, 1H; CH=CHCH2), 6.35 (m, 1H; CH=CHCH2), 4.26 ppm (d, J=
7.0 Hz, 2H; CH2Cl); 13C NMR (50 MHz, CDCl3): d=135.2, 132.1 (2C),
129.7, 128.4 (2C), 124.2, 122.6, 45.6 ppm.
(E)-3-(2,4,6-Trimethoxyphenyl)prop-2-en-1-ol:[33]
99%.
1H NMR
(E)-2-(3-Chloroprop-1-enyl)-1,3,5-trimetylbenzene: 1H NMR (200 MHz,
CDCl3): d=6.90 (s, 2H), 6.65 (d, J=16.0 Hz, 1H; CH=CHCH2), 5.85 (m,
1H; CH=CHCH2), 4.30 (d, J=7.0 Hz, 2H; CH2Cl), 2.30 ppm (s, 9H;
3CH3); 13C NMR (50 MHz, CDCl3): d=137.0, 136.2 (2C), 132.3, 129.4,
128.6 (2C), 123.8, 46.7, 26.0, 20.8 ppm (2C).
(200 MHz, CDCl3): d=6.90 (d, J=16.1 Hz, 1H; CH=CHCH2), 6.70 (m,
1H; CH=CHCH2), 6.10 (s, 2H), 4.40 (d, J=5.6 Hz, 2H; CH2OH), 3.85 (s,
9H; 3OCH3), 2.50 ppm (br. s, 1H; OH); 13C NMR (50 MHz, CDCl3): d=
159.0 (3C), 129.2, 122.3, 107.0, 91.0 (2C), 65.9, 56.1 ppm (3C).
(E)-3-{4-(N,N-Dimethylamino)phenyl}prop-2-en-1-ol:[39] 99%. 1H NMR
(200 MHz, CDCl3): d=7.30 (d, J=8.7 Hz, 2H), 6.70 (d, J=8.7 Hz, 2H),
6.65 (d, J=16.2 Hz, 1H; CH=CHCH2), 6.20 (m, 1H; CH=CHCH2), 4.30
(d, J=6.3 Hz, 2H; CH2OH), 3.00 (s, 6H; 2CH3), 2.30 ppm (br. s, 1H;
OH); 13C NMR (50 MHz, CDCl3): d=150.6, 132.3, 127.9 (2C), 125.4,
124.4, 112.7 (2C), 64.7, 40.9 ppm (2C).
(E)-2-(3-Chloroprop-1-enyl)-1,3,5-trimethoxybenzene:
1H NMR
(200 MHz, CDCl3): d=6.90 (d, J=16.0 Hz, 1H; CH=CHCH2), 6.67 (m,
1H; CH=CHCH2), 6.10 (s, 2H), 4.30 (d, J=7.0 Hz, 2H; CH2Cl),
3.85 ppm (s, 9H; 3 OCH3); 13C NMR (50 MHz, CDCl3): d=160.1, 159.0
(2C), 131.0, 122.7, 105.0, 92.9 (2C), 56.1 (3C), 43.5 ppm.
(E)-3-(4-(Benzyloxy)phenyl)prop-2-en-1-ol:[40] 99%. 1H NMR (200 MHz,
CDCl3): d= 7.50 (m, 7H), 6.96 (d, J=8.5 Hz, 2H), 6.59 (d, J=15.8 Hz,
1H; CH=CHCH2), 6.30 (m, 1H; CH=CHCH2), 5.10 (s, 2H; H10), 4.33 (d,
J=6.2 Hz, 2H; CH2OH), 3.10 ppm (br. s, 1H; OH); 13C NMR (50 MHz,
CDCl3): d=159.0, 137.3, 131.0 (2C), 130.0, 129.0, 128.5 (2C), 128.0, 127.6
(2C), 126.9 (C2), 115.7 (2C), 70.4, 64.4 ppm.
(E)-4-(3-Chloroprop-1-enyl)-N,N-dimethylbenzenamine:
1H NMR
(200 MHz, CDCl3): d=7.30 (d, J=8.8 Hz, 2H), 6.80 (d, J=8.8 Hz, 2H),
6.65 (d, J=16.2 Hz, 1H; CH=CHCH2), 6.25 (m, 1H; CH=CHCH2), 4.20
(d, J=6.3 Hz, 2H; CH2Cl), 3.00 ppm (s, 6H; 2CH3); 13C NMR (50 MHz,
CDCl3): d=148.6, 132.3, 127.9 (2C), 125.0, 124.0, 114.1 (2C), 46.7,
40.9 ppm (2C).
(E)-3-(4-(Methoxyphenyl)prop-2-en-1-ol:[35] 87%. 1H NMR (200 MHz,
CDCl3): d=7.40–7.25 (m, 2H), 6.95–6.85 (m, 2H), 6.60 (d, J=15.9 Hz,
1H; CH=CHCH2), 6.25 (m, 1H; CH=CHCH2), 4.30 (d, J=5.8 Hz, 2H;
CH2OH), 3.85 (s, 3H; OCH3), 2.90 ppm (br. s, 1H; OH); 13C NMR
(50 MHz, CDCl3): d=159.6, 129.9, 128.1, 126.7 (2C), 126.1, 114.4 (2C),
64.2, 55.7 ppm.
(E)-1-(Benzyloxy)-4-(3-chloroprop-1-enyl)benzene: 1H NMR (200 MHz,
CDCl3): d=7.55–7.25 (m, 7H), 7.10 (d, J=8.5 Hz, 2H), 6.68 (d, J=
15.9 Hz, 1H; CH=CHCH2), 6.20 (m, 1H; CH=CHCH2), 5.10 (s, 2H;
H10), 4.20 ppm (d, J=6.2 Hz, 2H; CH2Cl); 13C NMR (50 MHz, CDCl3):
d=160.0, 140.2, 132.0, 131.0 (2C), 129.0, 128.7 (2C), 128.1 (2C), 126.0,
124.1, 113.9 (2C), 70.4, 44.9 ppm.
(E)-3-(Naphthalen-2-yl)prop-2-en-1-ol:[35] 93%. 1H NMR (200 MHz,
CDCl3): d=8.10–7.40 (m, 7H), 7.20 (d, J=15.9 Hz, 1H; CH=CHCH2),
6.40 (m, 1H; CH=CHCH2), 4.45 ppm (d, J=6.1 Hz, 2H; CH2OH);
13C NMR (50 MHz, CDCl3): d=133.5, 133.0, 132.0, 131.1, 128.8, 128.2,
127.9, 127.6, 126.4, 126.2, 125.8, 123.5, 63.7 ppm.
(E)-1-(3-Chloroprop-1-enyl)-4-methoxybenzene:[41] 1H NMR (200 MHz,
CDCl3): d=7.30 (m, 2H), 6.90 (m, 2H), 6.60 (d, J=15.6 Hz, 1H; CH=
CHCH2), 6.20 (m, 1H; CH=CHCH2), 4.20 (d, J=7.3 Hz, 2H; CH2Cl),
3.85 ppm (s, 3H; OCH3); 13C NMR (50 MHz, CDCl3): d=160.1, 130.2,
126.9 (3C), 123.1, 114.4 (2C), 55.8, 46.9 ppm.
(E)-3-(Naphthalen-1-yl)prop-2-en-1ol:[35] 90%. 1H NMR (300 MHz,
CDCl3): d=8.13 (d, J=9.1 Hz, 1H), 7.87–7.80 (m, 2H), 7.64–7.38 (m,
5H; CH=CHCH2), 6.47 (dt, J=15.6 Hz, J=5.6 Hz, 1H), 4.47 (dd, J=
5.6 Hz, J=1.4 Hz, 2H; CH2OH), 3.42 ppm (br. s, 1H; OH); 13C NMR
(75 MHz, CDCl3): d=133.6, 133.5, 131.7, 131.2, 128.5, 128.2, 128.0, 126.0,
125.8, 125.6, 123.9, 123.7, 63.9 ppm.
(E)-2-(3-Chloroprop-1-enyl)naphthalene: 1H NMR (200 MHz, CDCl3):
d=8.10–7.40 (m, 7H), 7.20 (d, J=15.9 Hz, 1H; CH=CHCH2), 6.40 (m,
1H; CH=CHCH2), 4.30 ppm (d, J=7.0 Hz, 2H; CH2Cl); 13C NMR
(50 MHz, CDCl3): d=135.0, 134.8, 134.0, 130.0 (2C), 129.0 (2C), 127.6,
126.8, 125.0, 124.0 (2C), 46.0 ppm.
(E)-1-(3-Chloroprop-1-enyl)naphthalene: 1H NMR (300 MHz, CDCl3):
d=8.11 (d, J=7.2 Hz, 1H), 7.91–7.83 (m, 2H), 7.65–7.43 (m, 5H), 6.37
(dt, J=15.4 Hz, J=7.1 Hz, 1H; CH=CHCH2), 4.38 ppm (dd, J=7.1 Hz,
J=1.1 Hz, 2H; CH2Cl); 13C NMR (75 MHz, CDCl3): d=133.6, 133.5,
131.2, 131.1, 128.7, 128.6, 128.0, 126.2, 125.9, 125.5, 124.2, 123.6, 45.5 ppm.
General procedure for the synthesis of allylic chloride: To a solution of
allylic alcohol (1 equiv) in diethyl ether (1 mmolmLÀ1), SOCl2 (1 equiv)
was slowly added at 08C. The reaction mixture was stirred until comple-
tion, as determined by TLC. Then, the resulting solution was diluted with
dichloromethane, washed with a saturated solution of NaHCO3 and then
brine, and then dried over Na2SO4, filtered, and concentrated. The allylic
chloride was used without further purifications.
General procedure for the allylic substitution catalyzed by ruthenium
complex: In a Schlenk tube under argon, allylic chloride (0.5 mmol,
1 equiv), phenylboronic acid (0.6 mmol, 1.2 equiv), K2CO3 (1.2 equiv),
(E)-1-(3-Chloroprop-1-enyl)-2-nitrobenzene:[41]
1H NMR
(200 MHz,
[Cp*Ru(MeCN)3]PF6 (2; 3 mol%) and acetonitrile (1 mL) were added.
G
CDCl3): d=8.10 (d, J=8.1 Hz, 1H), 7.90 (m, 1H), 7.70 (m, 1H), 7.48 (m,
1H), 7.25 (d, J=15.5 Hz, 1H; CH=CHCH2), 6.25 (m, 1H; CH=CHCH2),
4.30 ppm (d, J=6.9 Hz, 2H; CH2Cl); 13C NMR (50 MHz, CDCl3): d=
148.0, 133.7, 132.4 , 129.0, 128.6, 127.9, 124.7, 123.8, 45.9 ppm.
The reaction mixture was stirred for 24 h at room temperature. The
crude product was purified on silica gel by flash chromatography (Hept/
Et2O: 9/1) to furnish linear and branched allylic product.
1-Phenylprop-2-en-1-ol:[42] 1H NMR (200 MHz, CDCl3): d=7.50–7.25 (m,
5H), 6.10 (ddd, J=16.4 Hz, J=10.2 Hz, J=6.0 Hz, 1H; CH=CH2), 5.40
(m, 1H; CH=CH2), 5.20–5.10 (m, 2H; CH=CH2, CHOH), 3.10 ppm (br.
s, 1H; OH); 13C NMR (50 MHz, CDCl3): d=141.4, 138.5, 128.3, 127.4,
126.2, 116.2, 76.8 ppm.
1-(2-Nitrophenyl)prop-2-en-1-ol:[42] 1H NMR (300 MHz, CDCl3): d=7.95
(dd, J=8.1 Hz, J=0.9 Hz, 1H), 7.77 (m, 1H), 7.63 (m, 1H), 7.40 (m,
1H), 6.05 (ddd, J=17.1 Hz, J=10.4 Hz, J=5.3 Hz, 1H; CH=CH2), 5.71
(d, J=5.3 Hz, 1H; CHOH), 5.35 (dd, J=17.1 Hz, J=1.1 Hz, 1H; CH=
CH2), 5.22 (dd, J=10.4 Hz, J=1.1 Hz, 1H; CH=CH2), 3.20 ppm (br s.,
(E)-1-(3-Chloroprop-1-enyl)-3-nitrobenzene:[41]
1H NMR
(200 MHz,
CDCl3): d=8.25 (s, 1H), 8.10 (d, 1H; J=8.1 Hz), 7.70 (d, 1H; J=
7.8 Hz), 7.53 (m, 1H), 6.75 (d, J=15.7 Hz, 1H; CH=CHCH2), 6.55 (m,
1H; CH=CHCH2), 4.20 ppm (d, J=7.2 Hz, 2H; CH2Cl); 13C NMR
(50 MHz, CDCl3): d=138.0, 132.9, 132.3, 130.0, 128.9, 123.3, 122.4, 121.7,
32.4 ppm.
(E)-1-(3-Chloroprop-1-enyl)-4-nitrobenzene:[41]
1H NMR
(200 MHz,
CDCl3): d=8.20 (d, J=8.3 Hz, 2H), 7.60 (d, J=8.3 Hz, 2H), 6.80 (d, J=
15.7 Hz, 1H; CH=CHCH2), 6.53 (m, 1H; CH=CHCH2), 4.30 ppm (d, J=
Chem. Eur. J. 2008, 14, 5630 – 5637
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5635