Y.-L. Lin et al. / Tetrahedron 63 (2007) 10949–10957
10955
chromatography. After the reaction was completed, the reac-
tion mixture was extracted with diethyl ether three times
(3ꢃ2 mL), the combined ethereal solution was dried over
anhydrous sodium sulfate, filtered and then concentrated to
dryness in vacuo. The desired products were purified by flash
chromatography (ethyl acetate/hexane¼1:6, v/v) to finally
afford the corresponding rearranged allylphenols as light
yellow liquids with high isolated yields (69–82%). Satisfac-
(100 MHz, CDCl3) d 20.4, 35.1, 115.6, 116.3, 125.0,
128.2, 130.1, 130.9, 136.5, 151.8; FAB-HRMS m/z [M]+
calcd for C10H12O 148.0888, found 148.0890.
2-Allyl-6-methoxyphenol (2e): 64 mg (64% yield, 90 s reac-
tion time), yellow liquid; Rf¼0.46 (ethyl acetate/hexane¼
1
1:5); H NMR (400 MHz, CDCl3) d 3.41 (d, J¼6.8 Hz,
CH2, 2H), 3.87 (s, CH3, 3H), 5.02–5.09 (m, C]CH2, 2H),
5.69 (s, OH, 1H), 5.97–6.01 (m, C]CH, 1H), 6.72–6.81
(m, ArH, 3H); 13C NMR (100 MHz, CDCl3) d 33.8, 56.0,
108.6, 115.4, 119.4, 122.2, 125.9, 136.6, 143.4, 146.4;
FAB-HRMS m/z [M]+ calcd for C10H12O2 164.0837, found
164.0835.
1
tory H and 13C NMR results were obtained for all desired
products (for NMR spectra, see Supplementary data).
2-Allylphenol (2a): 75 mg (75% yield, 90 s reaction time),
yellow liquid; Rf¼0.35 (ethyl acetate/hexane¼1:5); 1H
NMR (400 MHz, CDCl3) d 3.40 (d, J¼6.3 Hz, CH2, 2H),
5.00 (s, OH, 1H), 5.12–5.16 (m, C]CH2, 2H), 5.96–6.06
(m, C]CH, 1H), 6.79–6.89 (m, ArH, 2H), 7.09–7.14 (m,
ArH, 2H); 13C NMR (100 MHz, CDCl3) d 35.0, 115.8,
116.4, 120.9, 125.3, 127.8, 130.4, 136.4, 154.0; FAB-
HRMS m/z [M]+ calcd for C9H10O 134.0732, found
134.0730.
4-Allyl-2-methoxyphenol (3e): 18 mg (18% yield, 90 s reac-
tion time), yellow liquid; Rf¼0.43 (ethyl acetate/hexane¼
1
1:5); H NMR (400 MHz, CDCl3) d 3.31 (d, J¼6.7 Hz,
CH2, 2H), 3.86 (s, CH3, 3H), 5.03–5.08 (m, C]CH2, 2H),
5.48 (s, OH, 1H), 5.91–5.97 (m, C]CH, 1H), 6.66–6.68
(m, ArH, 2H), 6.82–6.84 (m, ArH, 1H); 13C NMR
(100 MHz, CDCl3) d 39.8, 55.8, 111.1, 114.2, 115.5,
121.1, 131.9, 137.8, 143.8, 146.4; FAB-HRMS m/z [M]+
calcd for C10H12O2 164.0837, found 164.0835.
2-Allyl-6-methylphenol (2b): 49 mg (49% yield, 90 s reac-
tion time), yellow liquid; Rf¼0.56 (ethyl acetate/hexane¼
1
1:5); H NMR (400 MHz, CDCl3) d 2.23 (s, CH3, 3H),
3.40 (d, J¼6.4 Hz, CH2, 2H), 4.97 (s, OH, 1H), 5.15–5.21
(m, C]CH2, 2H), 5.96–6.04 (m, C]CH, 1H), 6.78 (t,
J¼7.5 Hz, ArH, 1H), 6.95 (d, J¼7.4 Hz, ArH, 1H), 7.01
(d, J¼7.4 Hz, ArH, 1H); 13C NMR (100 MHz, CDCl3)
d 15.8, 35.6, 116.6, 120.4, 124.2, 124.5, 128.0, 129.4,
136.5, 152.6; FAB-HRMS m/z [M]+ calcd for C10H12O
148.0888, found 148.0891.
2-Allyl-3-methoxyphenol (2f): 55 mg (55% yield, 120 s reac-
tion time), yellow liquid; Rf¼0.42 (ethyl acetate/hexane¼
1
1:5); H NMR (400 MHz, CDCl3) d 3.45–3.47 (m, CH2,
2H), 3.80 (s, CH3, 3H), 5.05–5.13 (m, C]CH2, 2H), 5.16
(s, OH, 1H), 5.94–6.02 (m, C]CH, 1H), 6.47–6.50 (m,
ArH, 2H), 7.07 (t, J¼8.2 Hz, ArH, 1H); 13C NMR
(100 MHz, CDCl3) d 27.3, 55.8, 103.3, 108.8, 113.7,
115.3, 127.5, 136.3, 155.1, 158.2; FAB-HRMS m/z [M]+
calcd for C10H12O2 164.0837, found 164.0839.
4-Allyl-2-methylphenol (3b): 21 mg (21% yield, 90 s reac-
tion time), yellow liquid; Rf¼0.43 (ethyl acetate/hexane¼
1
1:5); H NMR (400 MHz, CDCl3) d 2.21 (s, CH3, 3H),
2-Allyl-5-methoxyphenol (2f0): 16 mg (16% yield, 120 s re-
action time), yellow liquid; Rf¼0.32 (ethyl acetate/hexane¼
1:5); 1H NMR (400 MHz, CDCl3) d 3.33 (d, J¼6.3 Hz, CH2,
2H), 3.75 (s, CH3, 3H), 5.09–5.16 (m, C]CH2 and OH, 3H),
5.95–6.01 (m, C]CH, 1H), 6.40–6.46 (m, ArH, 2H), 6.98
(d, J¼8.4 Hz, ArH, 1H); 13C NMR (100 MHz, CDCl3)
d 34.5, 55.3, 102.0, 106.3, 116.2, 117.3, 130.8, 136.8,
155.0, 159.6; FAB-HRMS m/z [M]+ calcd for C10H12O2
164.0837, found 164.0834.
3.26 (d, J¼6.7 Hz, CH2, 2H), 4.58 (s, OH, 1H), 5.00–5.06
(m, C]CH2, 2H), 5.88–5.95 (m, C]CH, 1H), 6.69 (d,
J¼8.0 Hz, ArH, 1H), 6.88 (d, J¼9.9 Hz, ArH, 1H), 6.92
(s, ArH, 1H); 13C NMR (100 MHz, CDCl3) d 15.7, 39.3,
114.9, 115.3, 123.7, 127.0, 131.1, 132.2, 138.0, 152.1;
FAB-HRMS m/z [M]+ calcd for C10H12O 148.0888, found
148.0890.
2-Allyl-3-methylphenol and 2-allyl-5-methylphenol (2c):
74 mg (74% yield, a mixture of two 1.2:1 ortho-adducts,
120 s reaction time), yellow liquid; Rf¼0.46 (ethyl acetate/
2-Allyl-4-methoxyphenol (2g): 73 mg (73% yield, 90 s reac-
tion time), yellow liquid; Rf¼0.29 (ethyl acetate/hexane¼
1
1
hexane¼1:5); H NMR (400 MHz, CDCl3) d 2.27 (s, CH3,
1:5); H NMR (400 MHz, CDCl3) d 3.36 (d, J¼6.4 Hz,
3H), 2.28 (s, CH3, 3H), 3.35–3.37 (m, CH2, 2H), 3.41–
3.43 (m, CH2, 2H), 4.82 (s, OH, 1H), 4.88 (s, OH, 1H),
4.99–5.16 (m, C]CH2, 4H), 5.92–6.00 (m, C]CH, 2H),
6.63–6.77 (m, ArH, 4H), 6.98–7.02 (m, ArH, 2H); 13C
NMR (100 MHz, CDCl3) d 19.5, 21.0, 30.5, 34.7, 113.3,
115.3, 116.1, 116.5, 121.6, 122.2, 122.8, 123.9, 127.0,
130.2, 135.5, 136.7, 137.9, 138.2, 153.8, 153.9; FAB-
HRMS m/z [M]+ calcd for C10H12O 148.0888, found
148.0889.
CH2, 2H), 3.74 (s, CH3, 3H), 4.76 (s, OH, 1H), 5.11–5.16
(m, C]CH2, 2H), 5.95–6.02 (m, C]CH, 1H), 6.65–6.76
(m, ArH, 3H); 13C NMR (100 MHz, CDCl3) d 35.2, 55.7,
112.6, 114.8, 115.9, 116.5, 126.5, 136.1, 148.0, 153.7;
FAB-HRMS m/z [M]+ calcd for C10H12O2 164.0837, found
164.0835.
2-Allyl-6-chlorophenol (2h): 69 mg (69% yield, 120 s reac-
tion time), yellow liquid; Rf¼0.65 (ethyl acetate/hexane¼
1
1:5); H NMR (400 MHz, CDCl3) d 3.41 (d, J¼6.5 Hz,
2-Allyl-4-methylphenol (2d): 77 mg (77% yield, 90 s reac-
tion time), yellow liquid; Rf¼0.50 (ethyl acetate/hexane¼
CH2, 2H), 5.05–5.10 (m, C]CH2, 2H), 5.60 (s, OH, 1H),
5.94–6.01 (m, C]CH, 1H), 6.79 (t, J¼7.8 Hz, ArH, 1H),
7.03 (d, J¼7.5 Hz, ArH, 1H), 7.16–7.18 (m, ArH, 1H); 13C
NMR (100 MHz, CDCl3) d 34.5, 116.1, 119.9, 120.8,
126.9, 127.8, 128.9, 136.0, 149.2; FAB-HRMS m/z [M]+
calcd for C9H9OCl 168.0342, found 168.0342.
1
1:5); H NMR (400 MHz, CDCl3) d 2.25 (s, CH3, 3H),
3.36 (d, J¼6.4 Hz, CH2, 2H), 4.83 (s, OH, 1H), 5.12–5.17
(m, C]CH2, 2H), 5.95–6.05 (m, C]CH, 1H), 6.70 (d,
J¼8.0 Hz, ArH, 1H), 6.90–6.92 (m, ArH, 2H); 13C NMR