The Journal of Organic Chemistry
FEATURED ARTICLE
mixture was allowed to stir at 25 °C. On completion, the reaction was
diluted with EtOAc (5 mL) and filtered through a short plug of Celite.
The combined organic layer was washed with brine and dried over
Na2SO4. After removal of the solvents under reduced pressure, the crude
reaction mixture was subjected to purification by flash column chroma-
tography using EtOAc/hexanes as eluent to afford 144 mg of cinnamyl
cinnamate 3a in 72% yield.
(CDCl3, 100 MHz) δ 166.4, 145.2, 136.4, 134.1, 128.7 (2C), 128.2,
126.7 (2C), 123.5, 122.6, 64.9, 18.1; HRMS (EI) calcd for C13H14O2
203.1072 m/z (M þ H)þ, found 203.1072 m/z.
3-(2-Methoxyphenyl)acrylic acid 3-phenyl allyl ester (3i):
1H NMR (CDCl3, 400 MHz) δ 8.04 (d, J = 16.0 Hz, 1H), 7.52ꢀ7.50 (m,
1H), 7.44ꢀ7.23 (m, 6H), 6.97ꢀ6.90 (m, 1H), 6.92 (d, J = 8.0 Hz, 1H),
6.72 (d, J = 16.0 Hz, 1H), 6.59 (d, J = 16.0 Hz, 1H), 6.40ꢀ6.35 (m, 1H),
4.87 (dd, J = 6.4, 1.2 Hz, 2H), 3.88 (s, 3H); 13C NMR (CDCl3, 125
MHz) δ 167.3, 158.4, 140.6, 136.3, 134.0, 131.6, 129.0, 128.6 (2C),
128.0, 126.7 (2C), 123.6, 123.4, 120.7, 118.4, 111.2, 65.0, 55.5; HRMS
(EI) calcd for C19H18O3 295.1334 m/z (M þ H)þ, found 295.1333 m/z.
3-Phenyl acrylic acid 3-(2-chlorophenyl)allyl ester (3j): 1H
NMR (CDCl3, 400 MHz) δ 7.77 (d, J = 16.0 Hz, 1H), 7.59ꢀ7.55 (m,
3H), 7.41ꢀ7.36 (m, 4H), 7.26ꢀ7.20 (m, 2H), 7.13 (d, J = 16.0 Hz, 1H),
6.51 (d, J = 16.0 Hz, 1H), 6.41ꢀ6.34 (m, 1H), 4.93 (d, J = 6.0 Hz, 2H); 13C
NMR (CDCl3, 100 MHz) δ 166.7, 145.2, 134.42, 134.4, 133.3, 130.4,
130.1, 129.8, 129.1, 128.9 (2C), 128.1 (2C), 127.0, 126.9, 126.2, 117.8,
65.0; HRMS (EI) calcd for C18H15O2Cl 321.0658 m/z (M þ Na)þ, found
321.0655 m/z.
Characterization of 3-Phenylacrylic acid-3-phenyl allyl
ester2e (3a): H NMR (CDCl3, 500 MHz) δ 7.78 (d, J = 16.0 Hz,
1
1H), 7.53ꢀ7.51 (m, 2H), 7.42ꢀ7.26 (m, 8H), 6.70 (d, J = 16.0 Hz, 1H),
6.48 (d, J = 16.0 Hz, 1H), 6.39ꢀ6.33 (m, 1H), 4.87 (dd, J = 6.4, 1.2 Hz,
2H); 13C NMR (CDCl3, 125 MHz) δ 166.8, 145.1, 136.3, 134.3, 130.4,
128.9 (2C), 128.6 (2C), 128.15 (2C), 128.11 (3C), 126.7, 123.3, 117.9,
65.2; HRMS (EI) calcd for C18H16O2 265.1229 m/z (M þ H)þ, found
265.1232 m/z.
3-(4-Bromophenyl)acrylic acid 3-phenyl allyl ester (3b): 1H
NMR (CDCl3, 400 MHz) δ 7.65 (d, J = 16.0 Hz, 1H), 7.52ꢀ7.49 (m,
2H), 7.41ꢀ7.24 (m, 7H), 6.70 (d, J = 16.0 Hz, 1H), 6.46 (d, J = 16.0 Hz,
1H), 6.38ꢀ6.31 (m, 1H), 4.86 (dd, J = 6.4, 1.2 Hz, 2H); 13C NMR
(CDCl3, 100 MHz) δ 166.5, 143.8, 136.3, 134.5, 133.4, 132.2 (2C),
129.6 (2C), 128.7 (2C), 128.2, 126.7 (2C), 124.7, 123.2, 118.7, 65.4;
HRMS (EI) calcd for C18H15O2Br 365.0153 m/z (M þ Na)þ, found
365.0149 m/z.
3-(4-Chlorophenyl)acrylic acid 3-(2-chlorophenyl)allyl es-
ter (3k): H NMR (CDCl3, 400 MHz) δ 7.68 (d, J = 16.0 Hz, 1H),
1
7.56ꢀ7.54 (m, 1H), 7.47ꢀ7.44 (m, 2H), 7.38ꢀ7.28 (m, 3H),
7.26ꢀ7.18 (m, 2H), 7.10 (d, J = 16.0 Hz, 1H), 6.46 (d, J = 16.0 Hz,
1H), 6.38ꢀ6.30 (m, 1H), 4.91 (dd, J = 6.4, 1.6 Hz, 2H); 13C NMR
(CDCl3, 100 MHz) δ 166.5, 143.8, 136.4, 134.5, 133.4, 132.9, 130.2,
129.8, 129.4 (2C), 129.3 (2C), 129.2, 127.1, 127.0, 126.1, 118.5, 65.1;
HRMS (EI) calcd for C18H14O2Cl2 355.0269 m/z (M þ Na)þ, found
355.0273 m/z.
3-(4-Chlorophenyl)acrylic acid 3-(4-chlorophenyl)allyl es-
ter (3l): 1H NMR (CDCl3, 400 MHz) δ 7.67 (d, J = 16.0 Hz, 1H), 7.45
(d, J = 8.2 Hz, 2H), 7.36ꢀ7.23 (m, 6H), 6.65 (d, J = 16.0 Hz, 1H), 6.44
(d, J = 16.0 Hz, 1H), 6.36ꢀ6.28 (m, 1H), 4.86 (dd, J = 6.4, 1.2 Hz, 2H);
13C NMR (CDCl3, 100 MHz) δ 166.5, 143.9, 136.4, 134.8, 133.9, 133.1,
132.9, 129.4 (2C), 129.3 (2C), 128.9 (2C), 127.9 (2C), 123.4, 118.5,
65.1; HRMS (EI) calcd for C18H14O2Cl2 355.0269 m/z (M þ Na)þ,
found 355.0271 m/z.
3-(3-Bromophenyl)acrylic acid 3-phenyl allyl ester (3c): 1H
NMR (CDCl3, 400 MHz) δ 7.66 (d, J = 4.1 Hz, 1H), 7.63 (d, J = 16.0
Hz, 1H), 7.51ꢀ7.48 (m, 1H), 7.43ꢀ7.34 (m, 3H), 7.33ꢀ7.30 (m, 2H),
7.32ꢀ7.23 (m, 2H), 6.70 (d, J = 16.0 Hz, 1H), 6.46 (d, J = 16.0 Hz, 1H),
6.38ꢀ6.31 (m, 1H), 4.87 (d, J = 6.9 Hz, 2H); 13C NMR (CDCl3, 100
MHz) δ 166.4, 143.4, 136.5, 136.3, 134.5, 133.2, 130.9, 130.5, 128.7
(2C), 128.2, 126.7, 126.8 (2C), 123.2, 123.1, 119.5, 65.4; HRMS (EI)
calcd for C18H15O2Br 365.0153 m/z (M þ Na)þ, found 365.0150 m/z.
3-(2-Chlorophenyl)acrylic acid 3-phenyl allyl ester (3d): 1H
NMR (CDCl3, 400 MHz) δ 8.13 (d, J = 16.4 Hz, 1H), 7.63ꢀ7.61 (m,
1H), 7.42ꢀ7.25 (m, 8H), 6.72 (d, J = 16.0 Hz, 1H), 6.47 (d, J = 16.0 Hz,
1H), 6.39ꢀ6.32 (m, 1H), 4.89 (d, J = 6.4 Hz, 2H); 13C NMR (CDCl3,
100 MHz) δ 166.4, 141.1, 136.3, 135.1, 134.5, 132.8, 131.3, 130.3, 128.8
(2C), 128.2, 127.8, 127.2, 126.8 (2C), 123.3, 120.7, 65.5; HRMS (EI)
calcd for C18H15O2Cl 321.0658 m/z (M þ Na)þ, found 321.0654 m/z.
3-(4-Chlorophenyl)acrylic acid 3-phenyl allyl ester (3e): 1H
NMR (CDCl3, 400 MHz) δ 7.66 (d, J = 16.4 Hz, 1H), 7.46ꢀ7.26 (m,
9H), 6.70 (d, J = 16.0 Hz, 1H), 6.47 (d, J = 16.0 Hz, 1H), 6.38ꢀ6.31 (m,
1H), 4.86 (d, J = 6.4 Hz, 2H); 13C NMR (CDCl3, 100 MHz) δ 166.5,
143.7, 136.3, 136.2, 134.4, 132.9, 129.35 (2C), 129.3 (2C), 128.7 (2C),
128.2, 126.7 (2C), 123.2, 118.6, 63.3; HRMS (EI) calcd for C18H15O2Cl
321.0658 m/z (M þ Na)þ, found 321.0656 m/z.
3-Phenyl acrylic acid 5-phenylpenta-2,4-dienyl ester
(3m): H NMR (CDCl3, 400 MHz) δ 7.73 (d, J = 16.0 Hz, 1H),
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7.55ꢀ7.52 (m, 2H), 7.43ꢀ7.20 (m, 8H), 6.83ꢀ6.77 (m, 1H), 6.61 (d, J
= 16.0 Hz, 1H), 6.54ꢀ6.47 (m, 2H), 6.00ꢀ5.91 (m, 1H), 4.80 (d, J = 6.4
Hz, 2H); 13C NMR (CDCl3, 100 MHz) δ 166.8, 145.2, 137.0, 134.7,
134.5, 133.9, 130.4, 129.0 (2C), 128.7 (2C), 128.2 (2C), 127.9, 127.8,
127.1, 126.6 (2C), 118.0, 65.0; HRMS (EI) calcd for C20H18O2
313.1204 m/z (M þ Na)þ, found 313.1215 m/z.
3-Phenyl acrylic acid benzyl ester2e (3n): 1H NMR (CDCl3,
400 MHz) δ 7.72 (d, J = 16.0 Hz, 1H), 7.51ꢀ7.50 (m, 2H), 7.45ꢀ7.31
(m, 8H), 6.48 (d, J = 16.0 Hz, 1H), 5.24 (s, 2H); 13C NMR (CDCl3, 100
MHz) δ 166.9, 145.3, 136.1, 134.4, 130.4, 129.0 (2C), 128.7 (2C),
128.4, 128.3 (2C), 128.2 (2C), 118.0, 66.4; HRMS (EI) calcd for
C16H14O2 261.0891 m/z (M þ Na)þ, found 261.0904 m/z.
1
3-(4-Nitrophenyl)acrylic acid 3-phenyl allyl ester (3f): H
NMR (CDCl3, 400 MHz) δ 8.25 (d, J = 8.7 Hz, 2H), 7.75 (d, J = 16.0
Hz, 1H), 7.68 (d, J = 9.1 Hz, 2H), 7.44ꢀ7.26 (m, 5H), 6.72 (d, J = 16.0
Hz, 1H), 6.60 (d, J = 16.0 Hz, 1H), 6.39ꢀ6.31 (m, 1H), 4.89 (dd, J = 6.4,
1.2 Hz, 2H). 13C NMR (CDCl3, 100 MHz) δ 165.9, 148.6, 142.2, 140.5,
136.2, 134.8, 128.8 (4C), 128.3, 126.7 (2C), 124.3 (2C), 122.8, 122.3,
65.7; HRMS (EI) calcd for C18H15O4N 332.0899 m/z (M þ Na)þ,
found 332.0902 m/z.
3-Phenyl acrylic acid 4-chlorobenzyl ester24 (3o): 1H NMR
(CDCl3, 400 MHz) δ 7.72 (d, J = 16.0 Hz, 1H), 7.53ꢀ7.50 (m, 2H),
7.41ꢀ7.32 (m, 7H), 6.47 (d, J = 16.0 Hz, 1H), 5.21 (s, 2H); 13C NMR
(CDCl3, 100 MHz) δ 166.8, 145.5, 134.7, 134.4, 134.3, 130.6, 129.8
(2C), 129.0 (2C), 128.9 (2C), 128.2 (2C), 117.7, 65.6.
1
3-Furan-2-yl acrylic acid 3-phenyl allyl acetate (3g): H
NMR (CDCl3, 400 MHz) δ 7.49ꢀ7.23 (m, 7H), 6.69 (d, J = 16.0 Hz,
1H), 6.60 (d, J = 3.2 Hz, 1H), 6.47ꢀ6.45 (m, 1H), 6.38ꢀ6.30 (m, 2H),
4.84 (dd, J = 6.4, 1.4 Hz, 2H); 13C NMR (CDCl3, 100 MHz) δ 166.9,
151.0, 144.9, 136.4, 134.2, 131.5, 128.7 (2C), 128.1, 126.7 (2C), 123.4,
115.6, 115.0, 112.4, 65.2; HRMS (EI) calcd for C16H14O3 255.1021 m/z
(M þ H)þ, found 255.1029 m/z.
3-Phenyl acrylic acid allyl ester2e (3p): 1H NMR (CDCl3, 400
MHz) δ 7.73 (d, J = 16.0 Hz, 1H), 7.55ꢀ7.52 (m, 2H), 7.40ꢀ7.38 (m,
3H), 6.48 (d, J = 16.0 Hz, 1H), 6.08ꢀ5.96 (m, 1H), 5.38 (dd, J = 16.0,
1.4 Hz, 1H), 5.28 (dd, J = 16.0, 1.4 Hz, 1H), 4.72 (dd, J = 6.0, 1.4 Hz,
2H); 13C NMR (CDCl3, 100 MHz) δ 166.7, 145.2, 134.5, 132.4, 130.5,
129.0 (2C), 128.2 (2C), 118.4, 118.0, 65.4; HRMS (EI) calcd for
C12H12O2 189.0916 m/z (M þ H)þ, found 189.0909 m/z.
But-2-enoic acid 3-phenyl allyl ester23 (3h): 1H NMR
(CDCl3, 400 MHz) δ 7.40ꢀ7.20 (m, 5H), 7.07ꢀ6.97 (m, 1H), 6.65
(d, J = 16.0 Hz, 1H), 6.34ꢀ6.27 (m, 1H), 5.88 (dd, J = 16.0 Hz, 1.4 Hz,
1H), 4.78 (dd, J = 6.4, 1.4 Hz, 2H), 1.88 (d, J = 6.4, Hz, 3H); 13C NMR
1
3-Phenyl acrylic acid 3-phenyl-2-ynyl ester (3q): H NMR
(CDCl3, 400 MHz) δ 7.74 (d, J = 16.0 Hz, 1H), 7.55ꢀ7.52 (m, 2H),
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dx.doi.org/10.1021/jo200275c |J. Org. Chem. 2011, 76, 3016–3023