PAPER
Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling
2793
MS (EI, 70 eV): m/z (%) = 235 (34) [M]+, 129 (100).
13C NMR (125 MHz, CDCl3): d = 154.0, 143.0, 136.2, 133.5, 129.1,
128.7, 128.0, 127.3, 118.9, 89.5, 83.3, 36.3.
N-Methyl-N-phenyl-3-p-tolylpropiolamide (4)7
Pale-yellow solid; mp 84.0–85.3 °C (uncorrected).
MS (EI, 70 eV): m/z (%) = 269 (52) [M]+, 163 (100).
IR (KBr): 2231, 1634, 1589 cm–1.
3-(4-Iodophenyl)-N-methyl-N-phenylpropiolamide (10)6d
White solid; 54.1–55.6 °C (uncorrected).
IR (KBr): 2218, 1646, 1593 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.49 (d, J = 7.5 Hz, 2 H), 7.45–
7.34 (m, 3 H), 7.03 (s, 4 H), 3.39 (s, 3 H), 2.30 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 154.4, 143.2, 140.4, 132.3, 129.0,
1H NMR (500 MHz, CDCl3): d = 7.58 (d, J = 8.5 Hz, 2 H), 7.45 (t,
J = 7.5 Hz, 2 H), 7.39 (d, J = 7.5 Hz, 1 H), 7.35 (t, J = 7.0 Hz, 2 H),
6.84 (d, J = 8.5 Hz, 2 H), 3.39 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 154.0, 143.1, 137.6, 133.6, 129.1,
128.0, 127.4, 119.8, 96.5, 89.7, 83.6, 36.4.
129.0, 127.8, 127.3, 117.2, 91.2, 82.1, 36.3, 21.5.
MS (EI, 70 eV): m/z (%) = 249 (38) [M]+, 143 (100).
N-Methyl-N-phenyl-3-o-tolylpropiolamide (5)1c
Colorless oil.
IR (KBr): 2218, 1638, 1581 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.43 (t, J = 7.5 Hz, 2 H), 7.36 (t,
J = 8.5 Hz, 3 H), 7.24–7.19 (m, 2 H), 7.06 (t, J = 8.0 Hz, 2 H), 3.38
(s, 3 H), 1.92 (s, 3 H).
MS (EI, 70 eV): m/z (%) = 361 (64) [M]+, 255 (100), 128 (46).
3-(4-Acetylphenyl)-N-methyl-N-phenylpropiolamide (11)1a
Pale-yellow solid; mp 92.2–93.9 °C (uncorrected).
IR (KBr): 2222, 1681, 1626, 1594 cm–1.
13C NMR (125 MHz, CDCl3): d = 154.4, 143.3, 141.4, 133.1, 129.9,
1H NMR (500 MHz, CDCl3): d = 7.82 (d, J = 8.5 Hz, 2 H), 7.48–
7.45 (m, 2 H), 7.42–7.39 (m, 1 H), 7.37 (t, J = 4.5 Hz, 2 H), 7.22 (d,
J = 8.5 Hz, 2 H), 3.40 (s, 3 H), 2.56 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 197.0, 153.8, 142.9, 137.4, 132.4,
129.2, 128.1, 128.0, 127.3, 125.0, 89.3, 84.8, 36.3, 26.6.
129.4, 129.3, 128.0, 127.5, 125.5, 120.2, 89.9, 86.2, 36.5, 19.9.
MS (EI, 70 eV): m/z (%) = 248 (43) [M]+, 143 (100).
3-(4-Methoxyphenyl)-N-methyl-N-phenylpropiolamide (6)1a
Pale-yellow solid; mp 93.6–94.9 °C (uncorrected).
IR (KBr): 2210, 1636, 1593 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.45 (t, J = 7.5 Hz, 2 H), 7.40–
7.35 (m, 3 H), 7.07 (d, J = 9.0 Hz, 2 H), 6.75 (d, J = 8.5 Hz, 2 H),
3.77 (s, 3 H), 3.39 (s, 3 H).
MS (EI, 70 eV): m/z (%) = 277 (56) [M]+, 171 (100).
3-(4-Nitrophenyl)-N-methyl-N-phenylpropiolamide (12)7
Yellow solid; mp 96.1–98.3 °C (uncorrected).
IR (KBr): 2210, 1638, 1585 cm–1.
13C NMR (125 MHz, CDCl3): d = 160.8, 154.6, 143.3, 134.2, 129.0,
1H NMR (500 MHz, CDCl3): d = 8.10 (d, J = 8.0 Hz, 2 H), 7.47–
7.42 (m, 3 H), 7.36 (d, J = 6.0 Hz, 2 H), 7.29 (d, J = 8.5 Hz, 2 H),
3.41 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 153.4, 148.0, 142.8, 133.0, 129.3,
128.3, 127.4, 127.1, 123.5, 87.8, 86.3, 36.4.
127.8, 127.4, 113.9, 112.2, 91.4, 81.9, 55.2, 36.2.
MS (EI, 70 eV): m/z (%) = 256 (33) [M]+, 159 (100).
3-(2-Methoxyphenyl)-N-methyl-N-phenylpropiolamide (7)1a
Pale-yellow solid; mp 86.3–87.8 °C (uncorrected).
IR (KBr): 2210, 1638, 1581 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.43 (t, J = 7.5 Hz, 2 H), 7.39–
7.35 (m, 3 H), 7.29–7.26 (m, 1 H), 7.11–7.09 (m, 1 H), 6.82–6.75
(m, 2 H), 3.69 (s, 3 H), 3.39 (s, 3 H).
MS (EI, 70 eV): m/z (%) = 280 (83) [M]+, 174 (100).
N-Methyl-3-(3-nitrophenyl)-N-phenylpropiolamide (13)6d
Yellow oil.
IR (KBr): 2210, 1638, 1585 cm–1.
13C NMR (125 MHz, CDCl3): d = 161.0, 154.4, 143.2, 134.4, 131.5,
129.0, 127.5, 127.3, 120.2, 110.6, 109.7, 87.7, 86.4, 55.4, 36.4.
1H NMR (500 MHz, CDCl3): d = 8.18–8.16 (m, 1 H), 7.90 (s, 1 H),
7.51–7.44 (m, 5 H), 7.39–7.37 (m, 2 H), 3.42 (s, 3 H).
MS (EI, 70 eV): m/z (%) = 264 (9) [M]+, 159 (72), 147 (52), 131
(44), 115 (100).
13C NMR (125 MHz, CDCl3): d = 153.5, 147.9, 142.8, 137.8, 129.6,
129.4, 128.4, 127.4, 127.2, 124.5, 122.2, 87.7, 84.3, 36.4.
MS (EI, 70 eV): m/z (%) = 280 (99) [M]+, 174 (83), 128 (100).
3-(4-Fluorophenyl)-N-methyl-N-phenylpropiolamide (8)6d
White solid; mp 50.3–51.6 °C (uncorrected).
IR (KBr): 2231, 1638, 1597 cm–1.
3-(2-Formylphenyl)-N-methyl-N-phenylpropiolamide (14)6d
Yellow solid; mp 63.2–64.5 °C (uncorrected).
1H NMR (500 MHz, CDCl3): d = 7.46 (t, J = 8.0 Hz, 2 H), 7.40 (t,
J = 7.0 Hz, 1 H), 7.36 (d, J = 7.5 Hz, 2 H), 7.13–7.10 (m, 2 H), 6.93
(t, J = 8.5 Hz, 2 H), 3.40 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 163.4 (d, J = 251.0 Hz), 154.1,
143.1, 134.5, 134.4, 129.1, 127.9, 127.4, 115.7 (d, J = 22.3 Hz),
89.7, 82.3, 36.3.
IR (KBr): 2214, 1699, 1634, 1593 cm–1.
1H NMR (500 MHz, CDCl3): d = 9.36 (s, 1 H), 7.83 (d, J = 2.0 Hz,
1 H), 7.82 (d, J = 2.0 Hz, 1 H), 7.54–7.45 (m, 5 H), 7.37–7.35 (m,
2 H), 3.41 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 190.5, 153.6, 142.7, 136.8, 134.2,
133.6, 130.3, 129.5, 128.5, 127.4, 126.9, 123.6, 88.4, 85.9, 36.5.
MS (EI, 70 eV): m/z (%) = 253 (49) [M]+, 147 (100).
MS (EI, 70 eV): m/z (%) = 262 (10) [M]+, 234 (100), 101 (67).
3-(4-Chlorophenyl)-N-methyl-N-phenylpropiolamide (9)1a
Pale-yellow solid; mp 60.2–61.8 °C (uncorrected).
IR (KBr): 2224, 1640, 1595 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.45 (t, J = 7.5 Hz, 2 H), 7.39 (d,
J = 7.0 Hz, 1 H), 7.36 (t, J = 7.5 Hz, 2 H), 7.21 (d, J = 8.5 Hz, 2 H),
7.05 (d, J = 8.5 Hz, 2 H), 3.39 (s, 3 H).
N-Methyl-N-phenyl-3-(4-vinylphenyl)propiolamide (15)6d
Colorless oil.
IR (KBr): 2216, 1642, 1493 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.45 (t, J = 7.5 Hz, 2 H), 7.39 (d,
J = 7.0 Hz, 1 H), 7.36 (t, J = 4.5 Hz, 2 H), 7.26 (t, J = 4.0 Hz, 2 H),
Synthesis 2011, No. 17, 2789–2795 © Thieme Stuttgart · New York