The Journal of Organic Chemistry
Article
3H). 13C{1H} NMR (150 MHz, CDCl3) δ (ppm): 197.3 (Cq), 190.4
(Cq), 144.9 (Cq), 144.1 (Cq), 141.4 (Cq), 137.9 (CH), 133.4 (Cq),
132.2 (CH), 131.3 (Cq), 130.5 (CH), 130.4 (CH), 129.2 (CH), 128.3
(CH), 127.8 (CH), 53.3 (CH2), 45.1 (CH2), 28.0 (CH3), 21.7 (CH3).
HRMS (ESI) m/z: [M + H]+ calcd for C22H22NO4S+ 396.1264; found
396.1262.
45.1 (CH2), 28.4 (CH3), 26.8 (CH3), 21.7 (CH3). HRMS (ESI) m/z:
[M + Na]+ calcd for C24H23NO5SNa+ 460.1189; found 460.1182.
(E)-4-(4-Fluorophenyl)-5-(3-oxobut-1-en-1-yl)-1-tosyl-1,6-
dihydropyridin-3(2H)-one, 2g. Synthesized according to the general
procedure GP5. Yellow solid, 40 mg, 48% yield, mp 149−153 °C
(decomposition). Rf 0.16 (7/3 PE/EtOAc). 1H NMR (600 MHz,
CDCl3) δ (ppm): 7.70 (d, 2H, J = 8.3 Hz), 7.36 (d, 2H, J = 7.9 Hz),
7.08−7.05 (m, 2H), 7.01 (d, 1H, J = 16.4 Hz), 6.87−6.83 (m, 2H), 6.49
(d, 1H, J = 16.5 Hz), 4.31 (s, 2H), 4.04 (s, 2H), 2.44 (s, 3H), 2.22 (s,
3H). 13C{1H} NMR (150 MHz, CDCl3) δ (ppm): 197.1 (Cq), 190.4
(Cq), 163.2 (Cq, d, J = 250.1 Hz), 144.9 (Cq), 144.4 (Cq), 140.3 (Cq),
137.4 (CH), 133.3 (Cq), 132.4 (CH, d, J = 8.7 Hz), 132.3 (CH), 130.4
(CH), 127.8 (CH), 127.1 (Cq), 115.5 (CH, d, J = 21.5 Hz), 53.3
(CH2), 45.1 (CH2), 28.3 (CH3), 21.7 (CH3). 19F NMR (564 MHz,
CDCl3) δ (ppm): (−111.4)−(−112.0) (m). HRMS (ESI) m/z: [M +
Na]+ calcd for C22H20FNO4SNa+ 436.0989; found 436.0969.
(E)-5-(3-Oxobut-1-en-1-yl)-4-(thiophen-2-yl)-1-tosyl-1,6-
dihydropyridin-3(2H)-one, 2h. Synthesized according to the general
procedure GP5. Yellow solid, 24 mg, 30% yield, mp 146−148 (Et2O,
decomposition). Rf 0.23 (7/3 PE/EtOAc). 1H NMR (600 MHz,
CDCl3) δ (ppm): 7.70−7.67 (m, 2H), 7.52 (dd, 1H, J = 5.2, 1.2 Hz),
7.36 (d, 1H, J = 16.5 Hz), 7.32 (d, 2H, J = 8.0 Hz), 7.06 (dd, 1H, J = 5.1,
3.6 Hz), 6.81 (dd, 1H, J = 3.6, 1.2 Hz), 6.55 (d, 1H, J = 16.5 Hz), 4.31 (s,
2H), 4.1 (s, 2H), 2.39 (s, 3H), 2.29 (s, 3H). 13C{1H} NMR (150 MHz,
CDCl3) δ (ppm): 197.3 (Cq), 189.9 (Cq), 144.9 (Cq), 143.9 (Cq),
138.0 (CH), 134.4 (Cq), 133.2 (Cq), 132.4 (CH), 131.8 (CH),
131.1(Cq), 130.5 (CH), 130.4 (CH), 127.7 (CH), 126.7 (CH), 53.3
(CH2), 45.7 (CH2), 28.3 (CH3), 21.7 (CH3). HRMS (ESI) m/z: [M +
H]+ calcd for C20H20NO4S2+ 402.0828; found 402.0827.
(E)-4-(Naphthalen-1-yl)-5-(3-oxobut-1-en-1-yl)-1-tosyl-1,6-
dihydropyridin-3(2H)-one, 2i. Synthesized according to the general
procedure GP5. Yellow solid, 65 mg, 73% yield, mp 131−141 °C
(decomposition). Rf 0.16 (7/3 PE/EtOAc). 1H NMR (600 MHz,
CDCl3) δ (ppm): 7.89 (d, 1H, J = 8.3 Hz), 7.87 (d, 1H, J = 8.2 Hz), 7.77
(d, 2H, J = 8.4 Hz), 7.49−7.44 (m, 2H), 7.42 (d, 2H, J = 7.9 Hz), 7.38−
7.35 (m, 1H), 7.20 (d, 1H, J = 8.4 Hz), 6.91 (dd, 1H, J = 7.0, 1.0 Hz),
6.79 (d, 1H, J = 16.6 Hz), 6.45 (d, 1H, J = 16.6 Hz), 4.42 (d, 1H, J = 17.2
Hz), 4.34 (d, 1H, J = 17.4 Hz), 4.14 (dd, 1H, J = 16.7, 1.3 Hz), 4.04 (dd,
1H, J = 16.7, 1.4 Hz), 2.49 (s, 3H), 2.01 (s, 3H). 13C{1H} NMR (150
MHz, CDCl3) δ (ppm): 197.3 (Cq), 190.3 (Cq), 152.2 (CH), 146.4
(Cq), 145.0 (Cq), 140.8 (Cq), 137.5 (CH), 133.6 (Cq), 133.0 (Cq),
132.5 (CH), 132.0 (Cq), 130.5 (CH), 129.8 (CH), 129.4 (Cq), 128.8
(CH), 128.4 (CH), 127.9 (CH), 126.8 (CH), 126.4 (CH), 125.1
(CH), 125.0 (CH), 53.3 (CH2), 44.9 (CH2), 27.7 (CH3), 21.8 (CH3).
HRMS (ESI) m/z: [M + H]+ calcd for C26H24NO4S+ 446.1421; found
446.1410.
(E)-5-(3-Oxo-3-phenylprop-1-en-1-yl)-4-phenyl-1-tosyl-1,6-
dihydropyridin-3(2H)-one, 2j. Synthesized according to the general
procedure GP5. Yellow solid, 57 mg, 62% yield, mp 175−178 °C
(decomposition). Rf 0.23 (8/2 PE/EtOAc). 1H NMR (600 MHz,
CDCl3) δ (ppm): 7.92 (d, 2H, J = 7.2 Hz), 7.72 (d, 2H, J = 8.3 Hz),
7.64−7.60 (m, 1H), 7.51 (t, 2H, J = 7.8 Hz), 7.37−7.34 (m, 5H), 7.29
(d, 2H, J = 1.3 Hz), 6.82 (dd, 2H, J = 7.7, 1.6 Hz), 4.49 (s, 2H), 4.11 (s,
2H), 2.44 (s, 3H). 13C{1H} NMR (150 MHz, CDCl3) δ (ppm): 190.6
(Cq), 189.3 (Cq), 144.9 (Cq), 144.1 (Cq), 141.5 (Cq), 139.2 (CH),
137.2 (Cq), 133.7 (CH), 133.7 (Cq), 131.3 (Cq), 130.5 (CH), 130.5
(CH), 129.1 (CH), 129.0 (CH), 128.7 (CH), 128.3 (CH), 127.8
(CH), 127.7 (CH), 53.3 (CH2), 45.2 (CH2), 21.7 (CH3). HRMS (ESI)
m/z: [M + Na]+ calcd for C27H23NO4SNa+ 480.1240; found 480.1220.
(E)-4-(4-Methoxyphenyl)-5-(3-oxo-3-phenylprop-1-en-1-yl)-
1-tosyl-1,6-dihydropyridin-3(2H)-one, 2k. Synthesized according
to the general procedure GP5. Yellow solid, 77 mg, 78% yield, mp 159−
163 °C (decomposition). Rf 0.40 (99/1 DCM/EtOAc). 1H NMR (600
MHz, CDCl3) δ (ppm): 7.96−7.94 (m, 2H), 7.73−7.70 (m, 2H), 7.63
(tt, 1H, J = 7.1, 1.2 Hz), 7.54−7.51 (m, 2H), 7.36 (d, 1H, J = 16.0 Hz)
superimposed to 7.34 (d, 2H, J = 7.9 Hz), 7.28 (d, 1H, J = 16.0 Hz),
6.88−6.86 (m, 2H), 6.79−6.77 (m, 2H), 4.47 (s, 2H), 4.09 (s, 2H),
3.82 (s, 3H), 2.43 (s, 3H). 13C{1H} NMR (150 MHz, CDCl3) δ (ppm):
190.9 (Cq), 189.3 (Cq), 160.3 (Cq), 144.9 (Cq), 143.4 (Cq), 141.1
(Cq), 139.7 (CH), 137.7 (Cq), 133.7 (CH), 133.7 (Cq), 132.1 (CH),
(E)-4-(4-Methoxyphenyl)-5-(3-oxobut-1-en-1-yl)-1-tosyl-1,6-
dihydropyridin-3(2H)-one, 2b. Synthesized according to the general
procedure GP5. Yellow solid, 64 mg, 75% yield, mp 150−153 °C
1
(decomposition). Rf 0.24 (7/3 PE/EtOAc). H NMR (600 MHz,
CDCl3) δ (ppm): 7.69 (d, 2H, J = 8.3 Hz), 7.35 (d, 2H, J = 8.1 Hz), 7.09
(d, 1H, J = 16.6 Hz), 6.90−6.87 (m, 2H), 6.82−6.79 (m, 2H), 6.45 (d,
1H, J = 16.6 Hz), 4.29 (s, 2H), 4.03 (s, 2H), 3.83 (s, 3H), 2.44 (s, 3H),
2.22 (s, 3H). 13C{1H} NMR (150 MHz, CDCl3) δ (ppm): 197.4 (Cq),
190.7 (Cq), 160.3 (Cq), 144.8 (Cq), 143.5 (Cq), 140.9 (Cq), 138.2
(CH), 133.3 (Cq), 132.0 (CH), 131.8 (CH), 130.4 (CH), 127.8 (CH),
123.3 (Cq), 113.8 (CH), 55.4 (CH3), 53.3 (CH2), 45.2 (CH2), 28.1
(CH3), 21.7 (CH3). HRMS (ESI) m/z: [M + Na]+ C23H23NO5SNa+
448.1189; found 448.1094.
(E)-4-(4-Hydroxyphenyl)-5-(3-oxobut-1-en-1-yl)-1-tosyl-1,6-
dihydropyridin-3(2H)-one, 2c. Synthesized according to the general
procedure GP5. Yellow solid, 42 mg, 52% yield, mp 170−174 °C
1
(decomposition). Rf 0.25 (9/1 DCM/EtOAc). H NMR (600 MHz,
CD3OD) δ (ppm): 7.74−7.72 (m, 2H), 7.42 (d, 2H, J = 7.9 Hz), 7.07
(d, 1H, J = 16.4 Hz), 6.78−6.75 (m, 2H), 6.69 (d, 1H, J = 16.4 Hz),
6.64−6.62 (m, 2H), 4.51 (s, 2H), 4.17 (s, 2H), 2.45 (s, 3H), 2.24 (s,
3H), 2.19 (s, 1H). 13C{1H} NMR (150 MHz, CD3OD) δ (ppm): 200.5
(Cq), 193.7 (Cq), 160.2 (Cq), 146.9 (Cq), 145.9 (Cq), 143.0 (Cq),
140.2 (CH), 136.9 (Cq), 134.1 (CH), 133.4 (CH), 132.3 (CH), 129.6
(CH), 124.6 (Cq), 116.5 (CH), 55.2 (CH2), 47.1 (CH2), 29.1 (CH3),
22.3 (CH3). HRMS (ESI) m/z: [M + Na]+ calcd for C22H21NO5SNa+
434.1033; found 434.1024.
(E)-5-(3-Oxobut-1-en-1-yl)-4-(p-tolyl)-1-tosyl-1,6-dihydro-
pyridin-3(2H)-one, 2d. Synthesized according to the general
procedure GP5. Yellow solid, 71 mg, 86% yield, mp 166−167 °C
1
(Et2O). Rf 0.25 (75/25 PE/EtOAc). H NMR (600 MHz, CDCl3) δ
(ppm): 7.71−7.69 (m, 2H), 7.35 (d, 2H, J = 8.0 Hz), 7.16 (d, 2H, J =
7.8 Hz), 7.07 (d, 1H, J = 16.6 Hz), 6.75−6.72 (m, 2H), 6.45 (d, 1H, J =
16.5 Hz), 4.30 (s, 2H), 4.04 (s, 2H), 2.44 (s, 3H), 2.36 (s, 3H), 2.21 (s,
3H). 13C{1H} NMR (150 MHz, CDCl3) δ (ppm): 197.4 (Cq), 190.6
(Cq), 144.8 (Cq), 143.7 (Cq), 141.4 (Cq), 139.3 (Cq), 138.1 (CH),
133.4 (Cq), 131.9 (CH), 130.4 (CH), 129.1 (CH), 128.2 (Cq), 127.8
(CH), 53.3 (CH2), 45.1 (CH2), 28.1 (CH3), 21.7 (CH3), 21.5 (CH3).
HRMS (ESI) m/z: [M + H]+ calcd for C23H24NO4S+ 410.1421; found
410.1415.
Methyl (E)-4-(3-Oxo-5-(3-oxobut-1-en-1-yl)-1-tosyl-1,2,3,6-
tetrahydropyridin-4-yl)benzoate, 2e. Synthesized according to
the general procedure GP5. Light orange solid, 52 mg, 57% yield, mp
186−191 °C (decomposition). Rf 0.21 (65/35 PE/EtOAc). 1H NMR
(600 MHz, CDCl3) δ (ppm): 8.04−8.02 (m, 2H), 7.71−7.69 (m, 2H),
7.36 (d, 2H, J = 8.0 Hz), 6.95 (d, 1H, J = 16.6 Hz) superimposed to
6.94−6.92 (m, 2H), 6.50 (d, 1H, J = 16.5 Hz), 4.34 (s, 2H), 4.06 (s,
2H), 3.93 (s, 3H), 2.45 (s, 3H), 2.20 (s, 3H). 13C{1H} NMR (150
MHz, CDCl3) δ (ppm): 197.0 (Cq), 190.0 (Cq), 166.6 (Cq), 145.0
(Cq), 144.8 (Cq), 140.4 (Cq), 137.0 (CH), 136.0 (Cq), 133.4 (Cq),
132.7 (CH), 130.7 (Cq), 130.6 (CH), 130.5 (CH), 129.5 (CH), 127.8
(CH), 53.2 (CH2), 52.5 (CH3), 45.1 (CH2), 28.2 (CH3), 21.7 (CH3).
HRMS (ESI) m/z: [M + H]+ calcd for C24H24NO6S+ 454.1319; found
454.1307.
(E)-4-(4-Acetylphenyl)-5-(3-oxobut-1-en-1-yl)-1-tosyl-1,6-
dihydropyridin-3(2H)-one, 2f. Synthesized according to the general
procedure GP5. White solid, 37 mg, 43% yield, mp 161−164 °C
1
(decomposition). Rf 0.24 (6/4 PE/EtOAc). H NMR (600 MHz,
CDCl3) δ (ppm): 7.96−7.93 (m, 2H), 7.71 (d, 2H, J = 8.3 Hz), 7.37 (d,
2H, J = 8.0 Hz), 6.96 (d, 1H, J = 16.4 Hz) superimposed to 6.98−6.95
(m, 2H), 6.51 (d, 1H, J = 16.4 Hz), 4.34 (s, 2H), 4.06 (s, 2H), 2.62 (s,
3H), 2.45 (s, 3H), 2.22 (s, 3H). 13C{1H} NMR (150 MHz, CDCl3) δ
(ppm): 197.6 (Cq), 196.9 (Cq), 190.0 (Cq), 145.0 (Cq), 144.8 (Cq),
140.4 (Cq), 137.4 (Cq), 136.9 (CH), 136.2 (Cq), 133.4 (Cq), 132.7
(CH), 130.8 (CH), 130.5 (CH), 128.2 (CH), 127.8 (CH), 53.2 (CH2),
8303
J. Org. Chem. 2021, 86, 8295−8307