The Journal of Organic Chemistry
Article
bromothiophene (97 μL, 1.0 mmol) proceeded for 16 h, of which the
crude product was purified by column chromatography using
petroleum ether/EtOAc (1:3) to afford the title compound as a
yellow solid (159 mg, 85%): 1H NMR (600 MHz, CD3CN) δ = 8.57−
8.51 (m, 1 H), 7.82 (d, J = 15.8 Hz, 1 H), 7.71 (td, J = 7.7, 1.9 Hz, 1
H), 7.41−7.34 (m, 2 H), 7.25 (d, J = 3.5 Hz, 1 H), 7.18 (ddd, J = 7.7,
4.7, 1.1 Hz, 1 H), 7.07 (dd, J = 5.1, 3.5 Hz, 1 H), 7.02 (d, J = 15.8 Hz,
1 H) ppm; 13C{1H} NMR (151 MHz, CD3CN) δ = 155.7, 150.4,
142.7, 137.4, 128.7, 128.7, 128.1, 126.6, 125.9, 122.9, 122.9 ppm. The
physical data were in full accordance with the literature value.67
(E)-5-(2-(Phenylsulfonyl)vinyl)benzofuran (3c). Following general
method, the reaction of phenyl vinyl sulfone (219 mg, 1.3 mmol) and
5-bromobenzofuran (125 μL, 1.0 mmol) proceeded for 8 h, of which
the crude product was purified by column chromatography using
petroleum ether/EtOAc (1:1) to afford the title compound as a white
solid (239 mg, 84%): mp 96−99 °C; 1H NMR (600 MHz, CDCl3) δ =
8.00−7.94 (m, 2 H), 7.82−7.77 (m, 1 H), 7.75 (d, J = 1.8 Hz, 1 H),
7.66 (d, J = 2.2 Hz, 1 H), 7.63−7.60 (m, 1 H), 7.58−7.53 (m, 2 H),
7.52−7.49 (m, 1 H), 7.44 (dd, J = 8.6, 1.8 Hz, 1 H), 6.85 (d, J = 15.3
Hz, 1 H), 6.79 (dd, J = 2.2, 0.9 Hz, 1 H) ppm; 13C{1H} NMR (151
MHz, CDCl3) δ = 156.4, 146.4, 143.0, 140.9, 133.3, 129.3, 128.2,
127.6, 127.4, 125.9, 124.6, 122.5, 112.2, 106.8 ppm; IR (film) 3347,
2946, 2834, 158, 1449, 1115, 1027 cm−1; HRMS (ESI) calcd for
C16H12O3SNa+ [M + Na]+ 307.0403, found 307.0399.
H), 7.23 (ddd, J = 7.8, 4.9, 0.9 Hz, 1 H), 3.32 (dd, J = 7.8, 7.0 Hz, 2
H), 3.09 (t, J = 7.4 Hz, 2 H) ppm; 13C{1H} NMR (151 MHz, CDCl3)
δ = 198.5, 149.8, 147.5, 136.9, 136.71, 136.5, 133.4, 128.8, 128.1,
123.6, 39.8, 27.2 ppm. The physical data were in full accordance with
the literature value.69
3-(Benzo[b]thiophen-6-yl)-1-phenylpropan-1-one (3h). Following
general method, the reaction of vinylbenzyl alcohol (171 μL, 1.3
mmol) and 6-bromobenzo[b]thiophene (213 mg, 1.0 mmol)
proceeded for 16 h, of which the crude product was purified by
column chromatography using petroleum ether/EtOAc (4:1) to afford
the title compound as a pale yellow solid (332 mg, 83%): mp 81−84
°C; 1H NMR (600 MHz, CDCl3) δ = 7.99−7.94 (m, 2 H), 7.78−7.73
(m, 2 H), 7.59−7.53 (m, 1 H), 7.48−7.43 (m, 2 H), 7.38 (d, J = 5.4
Hz, 1 H), 7.29 (dd, J = 5.5, 0.8 Hz, 1 H), 7.27 (dd, J = 8.2, 1.6 Hz, 1
H), 3.40−3.31 (m, 2 H), 3.20 (dd, J = 8.4, 6.9 Hz, 2 H) ppm; 13C{1H}
NMR (151 MHz, CDCl3) δ = 199.2, 140.2, 138.1, 137.7, 136.9, 133.2,
128.7, 128.1, 125.8, 125.3, 123.7, 123.6, 121.9, 40.8, 30.2 ppm; IR
(film) 3365, 2836, 1682, 1440, 1205, 1116, 1022 cm−1; HRMS (ESI)
calcd for C17H14OSNa+ [M + Na]+ 289.0663, found 289.0677.
1-Phenyl-3-(thiophen-2-yl)propan-1-one (3i). Following general
method, the reaction of α-vinyl benzyl alcohol (170 μL, 1.3 mmol) and
2-bromothiophene (97 μL, 1.0 mmol) proceeded for 8 h, of which the
crude product was purified by column chromatography using
petroleum ether/EtOAc (1:2) to afford the title compound as a
1
(E)-3-(2-(Phenylsulfonyl)vinyl)pyridine (3d). Following general
method, the reaction of phenyl vinyl sulfone (219 mg, 1.3 mmol)
and 3-bromopyridine (96 μL, 1.0 mmol) proceeded for 8 h, of which
the crude product was purified by column chromatography using
petroleum ether/EtOAc (1:1) to afford the title compound as a yellow
oil (226 mg, 92%): 1H NMR (600 MHz, CDCl3) δ = 8.71 (d, J = 2.1
Hz, 1 H), 8.61 (dd, J = 4.8, 1.6 Hz, 1 H), 7.98−7.90 (m, 2 H), 7.78
(dddd, J = 8.0, 2.3, 1.6, 0.5 Hz, 1 H), 7.69−7.64 (m, 1 H), 7.64−7.60
(m, 1 H), 7.58−7.53 (m, 2 H), 7.34−7.29 (m, 1 H), 6.97 (d, J = 15.5
Hz, 1 H) ppm; 13C{1H} NMR (151 MHz, CDCl3) δ = 151.9, 150.0,
140.2, 138.8, 134.9, 133.8, 129.7, 129.6, 128.4, 127.9, 124.0 ppm. The
physical data were in full accordance with the literature value.68
(E)-6-(2-(Phenylsulfonyl)vinyl)imidazo[1,2-a]pyridine (3e). Fol-
lowing general method, the reaction of phenyl vinyl sulfone (219
mg, 1.3 mmol) and 6-bromoimidazo[1,2-a]pyridine (197 mg, 1.0
mmol) proceeded for 16 h, of which the crude product was purified by
column chromatography using petroleum ether/EtOAc (1:3) to afford
the title compound as a yellow solid (247 mg, 87%): mp 159−161 °C;
1H NMR (600 MHz, CDCl3) δ = 8.34−8.31 (m, 1 H), 7.93 (dd, J =
8.4, 1.3 Hz, 2 H), 7.65−7.53 (m, 7 H), 7.25 (dd, J = 9.5 Hz, 1.8, 1H)
6.87 (d, J = 15.3 Hz, 1 H) ppm; 13C{1H} NMR (151 MHz, CDCl3) δ
= 145.1, 140.5, 138.5, 134.9, 133.7, 129.5, 128.9, 127.8, 127.7, 121.7,
119.0, 118.5, 113.7 ppm; IR (film) 3351, 2948, 2835, 1650, 1449,
1114, 1023 cm−1; HRMS (ESI) calcd for C15H12N2O2SNa+ [M + Na]+
307.0512, found 307.0514.
Methyl 2-(3-oxo-3-phenylpropyl)benzoate (3f). Following general
method, the reaction of α-vinyl benzyl alcohol (170 μL, 1.3 mmol) and
methyl 2-bromobenzoate (140 μL, 1.0 mmol) proceeded for 8 h, of
which the crude product was purified by column chromatography
using petroleum ether/EtOAc (1:1) to afford the title compound as a
colorless oil (247 mg, 92%): 1H NMR (600 MHz, CDCl3) δ = 8.00−
7.96 (m, 2 H), 7.92 (dt, J = 7.8, 0.9 Hz, 1 H), 7.57−7.52 (m, 1 H),
7.47−7.41 (m, 3 H), 7.36 (dd, J = 7.5, 1.2 Hz, 1 H), 7.30−7.27 (m, 1
H), 3.89 (s, 3 H), 3.38−3.33 (m, 4 H) ppm; 13C{1H} NMR (151
MHz, CDCl3) δ = 199.5, 168.0, 143.5, 137.1, 133.1, 132.4, 131.6,
131.0, 129.6, 128.7, 128.3, 126.5, 52.2, 40.7, 29.5 ppm; IR (film) 3354,
2949, 2835, 1718, 1684, 1449, 1257, 1081, 1024 cm−1; HRMS (ESI)
calcd for C17H16O3H+ [M + H]+ 269.1172, found 269.1176.
yellow solid (197 mg, 91%): H NMR (600 MHz, CDCl3) δ = 7.98
(dt, J = 8.1, 1.1 Hz, 2 H), 7.60−7.54 (m, 1 H), 7.47 (t, J = 7.8 Hz, 2
H), 7.14 (dd, J = 5.1, 1.2 Hz, 1 H), 6.94 (dd, J = 5.1, 3.5 Hz, 1 H), 6.88
(dt, J = 3.4, 1.1 Hz, 1 H), 3.37 (ddd, J = 7.8, 6.5, 1.6 Hz, 2 H), 3.34−
3.28 (m, 2 H) ppm; 13C{1H} NMR (151 MHz, CDCl3) δ = 198.5,
143.9, 136.7, 133.2, 128.7, 128.6, 128.1, 128.0, 126.9, 124.7, 123.4,
40.6, 40.5, 24.2 ppm. The physical data were in full accordance with
the literature value.70
1-Mesitylpentan-3-one (3j). Following the general method, the
reaction of 2-bromomesitylene (199.1 mg, 1 mmol) and 1-penten-3-ol
(112 mg, 1.3 mmol) proceeded for 8 h, of which the crude product
was purified by column chromatography using petroleum/EtOAc
(9:1) as the eluent to give the title compounds as a colorless oil (186
mg, 91%): 1H NMR (400 MHz, CDCl3) δ = 6.83 (s, 2 H), 2.91−2.82
(m, 2 H), 2.58−2.50 (m, 2 H), 2.45 (q, J = 7.3 Hz, 2 H), 2.27 (s, 6 H),
2.25 (s, 3 H), 1.08 (t, J = 7.3 Hz, 3 H) ppm; GC−MS calcd for
C14H20O+ [M]+ 204.15, found 204.2. The physical data were in full
accordance with the literature value.71
(E)-4-(2-Aminopyrimidin-5-yl)but-3-en-2-one (3k). Following the
general method, the reaction of 2-amino-5-bromopyrimidine (174 mg,
1 mmol) and methyl vinyl ketone (91.1 mg, 1.3 mmol) proceeded for
8 h, of which the crude product was purified by column
chromatography using MeOH/EtOAc/CH2Cl2 (5:30:65) as the eluent
to give the title compound as a pale yellow solid (150 mg, 92%): mp
1
187−189 °C; H NMR (400 MHz, CD3OD) δ = 8.55 (s, 2 H), 7.50
(d, J = 16.4 Hz, 1 H), 6.72 (d, J = 16.4 Hz, 1 H), 2.35 (s, 3 H) ppm;
13C{1H} NMR (101 MHz, CD3OD) δ = 200.8, 165.1, 159.7, 139.9,
125.1, 119.2, 27.2 ppm; IR (film) 3390, 1650, 16226, 1592, 1500,
1280, 1248,1218, 992 cm−1; HRMS (ESI) calcd for C8H9N3OH+ [M +
H]+ 164.0818, found 164.0823.
Methyl (E)-3-(imidazo[1,2-a]pyridin-6-yl)acrylate (3l). Following
general method, the reaction of methyl acrylate (117 μL, 1.3 mmol)
and 6-bromoimidazopyridine (197.0 mg, 1 mmol) proceeded for 8 h,
of which the crude product was purified by column chromatography
using petroleum/EtOAc (1:3) as the eluent to afford the title
1
compound as a brown solid (173.9 mg, 86%): mp 177−180 °C; H
NMR (400 MHz, CDCl3) δ = 8.23 (d, J = 1.9 Hz, 1 H), 7.69−7.54 (m,
4 H), 7.37 (dd, J = 9.4, 1.8 Hz, 1 H), 6.40 (d, J = 15.9 Hz, 1 H), 3.80
(s, 3 H) ppm; 13C{1H} NMR (101 MHz, CDCl3) δ = 167.0, 145.3,
140.6, 134.7, 127.6, 121.89, 120.9, 118.5, 118.3, 113.4, 51.9 ppm; IR
(film) 3349, 2947, 1650, 1449, 1113, 1024 cm−1; HRMS (ESI) calcd
for C11H10N2O2H+ [M + H]+ 203.0821, found 203.0812.
1-Phenyl-3-(pyridin-3-yl)propan-1-one (3g). Following general
method, the reaction of α-vinyl benzyl alcohol (170 μL, 1.3 mmol)
and 3-bromopyridine (96 μL, 1.0 mmol) proceeded for 8 h, of which
the crude product was purified by column chromatography using
petroleum ether/EtOAc (1:3) to afford the title compound as a pale
yellow solid (188 mg, 89%): 1H NMR (600 MHz, CDCl3) δ = 8.53 (d,
J = 2.3 Hz, 1 H), 8.45 (dd, J = 4.8, 1.6 Hz, 1 H), 8.01−7.89 (m, 2 H),
7.61 (dt, J = 7.8, 1.8 Hz, 1 H), 7.58−7.52 (m, 1 H), 7.49−7.40 (m, 2
(E)-4-Mesityl-2-methylbut-3-en-2-ol (3m). Following general
method, the reaction of 2-methyl-3-buten-2-ol (160 μL, 1.3 mmol)
and 2-bromomesitylene (153 μL, 1 mmol) proceeded for 8 h, of which
the crude product was purified by column chromatography using
4060
J. Org. Chem. 2015, 80, 4054−4063