The Journal of Organic Chemistry
Note
137.3, 136.3, 133.7, 133.3, 130.3, 129.7, 128.8, 127.7, 125.2. HRMS
(ESI-TOF) m/z: [M + Na ]+ calcd for C15H10BrNO3Na 353.9742;
found 353.9737.
NMR (CDCl3, 500 MHz) δ 8.07 (d, J = 7.8, 1H), 7.68 (d, J = 7.7, 2H),
7.46 (m, 1H), 7.28−7.38 (m, 4H), 7.26−7.29 (m, 1H), 7.12 (d, J =
7.3, 1H), 7.03 (m, 1H), 6.68−6.73 (m, 2H), 5.10−5.13 (m, 1H), 4.48
(s, 1H), 3.67 (m, 3H), 2.70−2.75 (m, 1H), 2.40−2.45 (m, 1H). 13C
NMR (CDCl3, 100 MHz) δ 197.9, 172.7, 146.3, 137.1, 137.0, 132.8,
132.6, 131.8, 130.2, 129.6, 128.9, 128.6, 128.3, 128.0, 127.8, 127.0,
125.6, 120.1, 109.4, 52.9, 42.1, 41.5. HRMS (ESI-TOF) m/z: [M +
H]+ calcd for C24H21ClNO3 406.1210; found 406.1206.
anti-Methyl 3-(1-Phenylethanone-2-yl)-2-p-tolylindoline-2-
carboxylate (4g). Amorphous solid (20 mg, 53%). 1H NMR
(CDCl3, 500 MHz) δ 7.61 (d, J = 7.4, 2H), 7.51 (d, J = 8.0, 2H),
7.42−7.44 (m, 1H), 7.30 (t, J = 7.7, 1H), 7.07−7.15 (m, 4H), 6.81 (d,
J = 7.0, 1H), 6.71 (m, 1H), 5.01 (s, 1H), 4.87 (t, J = 7.0, 1H), 3.70 (s,
3H), 2.71 (d, J = 7.0, 2H), 2.26 (s, 3H). 13C NMR (CDCl3, 100 MHz)
δ 198.6, 175.4, 148.3, 137.9, 137.0, 134.2, 132.7, 131.3, 129.3, 128.2,.
128.1, 127.9, 126.6, 125.5, 120.0, 110.1, 53.1, 44.5, 40.9, 21.0. HRMS
(ESI-TOF) m/z: [M + Na]+ calcd for C25H23NO3Na 408.1570; found
408.1577.
(E)-3-(2-Amino-4-bromophenyl)-1-phenylprop-2-en-1-one
1
(2h). Crystalline solid, mp 100.3−102.2 °C (85 mg, 70%). H NMR
(400 MHz, CDCl3) δ 8.02 (d, J = 7.7 Hz, 2H), 7.90 (d, J = 15.3 Hz,
1H), 7.59 (t, J = 7.3 Hz, 1H), 7.55−7.41 (m, 4H), 6.90−6.63 (m, 2H),
4.13 (s, 2H). 13C NMR (101 MHz, CDCl3) δ 190.0, 147.0, 138.8,
138.2, 137.3, 132.9, 129.2, 128.7, 128.5, 122.0, 119.2, 118.7, 116.3.
HRMS (ESI-TOF) m/z: [M + Na ]+ calcd for C15H12BrNONa
324.0000; found 323.9984.
(E)-3-(3-(2-Aminophenyl)acryloyl)oxazolidin-2-one (7).
Amorphous solid (63 mg, 68%).1H NMR (400 MHz, CDCl3) δ
7.99 (d, J = 15.6 Hz, 1H), 7.78 (d, J = 15.6 Hz, 1H), 7.49 (d, J = 7.8
Hz, 1H), 7.18 (t, J = 7.6 Hz, 1H), 6.89−6.63 (m, 2H), 4.45 (t, J = 8.0
Hz, 2H), 4.12 (dd, J = 16.0, 7.9 Hz, 4H). 13C NMR (101 MHz,
CDCl3) δ 165.7, 153.7, 146.2, 141.8, 131.8, 129.1, 119.8, 118.9, 116.8,
116.2, 62.1, 42.9. HRMS (ESI-TOF) m/z: [M + Na ]+ calcd for
C12H12N2O3Na 255.0740; found 255.0754.
anti-Methyl 2-(3-Methoxyphenyl)-3-(1-phenylethanone-2-
yl)indoline-2-carboxylate (4h). Amorphous solid (20 mg, 49%).
1H NMR (CDCl3, 500 MHz) δ 7.62 (d, J = 8.0, 2H), 7.42−7.44 (m,
anti-Methyl 2-(4-Bromophenyl)-3-(1-phenylethanone-2-yl)-
1
indoline-2-carboxylate (4a). Amorphous solid (32 mg, 71%). H
NMR (CDCl3, 500 MHz) δ 7.47 (d, J = 8.0 Hz, 2H), 7.39 (d, J = 8.3
Hz, 2H), 7.28−7.33 (m, 3H), 7.12−7.20 (m, 2H), 7.01 (d, J = 7.4 Hz,
1H), 6.94 (m, 1H), 6.69 (d, J = 7.7 Hz, 1H), 6.60 (m, 1H), 4.86 (s,
1H), 4.75 (m, 1H), 3.58 (s, 3H), 2.57 (d, J = 6.8 Hz, 2H). 13C NMR
(125 MHz, CDCl3) δ 198.3, 174.9, 148.1, 136.3, 132.9, 131.7, 131.0,
128.6, 128.30, 128.26, 127.8, 125.5, 122.4, 120.3, 110.3, 53.3, 44.5,
40.9; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C24H20BrNO3Na
472.0519; found 472.0529.
anti-Methyl 1-Methyl-3-(2-oxo-2-phenylethyl)-2-phenyl-
indoline-2-carboxylate (4b). Oil (27 mg, 70%). 1H NMR (400
MHz, CDCl3) δ 7.60 (d, J = 7.6 Hz, 2H), 7.45 (t, J = 7.2 Hz, 1H),
7.35−7.23 (m, 6H), 7.22−7.10 (m, 2H), 7.03 (d, J = 7.2 Hz, 1H), 6.66
(t, J = 7.4 Hz, 1H), 6.49 (d, J = 7.8 Hz, 1H), 4.85 (t, J = 6.8 Hz, 1H),
3.77 (s, 3H), 2.86 (s, 3H), 2.73 (dd, J = 16.1, 9.5 Hz, 2H). 13C NMR
(100 MHz, CDCl3) δ 198.2, 173.1, 150.4, 136.9, 136.0, 132.8, 130.8,
128.4, 128.3, 128.2, 128.1, 127.9, 127.7, 124.2, 118.2, 106.0, 81.6, 52.2,
45.4, 41.9, 32.2. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C25H23NO3Na 408.1570; found 408.1562.
1H), 7.30−7.32 (m, 2H), 7.21−7.22 (m, 3H), 7.14 (d, J = 7.5, 1H),
7.06−7.07 (m, 1H), 6.81 (d, J = 7.8, 1H), 6.71−6.75 (m, 2H), 5.01 (s,
1H), 4.88 (t, J = 6.9, 1H), 3.78 (s, 3H), 3.71 (s, 3H), 2.73 (d, J = 6.9,
2H). 13C NMR (CDCl3, 100 MHz) δ 198.3, 175.1, 159.7, 148.2, 138.8,
132.8, 131.3, 129.7, 128.2, 128.1, 127.9, 125.5, 120.1, 119.0, 113.5,
112.6, 110.2, 55.2, 53.2, 44.4, 40.8. HRMS (ESI-TOF) m/z: [M +
Na]+ calcd for C25H23NO4Na 424.1519; found 424.1521.
anti-Methyl 3-(2-Oxo-2-phenylethyl)-2-(thiophen-2-yl)-
1
indoline-2-carboxylate (4i). Amorphous solid (17 mg, 46%). H
NMR (500 MHz, CDCl3) δ 7.61−7.67 (m, 2H), 7.30−7.42 (m, 1H),
7.26−7.28 (m, 2H), 7.02−7.07 (m, 4H), 6.83 (m, 1H), 6.74−6.76 (m,
1H), 6.66 (m, 1H), 5.22 (s, 1H), 4.73 (m, 1H), 3.72 (s, 3H), 2.76−
2.88 (m, 2H). 13C NMR (CDCl3, 100 MHz) δ 197.4, 173.4, 147.0,
140.9, 136.5, 131.9, 130.0, 127.3, 127.3, 126.9, 126.7, 125.2, 124.5,
124.3, 119.4, 109.4, 73.6, 52.4, 44.5, 40.1. HRMS (ESI-TOF) m/z: [M
+ Na]+ calcd for C22H19NNaO3S 400.0978; found 400.0999.
anti-tert-Butyl 3-(2-(Methoxycarbonyl)-3-(2-oxo-2-phenyl-
ethyl)indolin-2-yl)-1H-indole-1-carboxylate (4j). Amorphous
1
solid (15 mg, 30%). H NMR (CDCl3, 500 MHz) δ 7.99 (m, 1H),
anti-Methyl 3-(1-Phenylethanone-2-yl)-2-phenylindoline-2-
carboxylate (4c). Amorphous solid (24 mg, 64%). 1H NMR
(CDCl3, 500 MHz) δ 7.60−7.65 (m, 4H), 7.42 (m, 1H), 7.284−
7.34 (m, 4H), 7.24−7.26 (m, 1H), 7.14 (d, J = 7.4, 1H), 7.08 (m, 1H),
6.82 (d, J = 7.7, 1H), 6.71 (m, 1H), 5.03 (s, 1H), 4.88 (m, 1H), 3.71
(s, 3H), 2.64−2.76 (m, 2H). 13C NMR (CDCl3, 100 MHz) δ198.5,
175.2, 148.3, 137.2, 137.0, 132.8, 131.3, 128.6, 128.2, 128.1, 127.8,
126.7, 125.6, 120.0, 110.2, 53.1, 44.3, 40.9. HRMS (ESI-TOF) m/z:
[M + Na]+ calcd for C24H21NO3Na 394.1414; found 394.1422.
anti-Methyl 2-(4-Fluorophenyl)-3-(1-phenylethanone-2-yl)-
7.80 (m, 1H), 7.72(s, 1H), 7.40−7.49 (m, 2H), 7.32 (m, 1H), 7.12−
7.30 (m, 5H), 7.02 (m, 1H), 6.80 (m, 1H), 6.66 (m, 1H), 5.09 (s, 1H),
5.01(m, 1H), 3.60 (s, 3H), 2.80 (m, 2H), 1.60 (s, 9H). 13C NMR
(CDCl3, 100 MHz) 197.4, 173.5, 148.3, 146.7, 135.8, 131.7, 130.4,
127.2, 127.1, 126.7, 124.7, 124.2, 123.7, 122.1, 119.9, 119.2, 116.9,
114.2, 109.2, 83.0, 72.4., 52.1, 42.7, 39.6, 27.1. HRMS (ESI-TOF) m/
z: [M + Na]+ calcd for C31H30N2O5Na 533.2060; found 533.2075.
anti-Methyl 2-(4-Bromophenyl)-3-(1-(4-chlorophenyl)-
ethanone-2-yl)indoline-2-carboxylate (4k). Amorphous solid
1
1
indoline-2-carboxylate (4d). Amorphous solid (32 mg, 81%). H
(32 mg, 67%). H NMR (CDCl3, 500 MHz) δ 7.52 (m, 4H), 7.40
NMR (CDCl3, 500 MHz) δ 7.60−7.65 (m, 4H), 7.45 (m, 1H), 7.30−
7.33 (m, 2H), 7.15 (d, J = 7.3, 1H), 7.08−7.10 (m, 1H), 6.99 (t, J =
8.6, 2H), 6.82 (d, J = 7.8, 1H), 6.73 (m, 1H), 5.02 (s, 1H), 4.88 (t, J =
6.7, 1H), 3.72 (s, 3H), 2.70 (d, J = 7.5, 2H). 13C NMR (CDCl3, 100
MHz) δ198.3, 175.1, 163.4, 161.5,148.2, 136.9, 133.0, 132.9, 131.2,
128.7, 128.6, 128.3, 128.2, 127.8, 125.5, 120.3, 115.6, 115.4, 110.3,
53.2, 44.5, 40.9, 29.7. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C24H20FNO3Na 412.1319; found 412.1322.
(d, J = 8.7, 2H), 7.29 (d, J = 8.5, 2H), 7.08−7.13 (m, 2H), 6.82 (d, J =
7.7, 1H), 6.74 (t, J = 7.5, 1H), 4.99 (s, 1H), 4.86 (t, J = 7.7, 1H), 3.71
(s, 3H), 2.67 (m, 2H). 13C NMR (CDCl3, 100 MHz) δ 197.1, 175.4,
148.0, 136.2, 135.1, 131.8, 129.3, 128.64, 128.60, 128.4, 125.4, 122.5,
120.4, 110.4, 53.3, 44.7, 40.7. (ESI-TOF) m/z: [M + Na]+ calcd for
C24H19BrClNO3Na 506.0129; found 506.0122.
anti-Methyl 2-(4-Bromophenyl)-3-(2-oxo-2-(p-tolyl)ethyl)-
1
indoline-2-carboxylate (4l). Amorphous solid (25 mg, 52%). H
NMR (CDCl3, 500 MHz) δ 7.49−7.52 (m, 4H), 7.40 (d, J = 8.6, 2H),
7.06−7.14 (m, 4H), 6.81 (d, J = 7.7, 1H), 6.72 (t, J = 7.4, 1H), 4.98 (s,
1H), 4.87 (t, J = 7.2, 1H), 2.91(s, 3H), 2.66 (d, J = 6.8, 2H), 2.34 (s,
3H). 13C NMR (CDCl3, 100 MHz) δ 197.9, 174.9, 148.1, 143.8, 136.3,
134.4, 131.7, 131.2, 129.0, 128.6, 128.2, 128.0, 125.5, 122.4, 120.3,
110.3, 53.3, 44.6, 40.7, 21.6. HRMS (ESI-TOF) m/z: [M + Na]+ calcd
for C25H22BrNO3Na 486.0681; found 486.0674.
anti-Methyl-3-(2-(furan-2-yl)-2-oxoethyl)-2-phenylindoline-
2-carboxylate (4m). Amorphous solid (25 mg, 70%). 1H NMR
(CDCl3, 500 MHz) δ 7.64 (d, J = 7.6, 2H), 7.40 (s, 1H), 7.32 (m,
2H), 7.24−7.26 (m, 1H), 7.08 (m, 2H), 6.82 (m, 2H), 6.70 (t, J = 8.0,
1H), 6.34 (d, J = 2.0, 1H), 5.01 (s, 1H), 4.83 (t, J = 8.0, 1H), 3.70 (s,
anti-Methyl 2-(3-Bromophenyl)-3-(1-phenylethanone-2-yl)-
1
indoline-2-carboxylate (4e). Amorphous solid (30 mg, 66%). H
NMR (CDCl3, 500 MHz) δ 7.87 (s, 1H), 7.62 (d, J = 8.0, 2H), 7.55
(d, J = 7.5, 1H), 7.45 (m, 1H), 7.32 (m, 3H), 7.15 (t, J = 7.5, 2H), 7.08
(m, 1H), 6.83 (d, J = 8.0, 1H), 6.74 (t, J = 7.0, 1H), 5.01 (s, 1H), 4.90
(m, 1H), 3.73 (s, 3H), 2.72 (d, J = 6.5, 2H). 13C NMR (CDCl3, 100
MHz) δ 198.2, 174.7, 148.0, 139.5, 136.8, 132.9, 131.3, 131.0, 130.1,
129.9, 128.3, 127.9, 125.6, 125.5, 123.0, 120.4, 110.4, 53.4, 44.6, 40.8.
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C24H20BrNO3Na
472.0519; found 472.0534.
anti-Methyl 2-(2-Chlorophenyl)-3-(1-phenylethanone-2-yl)-
1
indoline-2-carboxylate (4f). Amorphous solid (24 mg, 59%). H
F
dx.doi.org/10.1021/jo501282h | J. Org. Chem. XXXX, XXX, XXX−XXX