ACCEPTED MANUSCRIPT
6
Tetrahedron
+
3
.84 (t, J = 5.6 Hz, 1H), 3.09 (dd, J = 4.0, 17.2 Hz, 1H), 2.88
26.8, 14.1; HRMS (ESI-TOF) Calcd for C13
284.0893; found: 284.0885.
3
H15NNaO [M+Na] :
1
3
(
(
1
5
1
dd, J = 7.6, 17.2 Hz, 1H), 1.21 (t, J = 7.2 Hz, 3H); C NMR
100 MHz, CDCl ) δ 178.2, 170.9, 147.1 (d, J = 242.5 Hz, 1C),
31.5 (d, J = 3.3 Hz, 1C), 128.9 (d, J = 2.2 Hz, 1C), 123.3 (d, J =
.8 Hz, 1C), 119.9 (d, J = 3.3 Hz, 1C), 115.7 (d, J = 17.0 Hz,
C), 61.3, 42.7, 34.8, 14.2; HRMS (ESI-TOF) Calcd for
3
4.7.15. Methyl 2-(2-oxoindolin-3-yl)acetate (2o). White solid,
1
yield 61%; mp 248.5-251.3 °C; H NMR (400 MHz, CDCl
.88 (br s, 1H), 7.24-7.20 (m, 2H), 7.01 (d, J = 7.6 Hz, 1H), 6.91
(d, J = 8.0 Hz, 1H), 3.82 (dd, J = 4.8, 8.0 Hz, 1H), 3.70 (s, 3H),
.09 (dd, J = 4.4, 16.8 Hz, 1H), 2.84 (ddd, J = 0.8, 8.0, 16.8 Hz,
3
) δ
8
+
C
12
H
12FNNaO
3
[M+Na] : 260.0693; found: 260.0693.
3
1
3
4
.7.9. Ethyl 2-(7-chloro-2-oxoindolin-3-yl)acetate (2i). Light
1H); C NMR (100 MHz, CDCl
128.3, 124.1, 122.5, 109.9, 52.1, 42.3, 34.5; HRMS (ESI-TOF)
Calcd for C11
3
) δ 179.2, 171.6, 141.5, 128.6,
1
yellow solid, yield 64%; mp 158.1-159.9 °C; H NMR (400
MHz, CDCl ) δ 8.74 (br s, 1H), 7.20 (d, J = 8.0 Hz, 1H), 7.13 (d,
J = 7.2 Hz, 1H),6.95 (t, J = 8.0 Hz, 1H), 4.19-4.07 (m, 2H), 3.88
+
3
3
H11NNaO [M+Na] : 228.0631; found: 228.0637.
4.7.16. Propyl 2-(2-oxoindolin-3-yl)acetate (2p). Light yellow
(
(
dd, J = 4.4, 7.6 Hz, 1H), 3.09 (dd, J = 4.4, 17.2 Hz, 1H), 2.85
1
1
3
solid, yield 78%; mp 97.3-98.8 °C; H NMR (400 MHz, CDCl
δ 9.45 (d, J = 15.2Hz, 1H), 7.22-7.18 (m, 2H), 6.99 (t, J = 7.2 Hz,
H), 6.91 (d, J = 7.6 Hz, 1H), 4.08-3.99 (m, 2H), 3.81 (dd, J =
4.8, 7.4 Hz, 1H), 3.09 (dd, J = 4.8, 17.2 Hz, 1H), 2.84 (dd, J =
.0, 17.2 Hz, 1H), 1.63-1.54 (m, 2H), 0.88 (t, J = 7.6 Hz, 3H);
3
)
dd, J = 8.0, 17.2 Hz, 1H), 1.20 (td, J = 1.2, 7.2 Hz, 3H);
) δ 178.2, 170.8, 139.5, 130.2, 128.4,
23.4, 122.5, 115.2, 61.2, 43.4, 34.8, 14.2; HRMS (ESI-TOF)
C
NMR (100 MHz, CDCl
1
3
1
+
3
Calcd for C12H12ClNNaO [M+Na] : 276.0398; found: 276.0395
8
13
4
.7.10. Ethyl 2-(2-oxo-7-(trifluoromethyl)indolin-3-yl)acetate (2j).
C NMR (100 MHz, CDCl
3
) δ 179.8, 171.3, 141.9, 128.9, 128.4,
1
Yellow solid, yield 52%; mp 194.3-195.8 °C; H NMR (400
MHz, CDCl ) δ 8.09 (br s, 1H), 7.43 (t, J = 8.8 Hz, 2H), 7.11 (t, J
7.6 Hz, 1H), 4.20-4.07 (m, 2H), 3.81 (dd, J = 4.4, 7.6 Hz, 1H),
.11 (dd, J = 4.4, 17.2 Hz, 1H), 2.89 (dd, J = 7.6, 17.2 Hz, 1H),
124.1, 122.5, 110.1, 66.7, 42.5, 34.8, 21.9, 10.4; HRMS (ESI-
TOF) Calcd for C13
256.0938.
+
3
3
H15NNaO [M+Na] : 256.0944; found:
=
3
1
1
=
3
1
3
4.7.17. Tert-butyl 2-(2-oxoindolin-3-yl)acetate (2q). Light yellow
solid, yield 65%; mp 146.3-147.8 °C; H NMR (400 MHz,
.19 (t, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl
70.70, 139.0, 130.4, 127.7, 125.2 (q, J = 4.0 Hz, 1C), 124.0 (q, J
270.0 Hz, 1C), 122.5, 112.2 (q, J = 33.0 Hz, 1C), 61.3, 41.4,
4.6, 14.1; HRMS (ESI-TOF) Calcd for NNaO
3
) δ 178.0,
1
CDCl
.8, 7.6 Hz, 1H), 7.00 (t, J = 7.6 Hz, 1H), 6.92 (d, J = 7.6 Hz,
1H), 3.75 (t, J = 5.6 Hz, 1H), 2.98 (dd, J = 4.8, 16.4 Hz, 1H),
3
) δ 9.42 (br s, 1H), 7.23 (d, J = 6.8 Hz, 1H), 7.20 (dd, J =
0
C
13
H
12
F
3
3
+
[
M+Na] : 310.0661; found: 310.0660.
13
2
.82 (dd, J = 7.2, 16.4 Hz, 1H), 1.33 (d, J = 0.8 Hz, 9H);
NMR (100 MHz, CDCl ) δ 180.2, 170.1, 141.9, 129.0, 128.3,
124.1, 122.5, 110.0, 81.5, 42.8, 36.0, 27.9; HRMS (ESI-TOF)
C
4.7.11. Ethyl 2-(6-chloro-2-oxoindolin-3-yl)acetate (2k). Light
3
1
yellow solid, yield 64%; mp 153.7-154.5 °C; H NMR (400
MHz, CDCl ) δ 9.34 (d, J = 9.6 Hz, 1H), 7.14 (d, J = 8.0 Hz,
H), 6.97 (dd, J = 2.0, 8.0 Hz, 1H),6.92 (d, J = 2.0 Hz, 1H), 4.19-
+
3
Calcd for C14
3
H17NNaO [M+Na] : 270.1101; found: 270.1091.
1
4
1
7
1
4.7.18. Ethyl 2-cyano-2-(2-oxoindolin-3-yl)acetate (2s). Light
.09 (m, 2H), 3.75 (dd, J = 4.4, 7.2 Hz, 1H), 3.06 (dd, J = 4.4,
7.2 Hz, 1H), 2.85 (dd, J = 8.0, 17.2 Hz, 1H), 1.21 (td, J = 1.6,
.2 Hz, 3H); C NMR (100 MHz, CDCl
1
brown oil, yield 57%; 57:43 dr; H NMR (400 MHz, CDCl
9.00 (s, 0.85H), 8.99 (s, 1.15H), 7.51 (d, J = 7.6 Hz, 1.15H),
.31-7.28 (m, 2H), 7.21 (d, J = 7.2 Hz, 0.85H), 7.06 (td, J = 2.8,
3
) δ
1
3
3
) δ 179.7, 171.0, 143.0,
7
34.1, 127.2, 125.0, 122.5, 110.8, 61.3, 42.1, 34.7, 14.2;HRMS
+
7.6 Hz, 2H), 6.93 (t, J = 8.4 Hz, 2H), 4.43-4.38 (m, 3H), 4.34 (d,
J = 3.6 Hz, 1H), 4.17 (d, J = 3.6 Hz, 0.85H), 4.15-4.06 (m, 2H),
(
3
ESI-TOF) Calcd for C12H12ClNNaO [M+Na] : 276.0398;
found: 276.0389
3.98 (d, J = 2.8 Hz, 1.15H), 1.38 (t, J = 7.2Hz, 2.56H), 1.09 (t, J
13
4
.7.12. Ethyl 2-(4,7-dichloro-2-oxoindolin-3-yl)acetate (2l).
3
= 7.2 Hz, 3.44H); C NMR (100 MHz, CDCl ) δ 175.6, 164.6,
163.3, 141.9, 141.8, 129.7, 129.6, 124.8, 124.2, 124.1, 124.1,
123.2, 123.0, 115.3, 113.4, 110.7, 110.4, 63.8, 63.3, 45.4, 45.3,
1
White solid, yield 60%; mp 199.3-200.9 °C; H NMR (400 MHz,
CDCl ) δ 8.46 (d, J = 22.4 Hz, 1H), 7.16 (d, J = 8.8 Hz, 1H), 6.92
d, J = 8.8 Hz, 1H), 4.11-3.97 (m, 2H), 3.81 (t, J = 4.8 Hz, 1H),
3
(
38.9, 37.7, 29.7, 14.0, 13.6; HRMS (ESI-TOF) Calcd for
+
3
1
1
1
3
.38 (dd, J = 5.6, 17.2 Hz, 1H), 3.24 (dd, J = 4.0, 17.2 Hz, 1H),
.14 (t, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl
70.2, 141.1, 129.5, 128.8, 126.8, 123.8, 113.7, 61.2, 43.9, 32.6,
4.1; HRMS (ESI-TOF) Calcd for C12
10.0008; found: 310.0006.
C
13
H
12
N
2
NaO
3
[M+Na] : 267.0740; found: 267.0746.
1
3
3
) δ 177.2,
Acknowledgements
+
2 3
H11Cl NNaO [M+Na] :
We are grateful for financial support from National Nature
Science Foundation of China (21262051), The Education
Department of Guizhou Province (Project No. Qian Jiao Ke
2010046); the Organization Department of the Provincial
Committee of Guizhou Province (Project No. TZJF-2010-063);
and the Technological Activities of Certification for the Returned
Oversea Students from the Department of Human Resources and
the Social Security (No. 2011-1).
4
.7.13. Ethyl 2-(1-methyl-2-oxoindolin-3-yl)acetate (2m). Light
2 1
yellow oil (lit. colourless liquid), yield 62%; H NMR (400
MHz, CDCl ) δ 7.29 (d, J = 8.0 Hz,1H), 7.24 (d, J = 7.2 Hz, 1H),
.02 (t, J = 7.6 Hz, 1H),6.83 (d, J = 8.0 Hz, 1H), 4.18-4.06 (m,
H), 3.77 (dd, J = 4.4, 8.0 Hz, 1H), 3.22 (d, J = 1.2 Hz, 3H), 3.07
3
7
2
(
ddd, J = 1.2, 4.4, 16.8 Hz, 1H), 2.78 (ddd, J = 1.2, 8.0, 16.8 Hz,
1
3
1
3
H), 1.19 (td, J = 1.2, 7.2 Hz, 3H); C NMR (100 MHz, CDCl )
δ 176.9, 171.2, 144.4, 128.4, 128.3, 123.9, 122.6, 108.2, 61.0,
1.9, 35.0, 26.4, 14.2; HRMS (ESI-TOF) Calcd for C13
References and notes
4
H15NNaO
3
+
[
M+Na] : 256.0944; found: 256.0935.
1. (a) Kagata, T.; Saito, S.; Shigemori, H.; Ohsaki, A.; Ishiyama, H.;
Kubota, T.; Kobayashi, J. J. Nat. Prod. 2006, 69, 1517−1521; (b) Wang,
K.; Zhou, X.-Y.; Wang, Y.-Y.; Li, M.-M.; Li, Y.-S.; Peng, L.-Y.; Cheng,
4
.7.14. Ethyl 2-(1-acetyl-2-oxoindolin-3-yl)acetate (2n). Light
1
X.; Li, Y.; Wang, Y.-P.; Zhao, Q.-S. J. Nat. Prod. 2011, 74, 12
−15; (c)
yellow oil, yield 41%; H NMR (400 MHz, CDCl
3
) δ 8.23 (d, J =
.0 Hz,1H), 7.32 (t, J = 8.0 Hz, 1H), 7.24 (d, J = 7.2 Hz,
H),7.18 (t, J = 7.2 Hz, 1H), 4.11-4.03 (m, 2H), 3.91 (t, J = 5.6
Tan, S.-J.; Lim, J.-L.; Low, Y.-Y.; Sim, K.-S.; Lim, S.-H.; Kam, T.-S. J.
Nat. Prod. 2014, 77, 2068−2080; (d) Tang, B.-Q.; Wang, W.-J.; Huang,
X.-J.; Li, G.-Q.; Wang, L.; Jiang, R.-W.; Yang, T.-T.; Shi, L.; Zhang, X.-
Q.; Ye, W.-C. J. Nat. Prod. 2014, 77, 1839−1846; (e) Chen, Y.-P.; Lu,
M.-N.; Hao, J.-C.; Li, M.-H.; Hattori, M.; Wang, W. J. Asian Nat. Prod.
Res. 2015, 17, 384−390.
8
1
Hz, 1H), 3.11-3.00 (m, 2H), 2.69 (d, J = 0.4 Hz, 3H), 1.15 (td, J
13
=
0.4, 7.2 Hz, 3H); C NMR (100 MHz, CDCl
3
) δ 177.7, 171.0,
1
70.4, 140.8, 128.8, 127.1, 125.2, 123.2, 116.7, 61.3, 42.7, 35.3,