H. Jin et al. / Tetrahedron 67 (2011) 1178e1182
1181
127.7, 126.1, 124.5, 124.2, 123.8, 110.4, 42.5, 36.4, 21.4; EIMS m/z 300
(Mþ); HRMS (EI) calcd for C16H16N2O2S ([M]þ), 300.0932; found,
300.0945.
124.1, 110.2, 36.3, 21.5; EIMS m/z 396 (Mþ); HRMS (EI) calcd for
C21H17ClN2O2S ([M]þ), 396.0699; found, 396.0715.
4.1.16. 1-(m-Nitrophenyl)-2-(p-toluenesulfonylimino)indoline
4.1.9. 1-(p-Chlorophenyl)-2-(butanesulfonylimino)indoline
(4p). White solid; mp 151e152 ꢀC; 1H NMR (CDCl3, 500 MHz)
(4i). White solid; mp 126e127 ꢀC; 1H NMR (CDCl3, 500 MHz)
d
8.31e8.28 (m, 2H), 7.80e7.70 (m, 4H), 7.43 (d, J¼7.5 Hz, 1H),
7.29e7.24 (m, 3H), 7.21e7.17 (m, 1H), 6.79 (d, J¼8.0 Hz, 1H), 4.48 (s,
2H), 2.40 (s, 3H), 13C NMR (CDCl3, 125 MHz)
169.4, 148.9, 143.3,
d
7.54e7.51 (m, 2H), 7.38 (d, J¼7.5 Hz, 1H), 7.36e7.34 (m, 2H),
7.27e7.21 (m, 1H), 7.16e7.14 (m, 1H), 6.75 (d, J¼7.5 Hz, 1H), 4.44 (s,
2H), 3.03 (t, J¼8.0 Hz, 2H), 1.80e1.73 (m, 2H), 1.44e1.36 (m, 2H),
d
143.2, 138.7, 135.5, 133.2, 130.6, 129.4, 128.2, 126.6, 125.9, 125.0,
124.5, 123.6, 122.6, 109.9, 36.3, 21.5; EIMS m/z 407 (Mþ); HRMS (EI)
calcd for C21H17N3O4S ([M]þ), 407.0940; found, 407.0977.
0.90 (t, J¼8.0 Hz, 3H), 13C NMR (CDCl3, 125 MHz)
d 169.4, 144.2,
134.6, 133.0, 129.9, 128.6, 128.0, 126.0, 124.7, 124.0, 110.0, 54.1, 36.3,
25.5, 21.4, 13.6; EIMS m/z 362 (Mþ); HRMS (EI) calcd for
C18H19ClN2O2S ([M]þ), 362.0856; found, 362.0868.
4.1.17. 1-(p-Nitrophenyl)-2-(p-toluenesulfonylimino)indoline
(4q). White solid; mp 188e190 ꢀC; 1H NMR (CDCl3, 500 MHz)
4.1.10. 1-(p-Chlorophenyl)-2-(methanesulfonylimino)indoline
d
8.37 (q, J¼7.0 Hz, 2H), 7.77 (d, J¼8.5 Hz, 2H), 7.61 (q, J¼7.0 Hz, 2H),
(4j). White solid; mp 184e185 ꢀC; 1H NMR (CDCl3, 500 MHz)
7.43 (d, J¼7.5 Hz, 1H), 7.28e7.24 (m, 2H), 7.21e7.17 (m, 2H), 6.82 (d,
d
7.55e7.51 (m, 2H), 7.40e7.34 (m, 3H), 7.27e7.22 (m, 1H),
J¼8.0 Hz, 1H), 4.50 (s, 2H), 2.41 (s, 3H), 13C NMR (CDCl3, 125 MHz)
7.17e7.13 (m, 1H), 6.75 (d, J¼7.5 Hz, 1H), 4.44 (s, 2H), 3.00(s, 3H),
d
169.1, 147.2, 143.2, 140.0, 138.7, 130.0, 129.4, 128.2, 128.0, 126.6,
13C NMR (CDCl3, 125 MHz)
d
169.3, 144.3, 134.7, 132.9, 130.1, 128.7,
125.0, 124.9,124.6, 110.0, 36.4, 21.5; EIMS m/z 407 (Mþ); HRMS (ESI)
calcd for C21H18N3O4S ([MþH]þ), 408.1018; found, 408.1005.
128.1, 126.0, 124.8, 124.1, 110.1, 42.5, 36.3; EIMS m/z 320 (Mþ);
HRMS (EI) calcd for C15H13ClN2O2S ([M]þ), 320.0386; found,
320.0402.
4.1.18. 1-Benzyl-2-(p-toluenesulfonylimino)indoline (4r). White solid;
mp 128e130 ꢀC; 1H NMR (CDCl3, 500 MHz)
d
7.85 (d, J¼8.0 Hz, 2H),
4.1.11. 1-(p-Methoxyphenyl)-2-(p-toluenesulfonylimino)indoline
7.32 (d, J¼7.0 Hz, 1H), 7.28e7.19 (m, 8H), 7.10e7.06 (m, 1H), 6.89 (d,
(4k). White solid; mp 184e185 ꢀC; 1H NMR (CDCl3, 500 MHz)
J¼8.0 Hz, 1H), 5.07 (s, 2H), 4.30 (s, 2H), 2.41 (s, 3H), 13C NMR (CDCl3,
d
7.79 (d, J¼8.0 Hz, 2H), 7.37 (d, J¼8.0 Hz, 1H), 7.27e7.19 (m, 5H),
125 MHz) d 169.7, 143.1, 142.7, 139.4, 134.7, 129.3, 128.8, 128.0, 127.9,
7.14e7.12 (m, 1H), 7.01 (q, J¼7.0 Hz, 2H), 6.73 (d, J¼8.0 Hz, 1H),
126.6, 124.5, 123.7, 110.0, 45.7, 36.2, 21.5; EIMS m/z 376 (Mþ); HRMS
(ESI) calcd for C22H21N2O2S ([MþH]þ), 377.1324; found, 377.1307.
4.40 (s, 2H), 3.86 (s, 3H), 2.39 (s, 3H), 13C NMR (CDCl3, 125 MHz)
d
170.0, 159.7, 145.0, 142.7, 139.4, 129.3, 128.3, 128.0, 127.0, 126.6,
126.1, 124.6, 123.9, 115.0, 110.5, 55.6, 36.4, 21.5; EIMS m/z 392
(Mþ); HRMS (EI) calcd for C22H20N2O3S ([M]þ), 392.1195; found,
392.1209.
4.1.19. 1-iso-Propyl-2-(p-toluenesulfonylimino)indoline (4s). White
solid; mp 116e117 ꢀC; 1H NMR (CDCl3, 500 MHz)
d
7.87 (t, J¼8.5 Hz,
2H), 7.33e7.25 (m, 4H), 7.15 (d, J¼8.0 Hz, 1H), 7.11e7.07 (m, 1H),
5.00e4.97 (m, 1H), 4.18 (s, 2H), 2.41 (s, 3H), 1.48 (d, J¼7.0 Hz, 6H),
4.1.12. 1-(3,5-Dimethylphenyl)-2-(p-toluenesulfonylimino)indoline
13C NMR (CDCl3, 125 MHz)
d 169.3, 142.6, 142.4, 139.6, 129.3, 127.7,
(4l). White solid; mp 158e159 ꢀC; 1H NMR (CDCl3, 500 MHz)
d
7.80
127.0, 126.6, 124.6, 123.2, 111.3, 67.1, 45.9, 36.2, 21.5, 18.9; EIMS m/z
328 (Mþ); HRMS (ESI) calcd for C18H23N2O2S ([MþH]þ), 329.1324;
found, 329.1323.
(d, J¼8.0 Hz, 2H), 7.36 (d, J¼7.5 Hz, 1H), 7.26e7.18 (m, 3H), 7.13e7.10
(m, 1H), 7.06 (s, 1H), 6.93 (s, 2H), 6.74 (d, J¼8.0 Hz, 1H), 4.39 (s, 2H),
2.39 (s, 3H), 2.35 (s, 6H), 13C NMR (CDCl3, 125 MHz)
d 169.7, 144.8,
142.6, 139.5, 139.4, 134.2, 130.6, 129.2, 127.9, 126.6, 124.6, 124.5,
123.8,110.6, 36.4, 21.5, 21.3; EIMS m/z 390 (Mþ); HRMS (EI) calcd for
C23H22N2O2S ([M]þ), 390.1402; found, 390.1416.
4.1.20. 1-(m-Tolyl)-2-(p-toluenesulfonylimino)-5-methoxyindo-line
(4t). White solid; mp 182e184 ꢀC; 1H NMR (CDCl3, 500 MHz)
d 7.79
(d, J¼8.5 Hz, 2H), 7.38 (t, J¼7.5 Hz, 1H), 7.26e7.21 (m, 3H), 7.14e7.11
(m, 2H), 6.96 (t, J¼1.0 Hz, 1H), 6.74e6.71 (m, 1H), 6.66 (d, J¼9.0 Hz,
1H), 4.37 (s, 2H), 3.79 (s, 3H), 2.39 (s, 3H), 2.38 (s, 3H), 13C NMR
4.1.13. 1-Phenyl-2-(p-toluenesulfonylimino)indoline (4m). White solid;
1
mp 160e161 ꢀC; H NMR (CDCl3, 500 MHz)
d
7.78 (d, J¼8.0 Hz, 2H),
(CDCl3, 125 MHz) d 169.1, 156.9, 142.5, 139.6, 139.5, 138.2, 134.4,
7.45e7.43 (m, 1H), 7.39e7.33 (m, 3H), 7.26e7.19 (m, 3H), 7.15e7.11 (m,
129.5, 129.3, 129.2, 127.4, 126.5, 123.9, 112.7, 111.2, 110.9, 55.8, 36.6,
21.4, 21.3; EIMS m/z 406 (Mþ); HRMS (ESI) calcd for C23H23N2O3S
([MþH]þ), 407.1429; found, 407.1427.
1H), 6.75 (d, J¼8.0 Hz, 1H), 4.43 (s, 2H), 2.38 (s, 3H), 13C NMR (CDCl3,
125 MHz)
d 169.6, 144.6, 142.6, 139.3, 134.4, 129.6, 129.2, 128.8, 127.9,
127.1, 126.5, 126.1, 124.6, 123.9, 110.4, 36.4, 21.5; EIMS m/z 362 (Mþ);
HRMS (ESI) calcd for C21H19N2O2S ([MþH]þ), 363.1167; found,
363.1166.
4.1.21. -(m-Tolyl)-2-(p-toluenesulfonylimino)-5-chloroindoline
(4u). White solid; mp 152e154 ꢀC; 1H NMR (CDCl3, 500 MHz)
d
7.77 (d, J¼8.5 Hz, 2H), 7.38 (t, J¼8.0 Hz, 1H), 7.34 (s, 1H), 7.27e7.23
(m, 3H), 7.17 (q, J¼8.5 Hz, 1H), 7.11e7.09 (m, 2H), 6.66 (d, J¼8.5 Hz,
1H), 4.40 (s, 2H), 2.38 (s, 6H), 13C NMR (CDCl3, 125 MHz)
169.0,
4.1.14. 1-(m-Chlorophenyl)-2-(p-toluenesulfonylimino)indoline
(4n). White solid; mp 118e119 ꢀC; 1H NMR (CDCl3, 500 MHz)
d
7.79
d
(d, J¼8.0 Hz, 2H), 7.48e7.36 (m, 4H), 7.29e7.22 (m, 4H), 7.17e7.13
143.2, 142.7, 139.8, 133.9, 129.8, 129.5, 129.2, 127.9, 127.7, 127.4,
126.5, 124.8, 123.9, 111.3, 36.2, 21.3; EIMS m/z 410 (Mþ); HRMS (ESI)
calcd for C22H20ClN2O2S ([MþH]þ), 411.0934; found, 411.0931.
(m, 1H), 6.77 (d, J¼8.0 Hz, 1H), 4.43 (s, 2H), 2.40 (s, 3H), 13C NMR
(CDCl3, 125 MHz)
d 169.5, 144.0, 142.9, 139.1, 135.5, 135.2, 130.7,
129.4, 129.2, 128.1, 127.5, 126.6, 126.0, 125.5, 124.8, 124.2,110.3, 36.4,
21.6; EIMS m/z 396 (Mþ); HRMS (EI) calcd for C21H17ClN2O2S ([M]þ),
396.0699; found, 396.0710.
4.2. Procedure for transformation of 2-iminoindoline 4a to
oxindole 5a
4.1.15. 1-(p-Chlorophenyl)-2-(p-toluenesulfonylimino)indoline
A solution of 4a (188 mg, 0.5 mmol) in concentrated HCl (20 mL)
was refluxed for 12 h. The reaction mixture was diluted with CH2Cl2
(20 mL). The organic layer was washed with water, dried over an-
hydrous Na2SO4, and concentrated in vacuo. The residue was puri-
fied by column chromatography on silica gel with petroleum ether
and ethylacetate(6:1) to provide pure 5a as awhite solid (50% yield).
(4o). White solid; mp 185e186 ꢀC; 1H NMR (CDCl3, 500 MHz)
d 7.78
(d, J¼8.0 Hz, 2H), 7.48 (q, J¼6.5 Hz, 2H), 7.31e7.29 (m, 2H),
7.27e7.22 (m, 3H), 7.16e7.14 (m, 1H), 6.75 (d, J¼8.0 Hz, 1H), 4.43 (s,
2H), 2.40 (s, 3H), 13C NMR (CDCl3, 125 MHz)
d 169.5, 144.1, 142.8,
139.0, 134.6, 132.8, 129.9, 129.3, 128.5, 128.0, 126.6, 126.0, 124.7,