8120
S. Wang et al. / Tetrahedron 71 (2015) 8117e8122
J¼11.5 Hz, 1H), 3.24 (s, 3H), 3.10e3.01 (m, 1H), 2.85e2.79 (m, 1H),
2.52e2.45 (m, 1H), 2.13e2.05 (m, 1H); 13C NMR (101 MHz, CDCl3)
d
7.35e7.28 (m, 2H), 7.09 (t, J¼7.5 Hz, 2H), 4.63 (h, 7.0 Hz, 1H), 4.53
(d, J¼11.4 Hz, 1H), 4.25 (d, J¼11.4 Hz, 1H), 3.09e3.01 (m, 1H),
2.82e2.77 (m, 1H), 2.52e2.42 (m, 1H), 2.12e2.02 (m, 1H), 1.50 (d,
d
176.0, 170.6, 142.0, 133.1, 132.0, 126.8, 115.9, 110.1, 72.3, 46.2, 28.5,
27.2, 26.6. HRMS (ESI): m/z calcd for C13H12BrNNaO3 [MþNa]þ:
J¼7.0 Hz, 6H); 13C NMR (101 MHz, CDCl3)
d 176.3, 171.1, 141.6, 131.7,
331.9893; found: 331.9898.
128.8, 123.8, 122.7, 110.3, 73.0, 45.7, 44.2, 28.7, 27.3, 19.4, 19.4. HRMS
(ESI): m/z calcd for C15H18NO3 [MþH]þ: 260.1281; found: 260.1281.
4.2.7. 1,7-Dimethyl-40,50-dihydrospiro[indoline-3,30-pyran]-
2,60(20H)-dione (3g). 86% yield, white solid, mp¼125e127 ꢀC; 1H
4.2.14. 1-Phenyl-40,50-dihydrospiro[indoline-3,30-pyran]-2,60(20H)-di-
NMR (400 MHz, CDCl3)
d
7.14e7.09 (m, 2H), 7.01 (t, J¼7.6 Hz, 1H),
one (3n). 75% yield, white solid, mp¼151e153 ꢀC; 1H NMR
4.52 (d, J¼11.6 Hz, 1H), 4.25 (d, J¼11.6 Hz, 1H), 3.54 (s, 3H),
(400 MHz, CDCl3)
d
7.57 (t, J¼7.6 Hz, 2H), 7.51e7.35 (m, 4H), 7.31 (t,
3.16e3.00 (m, 1H), 2.86e2.73 (m, 1H), 2.62 (s, 3H), 2.52e2.37 (m,
J¼7.8 Hz, 1H), 7.17 (t, J¼7.5 Hz, 1H), 6.92 (d, J¼7.9 Hz, 1H), 4.68 (d,
J¼11.4 Hz, 1H), 4.42 (d, J¼11.4 Hz, 1H), 3.16e3.05 (m, 1H), 2.95e2.79
(m, 1H), 2.71e2.57 (m, 1H), 2.32e2.17 (m, 1H); 13C NMR (101 MHz,
1H), 2.16e2.01 (m, 1H); 13C NMR (101 MHz, CDCl3)
d 177.5, 171.1,
140.1, 132.8, 131.9, 123.2, 121.3, 120.3, 73.0, 45.2, 29.8, 29.0, 27.3,
19.0. HRMS (ESI): m/z calcd for C14H15NNaO3 [MþNa]þ: 268.0944;
found: 268.0946.
CDCl3)
d 176.1, 170.9, 142.9, 133.8, 131.0, 129.8, 129.0, 128.5, 126.4,
123.8, 123.7, 110.0, 72.9, 46.2, 29.1, 27.3. HRMS (ESI): m/z calcd for
C
18H15NNaO3 [MþNa]þ: 316.0944; found: 316.0944.
4.2.8. 7-Bromo-1-methyl-40,50-dihydrospiro[indoline-3,30-pyran]-
2,60(20H)-dione (3h). 82% yield, white solid, mp¼69e71 ꢀC; 1H NMR
4.2.15. 1-Benzyl-40,50-dihydrospiro[indoline-3,30-pyran]-2,60(20H)-di-
(400 MHz, CDCl3)
d
7.48 (d, J¼8.2 Hz,1H), 7.22 (d, J¼7.0 Hz,1H), 6.97 (t,
one (3o). 94% yield, light yellow solid, mp¼42e44 ꢀC; 1H NMR
J¼7.8 Hz, 1H), 4.53 (d, J¼11.5 Hz, 1H), 4.24 (d, J¼11.5 Hz, 1H), 3.64 (s,
(400 MHz, CDCl3)
d
7.40e7.21 (m, 7H), 7.09 (t, J¼7.5 Hz, 1H), 6.84 (d,
3H), 3.13e2.98 (m, 1H), 2.88e2.72 (m, 1H), 2.58e2.39 (m, 1H),
J¼7.8 Hz, 1H), 4.94 (s, 2H), 4.61 (d, J¼11.4 Hz, 1H), 4.33 (d, J¼11.4 Hz,
1H), 3.16e2.99 (m, 1H), 2.89e2.80 (m, 1H), 2.59e2.50 (m, 1H),
2.16e2.01 (m, 1H); 13C NMR (101 MHz, CDCl3)
d 177.1, 170.8, 140.3,
134.7,134.4,124.4,122.5,103.0, 72.5, 45.7, 30.2, 29.0, 27.3. HRMS (ESI):
2.26e2.08 (m, 1H); 13C NMR (101 MHz, CDCl3)
d 176.8, 170.9, 142.0,
m/z calcd for C13H12BrNNaO3 [MþNa]þ: 331.9893; found: 331.9898.
135.4, 131.0, 129.0, 129.0, 127.9, 127.3, 123.6, 123.3, 109.7, 72.8, 46.0,
43.9, 28.8, 27.3. HRMS (ESI): m/z calcd for C19H17NNaO3 [MþNa]þ:
330.1101; found: 330.1104.
4.2.9. 7-Methoxy-1-methyl-40,50-dihydrospiro[indoline-3,30-pyran]-
2,60(20H)-dione (3i). 83% yield, white solid, mp¼111e113 ꢀC; 1H NMR
(400 MHz, CDCl3)
d
7.11e7.02 (t, J¼8.2 Hz, 1H), 6.95e6.90 (m, 2H),
4.2.16. Ethyl
3-(1-benzyl-3-(hydroxymethyl)-2-oxoindolin-3-yl)
7.41e7.15
4.53(d, J¼11.4Hz,1H), 4.24 (d, J¼11.4Hz,1H), 3.89 (s, 3H), 3.52(s, 3H),
propanoate (8o). Yellow oil, 1H NMR (400 MHz, CDCl3)
d
3.13e2.98 (m, 1H), 2.83e2.75 (m, 1H), 2.56e2.38 (m, 1H), 2.17e1.99
(m, 7H), 7.07 (t, J¼7.5 Hz, 1H), 6.76 (d, J¼7.8 Hz, 1H), 5.03e4.87 (m,
2H), 4.06e3.85 (m, 4H), 2.45e2.37 (m, 1H), 2.27e2.12 (m, 2H),
2.01e1.92 (m, 1H), 1.18 (t, J¼7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3)
(m, 1H); 13C NMR (101 MHz, CDCl3)
d 176.8, 171.1, 145.6, 132.8, 130.8,
123.9, 116.0, 112.8, 72.9, 56.0, 46.0, 29.8, 28.8, 27.3. HRMS (ESI): m/z
calcd for C14H15NNaO4 [MþNa]þ: 284.0893; found: 284.0896.
d
178.6, 172.7, 143.4, 135.6, 129.1, 128.8, 128.6, 127.7, 127.2, 123.4,
122.9, 109.4, 67.2, 60.5, 54.0, 43.8, 29.2, 27.9, 14.1.
4.2.10. 5,7-Dimethoxy-1-methyl-40,50-dihydrospiro[indoline-3,30-py-
ran]-2,60(20H)-dione (3j). 78% yield, white solid, mp¼45e47 ꢀC; 1H
4.2.17. 1-Methyl-20-propyl-40,50-dihydrospiro[indoline-3,30-pyran]-
NMR (400 MHz, CDCl3)
d
6.50 (d, J¼2.2 Hz, 1H), 6.47 (d, J¼2.2 Hz,
2,60(20H)-dione (3p). 74% yield, d.r.¼1.1:1. Major; Colorless oil, 1H
1H), 4.53 (d, J¼11.5 Hz, 1H), 4.24 (d, J¼11.5 Hz, 1H), 3.87 (s, 3H), 3.80
(s, 3H), 3.47 (s, 3H), 3.11e3.01 (m,1H), 2.83e2.74 (m,1H), 2.52e2.40
NMR (400 MHz, CDCl3)
d
7.36 (dt, J¼7.6, 1.2 Hz, 1H), 7.21e7.04 (m,
2H), 6.90 (d, J¼7.8 Hz, 1H), 4.56 (dd, J¼10.4, 1.8 Hz, 1H), 3.30e3.11
(m, 4H), 2.79e2.70 (m, 1H), 2.39e2.29 (m, 1H), 2.15e2.03 (m, 1H),
1.59e1.44 (m, 2H), 0.96e0.84 (m, 2H), 0.76 (t, J¼7.3 Hz, 3H); 13C
(m,1H), 2.12e2.02 (m,1H); 13C NMR (101 MHz, CDCl3)
d 176.6,171.4,
157.2, 146.3, 133.5, 124.2, 100.9, 100.1, 72.8, 55.9, 55.9, 46.5, 29.7,
28.9, 27.4. HRMS (ESI): m/z calcd for C15H18NO5 [MþH]þ: 292.1180;
found: 292.1182.
NMR (101 MHz, CDCl3)
d 176.1, 170.3, 143.6, 129.9, 129.1, 123.0,
122.0, 108.6, 83.1, 48.2, 32.4, 29.1, 26.4, 26.1, 18.8, 13.4. HRMS (ESI):
m/z calcd for C16H20NO3 [MþH]þ: 274.1438; found: 274.1440. Mi-
4.2.11. 4,5,50,60-Tetrahydrospiro[pyran-3,10-pyrrolo[3,2,1-ij]quino-
nor; Colorless oil, 1H NMR (400 MHz, CDCl3)
d
7.36 (dt, J¼7.6,
line]-20,6(2H,40H)-dione
(3k). 86%
yield,
white
solid,
1.2 Hz, 1H), 7.22 (d, J¼7.6 Hz, 1H), 7.10 (t, J¼7.6 Hz, 1H), 6.93 (d,
J¼7.6 Hz, 1H), 4.65 (dd, J¼10.0, 2.4 Hz, 1H), 3.25 (s, 3H),3.02e2.92
(m, 1H), 2.82e2.74 (m, 1H), 2.64e2.49 (m, 1H), 1.94e1.87 (m, 1H),
1.35e1.28 (m, 1H), 1.22e1.07 (m, 1H), 1.00e0.84 (m, 2H), 0.78 (t,
mp¼147e149 ꢀC; 1H NMR (400 MHz, CDCl3)
d 7.19e7.08 (m, 2H),
7.01 (t, J¼7.6 Hz, 1H), 4.59 (d, J¼11.3 Hz, 1H), 4.27 (d, J¼11.3 Hz, 1H),
3.76 (t, J¼5.8 Hz, 2H), 3.13e2.95 (m, 1H), 2.87e2.79 (m, 3H),
2.56e2.49 (m, 1H), 2.15e1.98 (m, 3H); 13C NMR (101 MHz, CDCl3)
J¼7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 177.0, 171.8, 143.3,
d
175.2, 170.8, 138.7, 129.7, 127.9, 122.7, 121.4, 120.8, 72.9, 47.4, 39.1,
129.5, 128.8, 124.5, 123.2, 108.6, 82.4, 50.4, 32.7, 29.7, 27.2, 26.4,
18.6, 13.6.
28.3, 27.3, 24.5, 21.0. HRMS (ESI): m/z calcd for C15H16NO3 [MþH]þ:
258.1125; found: 258.1126.
4.2.18. 20-Isopropyl-1-methyl-40,50-dihydrospiro[indoline-3,30-py-
4.2.12. 1-Methyl-40,50-dihydrospiro[benzo[g]indole-3,30-pyran]-
ran]-2,60(20H)-dione (3q). 68% yield, d.r.¼1.2:1. Major, white solid,
2,60(1H,20H)-dione (3l). 63% yield, yellow oil; 1H NMR (400 MHz,
mp¼103e106 ꢀC; 1H NMR (400 MHz, CDCl3)
7.35 (td, J¼7.7, 1.6 Hz,
d
CDCl3)
d
7.84 (dd, J¼8.0, 1.2 Hz 1H), 7.68e7.44 (m, 4H), 7.07 (d,
1H), 7.20e7.07 (m, 2H), 6.90 (d, J¼7.7 Hz, 1H), 4.54 (d, J¼3.7 Hz, 1H),
3.33e3.13 (m, 4H), 2.89e2.67 (m, 1H), 2.41e2.21 (m, 1H), 2.14e1.91
(m, 1H), 1.76e1.52 (m, 1H), 0.85 (d, J¼6.7 Hz, 3H), 0.77 (d, J¼7.0 Hz,
J¼7.8 Hz, 1H), 4.88 (d, J¼11.6 Hz, 1H), 4.43 (d, J¼11.6 Hz, 1H), 3.59 (s,
3H), 3.15e2.99 (m, 1H), 2.98e2.83 (m, 1H), 2.75e2.70 (m, 1H),
2.37e2.20 (m, 1H); 13C NMR (101 MHz, CDCl3)
d
172.4, 170.4, 136.2,
3H); 13C NMR (101 MHz, CDCl3)
d 176.4, 170.6, 143.3, 130.2, 129.0,
135.3, 133.4, 127.4, 127.3, 126.7, 123.6, 123.1, 118.8, 109.4, 75.4, 45.6,
34.0, 30.2, 28.8. HRMS (ESI): m/z calcd for C17H16NO3 [MþH]þ:
282.1125; found: 282.1128.
123.0, 122.0, 108.6, 87.8, 47.5, 30.8, 29.8, 26.3, 26.2, 21.1, 16.6. HRMS
(ESI): m/z calcd for C16H20NO3 [MþH]þ: 274.1438; found: 274.1440.
Minor, white solid, mp¼108e110 ꢀC; 1H NMR (400 MHz, CDCl3)
d
7.37 (t, J¼8.2 Hz, 1H), 7.27 (d, J¼7.5 Hz, 1H), 7.11 (t, J¼7.4 Hz, 1H),
4.2.13. 1,3-Dimethyl-3-(3-(naphthalen-2-yl)-3-oxopropyl)indolin-2-
6.94 (d, J¼7.8 Hz, 1H), 4.45 (d, J¼8.1 Hz, 1H), 3.25 (s, 3H), 3.01e2.93
(m, 1H), 2.80e2.68 (m, 1H), 2.51e2.44 (m, 1H), 1.90e1.77 (m, 1H),
one (3m). 90% yield, yellow oil; 1H NMR (400 MHz, CDCl3)