7
125.0, 126.0, 127.1, 127.6, 127.9, 128.6, 129.5, 131.1, 135.3,
141.8, 142.6, 143.8; MS (EI) m/z 349 (M+), 194, 165, 152, 139,
116, 91, 77, 65, 51.
7.43 (d, J = 8.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 21.4,
ACCEPTED MANUSCRIPT
37.7, 38.1, 65.1, 114.1, 123.0, 123.8, 125.3, 126.8, 128.1, 128.7,
128.8, 130.2, 138.5, 141.8, 142.2; MS (EI) m/z 287 (M+), 208,
193, 178, 165, 152, 130, 116, 103, 91, 77, 65, 51; HRMS (EI)
[M+Na]+ m/z calcd for C16H17NNaO2S 310.0872, found
310.0870.
4.3.2. N-Bs-2-Phenylindoline
99%, a white solid (EtOAc : n-Hexane = 1:4), mp 115-116 °C;
1H NMR (CDCl3, 400 MHz) δ 2.83 (dd, J = 2.8, 16.0 Hz, 1H),
3.22 (dd, J = 10.2, 16.2 Hz, 1H), 5.29 (dd, J = 2.6, 10.2 Hz, 1H),
6.99-7.00 (m, 2H), 7.17-7.24 (m, 6H), 7.31 (t, J = 7.8 Hz, 2H),
7.45 (t, J = 7.4 Hz, 1H), 7.60 (d, J = 7.2 Hz, 2H), 7.67 (d, J = 8.0
Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 37.8, 64.8, 116.4, 124.6,
125.1, 126.0, 127.0, 127.7, 127.9, 128.6, 128.9, 131.1, 132.9,
138.2, 141.7, 142.4; MS (EI) m/z 335 (M+), 194, 165, 152, 141,
116, 91, 77, 65, 51.
4.3.8. N-Ms-2-(o-Tolyl)indoline (4e)
100%, a white solid (EtOAc : n-Hexane = 1:4), mp 171-172
°C; 1H NMR (CDCl3, 400 MHz) δ 2.39 (s, 3H), 2.77 (s, 3H), 2.88
(dd, J = 3.6, 16.0 Hz, 1H), 3.78 (dd, J = 10.4, 16.0 Hz, 1H), 5.60
(dd, J = 3.8, 10.2 Hz, 1H), 7.03 (t, J = 7.4 Hz, 1H), 7.06-7.14 (m,
4H), 7.21-7.26 (m, 2H), 7.47 (d, J = 8.0 Hz, 1H); 13C NMR
(CDCl3, 100 MHz) δ 19.3, 37.7, 37.8, 61.8, 114.2, 124.0, 125.1,
125.6, 126.5, 127.6, 128.1, 129.9, 130.7, 133.9, 141.0, 142.0; MS
(EI) m/z 287 (M+), 208, 193, 178, 165, 152, 130, 116, 103, 91,
77, 65, 51; HRMS (EI) [M+Na]+ m/z calcd for C16H17NNaO2S
310.0872, found 310.0871.
4.3.3. N-Ns-2-Phenylindoline
99%, a white solid (EtOAc : n-Hexane = 1:4), mp 193-194 °C;
1H NMR (CDCl3, 400 MHz) δ 2.92 (dd, J = 2.0, 16.4 Hz, 1H),
3.35 (dd, J = 10.2, 16.2 Hz, 1H), 5.35 (dd, J = 2.2, 9.8 Hz, 1H),
7.04 (t, J = 7.8 Hz, 1H), 7.06 (t, J = 7.2 Hz, 1H), 7.14-7.26 (m,
6H), 7.64 (d, J = 8.4 Hz, 1H), 7.72 (d, J = 8.4 Hz, 2H), 8.11 (d, J
= 8.4 Hz, 2H); 13C NMR (CDCl3, 100 MHz) δ 37.8, 65.2, 115.5,
124.0, 125.0, 125.5, 126.1, 128.07, 128.09, 128.2, 128.7, 130.8,
140.9, 141.6, 144.1, 150.0; MS (EI) m/z 380 (M+), 194, 165, 152,
139, 122, 116, 91, 76, 65, 51.
4.3.9. N-Ms-2-(4-Chlorophenyl)indoline (4f)
86%, a white solid (EtOAc : n-Hexane = 1:4), mp 131-132 °C;
1H NMR (CDCl3, 400 MHz) δ 2.74 (s, 3H), 3.05 (dd, J = 3.2,
16.4 Hz, 1H), 3.79 (dd, J = 10.4, 16.4 Hz, 1H), 5.38 (dd, J = 3.4,
10.2 Hz, 1H), 7.09 (t, J = 7.4 Hz, 1H), 7.22 (d, J = 7.2 Hz, 1H),
7.24-7.30 (m, 5H), 7.44 (d, J = 7.6 Hz, 1H); 13C NMR (CDCl3,
100 MHz) δ 37.5, 38.0, 64.4, 114.3, 124.2, 125.4, 127.5, 128.3,
129.0, 129.7, 133.8, 140.9, 141.5; MS (EI) m/z 307 (M+), 228,
193, 165, 137, 117, 102, 96, 91, 82, 75, 65, 51; HRMS (EI)
[M+Na]+ m/z calcd for C15H14ClNNaO2S 330.0326, found
330.0328.
4.3.4. N-Ms-2-Phenylindoline (4a)
99% (80 °C for 24 h), 98% (120 °C for 6 h), a white solid
(EtOAc : n-Hexane = 1:4), mp 187-188 °C; 1H NMR (CDCl3,
400 MHz) δ 2.67 (s, 3H), 3.12 (dd, J = 2.4, 16.4 Hz, 1H), 3.79
(dd, J = 10.6, 16.2 Hz, 1H), 5.42 (dd, J = 3.2, 10.0 Hz, 1H), 7.07
(t, J = 7.4 Hz, 1H), 7.22 (d, J = 8.0 Hz, 1H), 7.25- 7.33 (m, 6H),
7.43 (d, J = 8.0 Hz, 1H);13C NMR (CDCl3, 100 MHz) δ 37.8,
38.0, 65.1, 114.0, 123.8, 125.4, 126.2, 128.12, 128.13, 128.8,
130.1, 141.7, 142.1; MS (EI) m/z 273 (M+), 194, 165, 152, 139,
116, 91, 77, 65, 51; HRMS (EI) [M+Na]+ m/z calcd for
C15H15NNaO2S 296.0716, found 296.0714.
4.3.10. N-Ms-2-(Naphthalen-1-yl)indoline (4h)
92%, a white solid (EtOAc : n-Hexane = 1:3), mp 145-146 °C;
1H NMR (CDCl3, 400 MHz) δ 2.93 (s, 3H), 3.07 (dd, J = 3.4,
16.2 Hz, 1H), 4.01 (dd, J = 10.6, 16.2 Hz, 1H), 6.17 (dd, J = 3.6,
10.4 Hz, 1H), 7.09 (t, J = 7.2 Hz, 1H), 7.15 (d, J = 7.2 Hz, 1H),
7.31 (t, J = 7.6 Hz, 1H), 7.41 (t, J = 7.8 Hz, 1H), 7.52 (t, J = 7.4
Hz, 1H), 7.56 (t, J = 7.6 Hz, 1H), 7.63 (d, J = 7.2 Hz, 1H), 7.65
(d, J = 8.0 Hz, 1H), 7.78 (d, J = 7.6 Hz, 1H), 7.90 (d, J = 7.6 Hz,
1H), 7.96 (d, J = 8.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ
37.4, 38.4, 62.5, 115.2, 122.8, 123.1, 124.5, 125.5, 125.7, 126.3,
128.21, 128.24, 129.2, 129.5, 130.4, 134.1, 137.8, 141.8 (1
carbon is missing due to overlapping); MS (EI) m/z 323 (M+),
244, 228, 215, 202, 189, 166, 153, 128, 121, 114, 91, 77, 65, 51;
HRMS (EI) [M+Na]+ m/z calcd for C19H17NNaO2S 346.0872,
found 346.0869.
4.3.5. N-Ms-2-(4-Methoxyphenyl)indoline (4b)
99% (1 mol% Bi(OTf)3 for 6 h), 86% (0.5 mol% Bi(OTf)3 for
24 h), a white solid (EtOAc : n-Hexane = 1:2), mp 117-118 °C;
1H NMR (CDCl3, 400 MHz) δ 2.62 (s, 3H), 3.10 (dd, J = 2.6,
16.2 Hz, 1H), 3.76 (dd, J = 10.4, 16.0 Hz, 1H), 3.78 (s, 3H), 5.39
(dd, J = 3.2, 10.0 Hz, 1H), 6.83 (d, J = 9.2 Hz, 2H), 7.06 (t, J =
7.4 Hz, 1H), 7.22-7.26 (m, 4H), 7.39 (d, J = 8.0 Hz, 1H); 13C
NMR (CDCl3, 100 MHz) δ 37.88, 37.93, 55.2, 64.7, 113.8,
114.1, 123.6, 125.3, 127.6, 128.1, 130.2, 134.1, 141.6, 159.4; MS
(EI) m/z 303 (M+), 224, 209, 193, 180, 165, 152, 133, 116, 91,
77, 65, 51; HRMS (EI) [M+Na]+ m/z calcd for C16H17NNaO3S
326.0821, found 326.0821.
4.3.11. N-Ms-2-(Thiophen-3-yl)indoline (4i)
92%, a white solid (EtOAc : n-Hexane = 1:3), mp 140-141 °C;
1H NMR (CDCl3, 400 MHz) δ 2.54 (s, 3H), 3.10 (d, J = 16.4 Hz,
1H), 3.68 (dd, J = 9.6, 16.0 Hz, 1H), 5.52 (d, J = 9.6 Hz, 1H),
6.91 (d, J = 5.2 Hz, 1H), 7.04 (t, J = 7.4 Hz, 1H), 7.19-7.26 (m,
4H), 7.33 (d, J = 8.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ
36.9, 37.7, 61.0, 114.0, 122.9, 123.7, 125.4, 125.5, 126.8, 128.2,
130.2, 141.1, 142.0; MS (EI) m/z 279 (M+), 200, 167, 154, 129,
116, 91, 77, 65, 51; HRMS (EI) [M+Na]+ m/z calcd for
C13H13NNaO2S2 302.0280, found 302.0281
4.3.6. N-Ms-2-(p-Tolyl)indoline (4c)
99%, a white solid (EtOAc : n-Hexane = 1:4), mp 96-97 °C;
1H NMR (CDCl3, 400 MHz) δ 2.32 (s, 3H), 2.65 (s, 3H), 3.10
(dd, J = 3.0, 16.2 Hz, 1H), 3.77 (dd, J = 10.0, 16.4 Hz, 1H), 5.39
(dd, J = 3.0, 10.2 Hz, 1H), 7.06 (t, J = 7.4 Hz, 1H), 7.11 (d, J =
7.6 Hz, 2H), 7.20-7.24 (m, 4H), 7.41 (d, J = 7.6 Hz, 1H); 13C
NMR (CDCl3, 100 MHz) δ 21.1, 37.8, 38.0, 64.9, 113.9, 123.7,
125.3, 126.2, 128.1, 129.4, 130.2, 137.9, 139.1, 141.7; MS (EI)
m/z 287 (M+), 208, 193, 178, 165, 152, 139, 128, 117, 103, 90,
77, 65, 51; HRMS (EI) [M+Na]+ m/z calcd for C16H17NNaO2S
310.0872, found 310.0874.
4.3.12. N-Ms-5-Methoxy-2-(o-tolyl)indoline (4j)
44%, a beige solid (EtOAc : n-Hexane = 1:4), mp 194-195 °C;
1H NMR (CDCl3, 400 MHz) δ 2.41 (s, 3H), 2.80 (s, 3H), 2.86
(dd, J = 3.6, 16.0 Hz, 1H), 3.78 (s, 3H), 3.79 (dd, J = 10.0, 16.0
Hz, 1H), 5.59 (dd, J = 3.4, 10.2 Hz, 1H), 6.73 (s, 1H), 6.80 (dd, J
= 2.2, 9.0 Hz, 1H), 7.10-7.17 (m, 3H), 7.31 (d, J = 7.2 Hz, 1H),
7.45 (d, J = 8.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 19.4,
36.7, 38.0, 55.7, 62.2, 111.5, 113.0, 115.8, 125.1, 126.5, 127.5,
130.6, 131.8, 133.7, 135.4, 141.0, 157.1; MS (EI) m/z 317 (M+),
4.3.7. N-Ms-2-(m-Tolyl)indoline (4d)
97%, a white solid (EtOAc : n-Hexane = 1:4), mp 121-122 °C;
1H NMR (CDCl3, 400 MHz) δ 2.30 (s, 3H), 2.68 (s, 3H), 3.08
(dd, J = 3.2, 16.4 Hz, 1H), 3.76 (dd, J = 10.2, 16.2 Hz, 1H), 5.37
(dd, J = 3.4, 10.6 Hz, 1H), 7.04-7.12 (m, 4H), 7.17-7.24 (m, 3H),