the royal society of chemistry1 regioselective oxidation of indoles to 2-oxindoles santosh v....
TRANSCRIPT
1
Regioselective oxidation of indoles to 2-oxindoles
Santosh V. Shelara,b and Narshinha P. Argade*,a,b
aDivision of Organic Chemistry, National Chemical Laboratory (CSIR), Pune 411 008, India
bAcademy of Scientific and Innovative Research (AcSIR), New Delhi 110 025, India
Table of Contents
Copies of 1H, 13C and DEPT NMR Spectra........................................................... 02 to 44
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2019
2
1H NMR of 2a
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
2.021.001.022.061.00
WaterCHLOROFORM-d
1.80
23
3.55
91
6.88
436.
9229
7.02
377.
0595
7.19
397.
2248
7.22
817.
2606
7.26
397.
2700
8.72
60
7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90
1.001.022.06
CHLOROFORM-d
7.27
007.
2639
7.26
067.
2281
7.22
487.
1939
7.19
06
7.06
457.
0595
7.02
376.
9896
6.98
46
6.92
29
6.88
436.
8794
C8H7NO1H NMR, 200 MHz
CDCl3
NH
O
3
13C NMR of 2a
184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
36.2
509
77.0
000
109.
7723
122.
3010
124.
5552
125.
2532
127.
9000
142.
5374
177.
9783
C8H7NO13C NMR, 50 MHz
CDCl3
NH
O
4
1H NMR of 2i
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.001.111.121.010.992.031.01
DMSO-d6Water
2.50
002.
6289
2.66
582.
7148
2.75
012.
8470
2.86
802.
9324
2.95
563.
3825
3.58
583.
6122
6.78
766.
8240
6.87
466.
9121
6.94
907.
1226
7.15
957.
1958
7.23
16
10.3
767
2.9 2.8 2.7
1.001.11
2.95
562.
9324
2.86
802.
8470
2.75
01
2.71
48
2.66
58
2.62
89
7.2 7.1 7.0 6.9 6.8
1.010.992.03
7.23
167.
1958
7.15
957.
1226
6.94
906.
9121
6.87
46
6.82
406.
7876
C10H9NO31H NMR, 200 MHz
DMSO-d6
NH
O O
OH
5
13C NMR of 2i
184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
DMSO-d6
33.9
990
39.5
100
41.8
460
109.
2364
121.
2309
123.
6527
127.
7716
129.
4402
142.
9411
172.
2886
178.
2763
C10H9NO313C NMR, 100 MHz
DMSO-d6
NH
O O
OH
6
1H NMR of 2j
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.051.053.031.031.001.032.031.01
CHLOROFORM-d
2.81
942.
8354
2.85
302.
8690
3.07
803.
0871
3.11
233.
1207
3.70
803.
8209
3.83
003.
8369
3.84
61
6.90
396.
9199
7.00
087.
0160
7.03
137.
2113
7.22
427.
2364
7.27
00
8.76
04
7.20 7.15 7.10 7.05 7.00 6.95 6.90
1.001.032.03
7.23
957.
2364
7.22
427.
2113
7.03
137.
0160
7.00
08
6.91
996.
9039
3.85 3.84 3.83 3.82
1.00
3.84
61
3.83
69
3.83
00
3.82
09
3.1 3.0 2.9 2.8
1.051.05
3.12
073.
1123
3.08
713.
0780
2.86
902.
8530
2.83
54
C11H11NO31H NMR, 500 MHz
CDCl3
NH
O O
OMe
7
13C NMR of 2j
192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
34.5
556
42.2
831
52.0
050
77.0
000
109.
8514
122.
4626
124.
0703
128.
3170
128.
6734
141.
5273
171.
5349
179.
1032
128 127 126 125 124 123 122
128.
6734
128.
3170
124.
0703
122.
4626
C11H11NO313C NMR, 125 MHz
CDCl3
NH
O O
OMe
8
DEPT of 2j
135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
34.5
556
42.2
907
52.0
202
109.
8666
122.
4702
124.
0855
128.
3246
C11H11NO3DEPT, 125 MHz
CDCl3
NH
O O
OMe
9
1H NMR of 2k
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.041.091.023.080.941.011.011.011.070.98
CHLOROFORM-d
1.94
992.
0269
2.05
512.
0696
2.08
342.
2153
2.22
752.
2390
2.25
502.
2672
3.46
703.
4792
3.48
603.
5005
3.51
273.
5257
6.41
886.
8886
6.90
397.
0358
7.05
117.
0663
7.20
447.
2197
7.23
497.
2700
7.27
617.
2914
8.65
36
7.3 7.2 7.1 7.0 6.9
1.011.011.011.07
CHLOROFORM-d
7.29
147.
2761
7.27
00
7.23
497.
2197
7.20
44
7.06
637.
0511
7.03
58
6.90
396.
8886
C12H14N2O21H NMR, 500 MHz
CDCl3
NH
O
N Me
O
H
10
13C NMR of 2k
192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
23.1
805
29.9
525
37.2
098
44.3
685
77.0
000
109.
8211
122.
7205
124.
1537
128.
1653
129.
1740
141.
1254
170.
4581
180.
2710
C12H14N2O213C NMR, 125 MHz
CDCl3
NH
O
N Me
O
H
11
DEPT of 2k
136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
23.1
805
29.9
449
37.2
022
44.3
610
109.
8211
122.
7129
124.
1462
128.
1578
C12H14N2O2DEPT, 125 MHz
CDCl3
NH
O
N Me
O
H
12
1H NMR of 2l
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
2.103.181.001.001.041.023.062.031.001.00
DMSO-d6Water
1.97
372.
1316
2.50
00
3.37
943.
4450
3.49
53
6.83
546.
8476
6.96
817.
1824
7.34
797.
3586
7.44
567.
4952
7.50
587.
8224
7.83
30
8.56
38
10.4
157
C17H16N2O21H NMR, 500 MHz
DMSO-d6
NH
O
N Ph
O
H
13
13C NMR of 2l
192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
DMSO-d6
30.0
762
36.5
600
39.5
100
43.2
714
109.
2699
121.
3199
124.
1789
127.
1516
127.
6976
128.
2285
129.
5404
131.
0798
134.
5151
142.
6142
166.
2290
178.
8554
128.0 127.5
128.
2285
127.
6976
127.
1516
C17H16N2O213C NMR, 125 MHz
DMSO-d6
NH
O
N Ph
O
H
14
DEPT of 2l
136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
30.0
762
36.5
600
43.2
789
109.
2775
121.
3275
124.
1940
127.
1592
127.
7052
128.
2436
131.
0950
C17H16N2O2DEPT, 125 MHz
DMSO-d6
NH
O
N Ph
O
H
15
1H NMR of 2m
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.001.034.073.031.001.001.041.001.00
DMSO-d6
1.86
761.
8985
1.93
261.
9629
1.99
822.
0942
2.12
382.
1623
2.19
202.
2311
2.50
00
3.40
893.
4360
3.46
823.
5212
3.55
913.
5875
3.62
60
6.80
076.
8386
6.92
576.
9623
6.99
967.
1435
7.18
137.
2186
7.27
927.
3151
10.4
009
C14H14N2O31H NMR, 200 MHz
DMSO-d6
NH
O
N
O
O
16
13C NMR of 2m
176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
DMSO-d6
27.2
140
27.9
412
35.1
835
39.5
100
43.1
312
109.
3302
121.
2699
123.
8585
127.
7560
129.
0358
142.
6624
177.
5362
178.
2633
C14H14N2O313C NMR, 50 MHz
DMSO-d6
NH
O
N
O
O
17
1H NMR of 2n
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.081.101.041.081.082.021.001.031.061.131.05
WaterCHLOROFORM-d
1.82
592.
2622
2.27
742.
2957
2.30
942.
3857
2.40
102.
4177
3.51
453.
6121
3.63
043.
6457
3.75
403.
7708
3.78
753.
8028
6.56
226.
8810
6.89
937.
0015
7.01
837.
0351
7.17
247.
1892
7.20
597.
2517
7.27
00
8.67
95
C14H12N2O31H NMR, 400 MHz
CDCl3
NH
O
N
O
O
18
13C NMR of 2n
184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
28.1
287
34.8
184
43.8
277
77.0
000
110.
0123
122.
4464
123.
9516
128.
1109
128.
4963
133.
8626
141.
4976
170.
4742
179.
2581
128 126 124
128.
4963
128.
1109
123.
9516
122.
4464
C14H12N2O313C NMR, 50 MHz
CDCl3
NH
O
N
O
O
19
1H NMR of 2o
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.062.001.151.051.091.011.001.051.151.591.01
WaterCHLOROFORM-d
1.97
211.
9809
2.22
582.
2378
2.27
062.
2965
2.37
792.
3855
2.40
632.
4145
2.44
86
3.47
933.
5077
3.53
423.
6036
3.62
953.
6371
3.70
403.
7374
3.74
563.
7785
3.84
92
6.16
496.
1737
6.18
326.
1914
6.84
466.
8831
7.00
317.
0069
7.03
977.
0447
7.19
187.
1956
7.24
997.
2700
7.28
65
8.16
25
7.2 7.1 7.0 6.9
1.001.051.151.59
CHLOROFORM-d
7.28
657.
2700
7.24
997.
2303
7.19
567.
1918
7.15
717.
1533
7.04
477.
0397
7.00
697.
0031
6.96
966.
9652
6.88
31
6.84
46
6.200 6.175 6.150
1.00
6.19
14
6.18
32
6.17
37
6.16
49
3.525 3.475
1.15
3.53
42
3.50
77
3.47
93
1.99 1.98 1.97 1.96
3.06
1.98
09
1.97
21
C15H14N2O31H NMR, 200 MHz
CDCl3
NH
O
N
O
O
Me
20
13C NMR of 2o
176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
10.8
009
28.2
742
34.8
766
43.7
914
109.
8669
122.
4028
123.
9953
127.
1292
127.
9873
128.
6344
141.
3958
145.
4314
170.
5760
171.
5068
179.
0618
C15H14N2O313C NMR, 50 MHz
CDCl3
NH
O
N
O
O
Me
21
1H NMR of 2p
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.191.033.093.111.011.001.031.051.051.00
DMSO-d6Water
1.95
981.
9763
1.98
361.
9928
2.00
992.
1083
2.12
362.
1425
2.15
722.
5000
3.41
613.
4302
3.43
753.
4552
3.49
923.
5182
3.53
413.
5530
3.84
39
5.75
37
6.79
086.
8097
6.92
596.
9448
6.96
377.
1391
7.15
817.
1770
7.25
047.
2687
10.3
904
7.2 7.1 7.0 6.9 6.8
1.001.031.051.05
7.26
877.
2504
7.17
707.
1581
7.13
91
6.96
376.
9448
6.92
59
6.80
976.
7908
C15H14N2O41H NMR, 400 MHz
DMSO-d6
NH
O
N
O
O
OMe
22
13C NMR of 2p
176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
DMSO-d6
28.1
509
34.1
560
39.5
100
43.0
181
59.1
337
96.8
951
109.
3802
121.
2984
123.
8260
127.
7094
128.
9273
142.
6378
160.
8139
165.
0726
170.
0589
178.
2086
C15H14N2O413C NMR, 100 MHz
DMSO-d6
NH
O
N
O
O
OMe
23
DEPT of 2p
130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
28.1
509
34.1
483
43.0
180
59.1
337
96.8
951
109.
3725
121.
2984
123.
8260
127.
7094
C15H14N2O4DEPT, 100 MHz
DMSO-d6
NH
O
N
O
O
OMe
24
1H NMR of 2q
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.061.081.081.121.141.051.011.021.014.161.06
DMSO-d6
2.06
982.
1019
2.11
712.
2300
2.24
532.
2636
2.27
882.
5000
3.50
683.
5205
3.53
273.
6227
3.63
793.
6547
3.70
513.
7234
3.74
01
6.77
726.
7970
6.84
436.
8626
6.88
097.
0761
7.09
457.
1128
7.27
607.
2928
7.78
70
10.3
954
C18H14N2O31H NMR, 500 MHz
DMSO-d6
NH
O
N
O
O
25
13C NMR of 2q
184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
DMSO-d6
28.0
054
34.7
075
39.5
100
43.1
712
109.
3419
121.
2295
122.
8839
123.
8107
127.
6481
128.
9426
131.
6541
134.
2123
142.
6608
167.
7151
178.
2776
C18H14N2O313C NMR, 125 MHz
DMSO-d6
NH
O
N
O
O
26
DEPT of 2q
140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
28.0
054
34.7
151
43.1
789
109.
3495
121.
2371
122.
8916
123.
8184
127.
6558
134.
2200
C18H14N2O3DEPT, 125 MHz
DMSO-d6
NH
O
N
O
O
27
1H NMR of 2t
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.031.082.103.011.121.021.031.071.081.061.04
DMSO-d6Water
1.79
681.
8135
1.82
731.
9463
1.96
301.
9798
1.99
512.
5000
3.10
103.
1178
3.13
303.
3954
3.41
223.
5052
6.81
226.
8305
6.93
126.
9495
6.96
787.
1539
7.17
227.
1905
7.22
567.
2698
7.28
66
10.3
847
C12H14N2O31H NMR, 500 MHz
DMSO-d6
NH
O
N OMe
O
H
7.2 7.1 7.0 6.9 6.8
1.021.031.071.081.06
7.28
667.
2698
7.22
56
7.19
057.
1722
7.15
39
6.96
786.
9495
6.93
12
6.83
056.
8122
28
13C NMR of 2t
184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
DMSO-d6
30.6
096
37.5
492
39.5
100
42.9
262
51.2
597
109.
2653
121.
3214
124.
1248
127.
7018
129.
5171
142.
5995
156.
7160
178.
7755
C12H14N2O313C NMR, 125 MHz
DMSO-d6
NH
O
N OMe
O
H
29
DEPT of 2t
135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
30.6
096
37.5
415
42.9
261
51.2
597
109.
2652
121.
3213
124.
1247
127.
7094
C12H14N2O3DEPT, 125 MHz
DMSO-d6
NH
O
N OMe
O
H
30
1H NMR of 2u
9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
2.123.021.511.043.551.011.031.520.511.01
CHLOROFORM-d
2.09
792.
1162
2.21
76
2.88
883.
3297
3.37
543.
4555
3.46
773.
4799
3.61
343.
6546
6.90
927.
0389
7.05
197.
2128
7.23
427.
2700
7.37
757.
3890
8.90
238.
9968
C13H16N2O31H NMR, 500 MHz
CDCl3Rotameric mixture
NH
O
N OMe
O
Me
31
13C NMR of 2u
184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
28.2
614
33.9
944
34.5
783
43.6
405
45.5
288
46.1
582
52.5
738
77.0
000
109.
7452
122.
3716
122.
4399
123.
8655
124.
1461
124.
2826
127.
9834
128.
9085
129.
2043
141.
4591
141.
6563
141.
7093
156.
8838
156.
9748
179.
7554
180.
0663
C13H16N2O313C NMR, 125 MHz
CDCl3Rotameric mixture
NH
O
N OMe
O
Me
32
DEPT of 2u
130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
28.2
614
33.9
945
34.5
784
43.6
330
45.4
985
46.1
810
52.5
738
109.
7528
109.
8514
122.
3413
122.
4399
123.
8353
124.
2675
127.
9531
128.
0516
C13H16N2O3DEPT, 125 MHz
CDCl3Rotameric mixture
NH
O
N OMe
O
Me
33
1H NMR of 3
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
2.173.072.063.201.071.021.071.121.021.14
DMSO-d6Water
1.94
47
2.50
00
2.69
68
3.16
503.
3908
3.45
493.
4945
5.97
94
6.79
706.
8153
6.95
416.
9724
6.99
077.
1875
7.20
737.
2256
7.27
447.
2912
10.2
733
C13H16N2O41H NMR, 400 MHz
DMSO-d6Rotameric mixture
NH
O
N OMe
O
MeOH
34
13C NMR of 3
176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
DMSO-d6
33.5
356
33.9
185
34.9
526
35.3
662
39.5
100
43.0
564
43.4
776
52.1
712
74.1
464
109.
6789
121.
6814
123.
9409
129.
0498
131.
6847
141.
6344
155.
7356
178.
8138
C13H16N2O413C NMR, 100 MHz
DMSO-d6Rotameric mixture
NH
O
N OMe
O
MeOH
35
DEPT of 3
135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
33.4
973
33.9
032
34.9
296
35.3
432
43.0
334
43.4
776
52.1
712
109.
6712
121.
6814
123.
9409
129.
0499
C13H16N2O4DEPT, 100 MHz
DMSO-d6Rotameric mixture
NH
O
N OMe
O
MeOH
36
1H NMR of 4
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.131.103.051.091.082.082.101.021.03
CHLOROFORM-d
2.41
592.
4235
2.44
182.
7439
2.74
622.
7569
2.75
912.
7721
2.78
512.
9742
3.25
653.
2694
3.27
553.
2885
3.32
593.
3282
3.34
57
4.69
42
6.70
186.
7170
6.73
306.
8665
6.86
886.
8825
6.88
487.
0999
7.10
227.
1175
7.13
277.
2700
7.1 7.0 6.9 6.8 6.7
2.101.021.03
7.13
277.
1304
7.11
757.
1022
7.09
99
6.88
486.
8825
6.86
886.
8665
6.73
306.
7170
6.70
18
3.350 3.325
1.08
3.36
553.
3632
3.34
57
3.32
823.
3259
2.775 2.750
1.10
2.78
512.
7820
2.77
212.
7698
2.75
912.
7569
2.74
622.
7439
2.450 2.425 2.400
1.13
2.45
94
2.44
182.
4342
2.42
352.
4159
2.39
76
C11H14N2O21H NMR, 500 MHz
CDCl3
NH
O
NHMeOH
37
13C NMR of 4
176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
30.1
648
32.8
645
45.6
881
77.0
000
79.3
736
118.
0718
118.
3600
125.
2154
125.
6628
129.
1967
145.
8271
175.
1598
C11H14N2O213C NMR, 125 MHz
CDCl3
NH
O
NHMeOH
38
DEPT of 4
130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
30.1
648
32.8
569
45.6
805
118.
0567
118.
3524
125.
6552
129.
1967
C11H14N2O2DEPT, 125 MHz
CDCl3
NH
O
NHMeOH
39
1H NMR, 400 MHz, CDCl3 of 4
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
2.191.082.073.231.141.191.020.360.671.032.071.03
WaterCHLOROFORM-d
1.37
881.
3922
1.50
471.
5181
1.60
78
2.45
892.
4685
2.47
802.
4837
2.49
522.
5009
2.51
052.
5162
2.96
473.
0162
3.41
893.
4303
3.43
793.
4437
3.44
943.
4532
3.46
283.
4742
3.58
873.
6154
4.07
92
4.74
714.
7605
4.77
57
5.51
245.
5257
5.54
105.
5543
6.69
946.
7166
6.80
626.
8272
6.84
446.
9131
6.91
696.
9322
6.93
607.
0849
7.10
787.
1269
7.27
00
4.800 4.775 4.750 4.725
0.36
4.77
57
4.76
054.
7471
Donaxarine (6)
Dehydrative cyclization (- H2O)
Hydrative ring cleavage (+ H2O)(Insepareble mixture, 5B:6 = 35:65)
5B (Boat-chair conformation)
NH
O
NOMe
Me
NH
O
O HO
N Me
Me
H
40
13C NMR, 100 MHz, CDCl3 of 4
176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
20.9
462
30.3
092
30.5
380
35.4
578
36.0
966
45.7
933
46.0
603
76.5
233
77.0
000
79.8
222
81.4
813
117.
2550
118.
7424
120.
0105
120.
8686
123.
8053
125.
2164
125.
3308
128.
0291
128.
1340
141.
3680
142.
9698
172.
8130
173.
9667
Donaxarine (6)
Dehydrative cyclization (- H2O)
Hydrative ring cleavage (+ H2O)(Insepareble mixture, 5B:6 = 35:65)
5B (Boat-chair conformation)
NH
O
NOMe
Me
NH
O
O HO
N Me
Me
H
41
DEPT, 100 MHz, CDCl3 of 4
130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
20.8
699
20.9
462
30.3
092
30.5
380
35.4
578
36.0
966
45.7
933
46.0
603
76.5
233
76.7
616
117.
2550
118.
7424
120.
0105
120.
8686
125.
2164
125.
3308
128.
0291
128.
1340
Donaxarine (6)
Dehydrative cyclization (- H2O)
Hydrative ring cleavage (+ H2O)(Insepareble mixture, 5B:6 = 35:65)
5B (Boat-chair conformation)
NH
O
NOMe
Me
NH
O
O HO
N Me
Me
H
42
1H NMR of 7
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.393.001.041.063.011.041.051.031.991.00
WaterCHLOROFORM-d
1.27
411.
2871
1.71
19
2.25
342.
3823
2.39
682.
4098
2.41
972.
7149
2.72
712.
7408
2.75
462.
7675
2.87
81
3.45
633.
4586
3.46
243.
4784
3.58
063.
5959
3.60
273.
6081
3.62
41
6.31
056.
3211
7.19
377.
2090
7.22
887.
2425
7.27
007.
3539
7.36
927.
3844
C15H18N2O31H NMR, 500MHz
CDCl3
N O
NOMe
Me
Ac
43
13C NMR of 7
176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
20.9
964
23.1
198
30.3
620
32.9
252
45.9
611
77.0
000
77.7
053
78.5
091
123.
6380
125.
7007
126.
2922
128.
5218
132.
3211
136.
2417
170.
3823
171.
4288
C15H18N2O313C NMR, 125MHz
CDCl3
N O
NOMe
Me
Ac
44
DEPT NMR of 7
130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0Chemical Shift (ppm)
20.9
964
23.1
122
30.3
619
32.9
175
45.9
534
77.6
976
123.
6228
125.
6931
126.
2770
128.
5141
C15H18N2O3DEPT NMR, 125MHz
CDCl3
N O
NOMe
Me
Ac
