a formal intermolecular [4+2] cycloaddition reaction of 1,3- … · 2017. 3. 28. · s1 supporting...
TRANSCRIPT
-
S1
Supporting Information for
A Formal Intermolecular [4+2] Cycloaddition Reaction of 1,3-
Disubstituted Indoles and Alkylquinone
Chao Lin, Hong-Jin Du, Hui Zhao, Ding-Fei Yan, Nai-Xin Liu, Hongbin Sun, Xiaoan
Wen* and Qing-Long Xu*
Jiangsu Key Laboratory of Drug Discovery for Metabolic Disease and State Key
Laboratory of Natural Medicines, China Pharmaceutical University, 24 Tongjia Xiang,
Nanjing 210009, China
E-mail: [email protected]; [email protected]
Table of Contents
Spectra copies of NMR…………………………………………………………..…S2
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2017
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S2
3.22
3.13
2.06
3.03
1.01
1.00
1.96
0.93
0.99
1.97
1.4298
2.1470
2.8249
2.9569
4.5087
5.2127
6.2129
6.2234
6.2367
6.2872
6.2949
6.5515
6.5759
6.8980
6.9502
7.2383
1.96
0.93
0.99
1.97
6.2129
6.2234
6.2367
6.2872
6.2949
6.5515
6.5759
6.6004
6.8980
6.9232
6.9502
6.9754
15.48
27.71
30.67
36.65
47.28
76.74
77.16
77.58
101.93
104.62
112.67
115.28
117.59
121.66
127.63
134.53
145.75
149.81
149.81
162.45
112.67
115.28
117.59
121.66
127.63
127.89
128.36
-
S3
3.26
3.01
3.07
2.12
3.04
0.95
1.00
1.98
1.02
0.96
0.98
1.3875
2.1740
2.3215
2.7722
3.2522
4.5781
5.0531
6.2258
6.2339
6.3038
6.3117
6.5165
6.5412
6.5657
6.6911
6.7159
6.7707
6.7947
1.98
1.02
0.96
0.98
6.2258
6.2339
6.3038
6.3117
6.5165
6.5412
6.5657
6.6911
6.7159
6.7707
6.7947
15.62
19.25
28.02
35.44
36.77
46.34
76.74
77.16
77.58
103.74
112.61
115.27
118.59
119.83
127.72
131.41
135.63
145.77
147.54
149.77
162.46
112.61
115.27
118.59
119.83
127.72
128.31
131.41
135.63
-
S4
3.24
2.79
2.94
1.90
3.00
1.23
1.00
0.91
0.91
0.95
1.88
1.4164
2.1518
2.1909
2.8158
2.9360
4.4370
5.1743
6.1343
6.1600
6.2548
6.3146
6.7327
6.7452
7.2504
0.91
0.91
0.95
1.88
6.1343
6.1600
6.2548
6.3146
6.7327
6.7452
6.7720
15.52
20.94
27.67
31.03
36.62
47.03
76.74
77.16
77.58
102.25
104.64
112.70
115.27
122.59
126.79
128.11
134.77
145.89
147.62
149.69
122.59
126.79
127.55
128.11
-
S5
2.91
3.06
1.94
2.89
3.02
1.00
1.00
0.92
0.94
0.92
0.97
1.02
1.4231
2.1631
2.8039
2.8095
2.9419
3.6967
4.2662
5.2216
5.8083
5.8156
6.0663
6.0930
6.2442
6.3476
6.7639
6.7906
7.2566
15.49
27.99
30.60
36.87
46.75
55.34
76.74
77.16
77.58
92.51
101.25
102.36
112.72
114.77
115.24
121.89
127.05
127.67
128.62
149.82
151.12
160.49
-
S6
3.35
3.24
2.04
2.98
0.86
1.00
0.96
0.97
0.98
0.97
0.93
1.4206
1.5903
2.1947
2.7545
2.8025
2.8130
2.8615
3.3774
4.3819
5.1285
6.2422
6.2512
6.3770
6.3860
6.4652
6.4913
6.7679
6.8452
7.2556
0.96
0.97
0.98
0.97
0.93
6.2422
6.2512
6.3770
6.3860
6.4652
6.4913
6.5161
6.7679
6.7919
6.8452
6.8720
15.55
28.06
34.25
36.56
46.86
76.74
77.16
77.58
102.95
112.56
115.48
118.92
120.36
128.08
128.16
130.05
137.90
144.82
145.70
149.95
-
S7
3.11
3.27
2.22
2.82
1.14
1.00
0.85
1.06
0.95
0.90
0.83
1.4311
2.1595
2.7521
2.7999
2.8254
2.8726
2.9388
4.3372
5.2437
6.1628
6.1686
6.2291
6.2386
6.3557
6.5275
6.7653
6.7911
7.2537
0.85
1.06
0.95
0.90
0.83
6.1628
6.1686
6.2291
6.2386
6.3557
6.3651
6.5016
6.5076
6.5275
6.5333
6.7653
6.7911
15.44
27.74
30.45
36.54
47.20
76.74
77.16
77.58
101.84
104.94
112.69
115.44
117.17
122.37
127.83
133.09
133.60
145.58
150.01
150.91
-
S8
3.21
3.16
1.96
3.04
0.96
1.00
0.94
0.97
1.02
1.89
1.4054
2.1283
2.7219
2.7699
2.7934
2.8414
2.9084
4.4177
5.1924
6.0674
6.0947
6.2224
6.2312
6.3312
6.3398
6.8157
6.8531
7.2262
15.46
27.65
30.69
36.50
47.51
76.74
77.16
77.58
101.83
105.29
112.75
115.46
122.12
127.65
127.99
136.40
145.67
148.41
149.95
-
S9
3.08
3.27
1.81
2.77
0.96
1.00
0.93
1.01
0.97
1.87
1.4319
2.1569
2.7945
2.8175
2.9311
4.3882
5.2093
6.0628
6.0902
6.2532
6.2603
6.3618
6.9728
6.9782
7.0146
7.2540
0.93
1.01
0.97
1.87
6.0628
6.0902
6.2532
6.2603
6.3618
6.3688
6.9728
6.9782
7.0146
7.0419
7.0476
15.45
27.70
30.62
36.51
47.51
76.74
77.16
77.58
101.72
105.94
109.13
112.76
115.47
124.85
127.81
127.99
130.55
136.87
145.58
148.82
150.00
-
S10
3.39
3.25
2.17
3.32
0.91
1.00
1.04
0.89
0.96
1.95
1.2573
1.4224
2.1527
2.7415
2.7892
2.8150
2.8627
2.9317
4.4824
5.2324
6.2199
6.2290
6.3156
6.3470
6.3557
6.6514
6.6772
6.7182
7.2497
1.04
0.89
0.96
1.95
6.2199
6.2290
6.3156
6.3470
6.3557
6.6514
6.6551
6.6772
6.6809
6.7182
15.44
27.67
30.42
36.45
47.25
76.74
77.16
77.58
101.72
107.69
112.68
120.09
127.83
133.64
145.51
150.01
151.06
120.09
121.61
122.84
127.83
128.26
133.64
-
S11
2.98
3.10
2.01
2.04
0.90
2.06
1.00
1.03
1.87
0.91
1.09
1.88
1.4384
2.1557
2.8501
3.8756
3.8914
3.9304
3.9464
4.0091
4.0284
4.0832
4.3983
5.1516
5.1564
5.1856
5.1906
5.2429
5.2916
5.8155
5.8886
6.2494
6.2735
6.5684
6.5930
6.9097
6.9267
6.9327
7.2522
15.51
27.95
36.54
46.32
47.32
76.57
76.99
77.42
100.10
105.23
112.49
115.10
116.63
121.69
127.60
127.66
133.51
134.45
148.83
149.70
-
S12
2.79
2.88
1.91
0.97
2.44
1.00
0.94
0.86
1.00
1.12
0.92
0.90
5.16
1.4540
2.1153
2.8764
2.8834
4.3900
4.4897
4.5431
4.6093
4.6638
5.2866
6.1755
6.2012
6.2832
6.2919
6.3541
6.5811
6.8734
7.2533
7.2756
7.2837
7.3013
0.94
0.86
1.00
1.12
0.92
0.90
6.1755
6.2012
6.2832
6.3541
6.3630
6.5811
6.6057
6.6303
6.8734
6.8989
6.9242
6.9509
6.9753
15.64
28.04
36.61
47.47
47.65
76.74
77.16
77.58
100.28
105.45
112.69
115.30
117.99
121.91
127.21
127.82
128.69
138.17
145.92
149.23
149.91
127.21
127.33
127.82
128.41
128.69
-
S13
3.19
3.09
4.25
1.15
1.00
1.05
1.04
1.02
1.28
1.07
3.38
3.18
1.2556
1.5613
2.1132
2.8147
2.8339
2.8619
2.9333
2.9776
3.0322
3.0535
3.0974
4.2448
5.3843
6.1398
6.1656
6.2081
6.2173
6.4894
6.6402
6.9147
7.2027
7.2104
7.2237
7.2535
1.05
1.04
1.02
1.28
1.07
3.38
6.1398
6.1656
6.2173
6.2856
6.2946
6.4894
6.5138
6.5382
6.6176
6.6402
6.9147
6.9401
6.9536
6.9612
6.9726
6.9848
15.44
30.43
34.54
46.35
52.03
76.74
77.16
77.58
99.85
104.56
112.79
115.19
117.14
123.10
126.73
128.05
136.66
146.25
149.84
150.57
126.73
127.47
127.94
128.05
128.14
130.71
131.96
-
S14
5.96
8.83
2.28
3.31
1.96
2.91
2.19
0.91
1.00
0.63
1.23
0.97
1.07
0.99
0.97
0.0117
0.8836
2.0113
2.0337
2.0563
2.1530
2.8336
2.8812
2.9277
2.9490
2.9752
3.5713
3.5935
3.6157
4.4602
5.5006
6.1821
6.2090
6.2196
6.2944
6.5349
6.5596
6.8673
6.9175
6.9430
7.2604
0.63
1.23
0.97
1.07
0.99
0.97
6.1821
6.2090
6.2196
6.2944
6.3034
6.5349
6.5596
6.5841
6.8673
6.8895
6.9175
6.9210
6.9430
6.9684
6.9718
-5.26
15.40
18.34
26.07
30.48
35.69
43.00
50.49
59.65
76.74
77.16
77.58
100.18
104.35
112.74
115.21
117.32
122.34
127.55
132.15
145.87
149.92
150.48
112.74
115.21
117.32
122.34
127.55
127.99
128.50
-
S15
1.02
2.85
1.23
1.90
2.92
1.93
0.77
1.00
0.90
0.88
0.90
1.01
0.94
0.98
1.92
1.84
2.0796
2.0965
2.1270
2.1416
2.1765
2.2478
2.2706
2.2802
2.3030
2.3255
2.3478
2.8110
2.8581
2.9818
3.5543
3.5844
3.6029
3.6161
4.4952
5.5318
6.1380
6.1639
6.2383
6.2465
6.3533
6.8278
7.2588
7.6498
7.6600
7.6674
7.6778
7.7516
7.7615
7.7691
7.7796
0.90
0.88
0.90
1.01
0.94
0.98
1.92
1.84
6.1639
6.2383
6.3533
6.4763
6.5007
6.5254
6.8278
6.8534
6.9311
7.2588
7.6498
7.6674
7.7516
7.7691
15.43
30.46
33.93
35.96
38.32
50.33
76.74
77.16
77.58
99.61
104.58
112.74
115.41
117.70
122.25
127.88
128.13
128.19
130.50
133.96
150.17
150.28
168.20
122.25
123.23
127.88
128.13
128.19
130.50
131.10
132.21
133.96
-
S16
3.35
1.97
3.13
0.87
1.00
1.06
2.02
1.07
1.05
1.96
1.4438
2.8470
2.9372
4.7199
5.1880
6.2157
6.2412
6.3964
6.4444
6.7093
6.9063
7.2480
1.06
2.02
1.07
1.05
1.96
6.2157
6.2412
6.3964
6.4161
6.4542
6.5517
6.6815
6.7093
6.9063
6.9302
6.9554
6.9768
6.9807
27.44
30.38
36.60
47.20
76.74
77.16
77.58
101.80
104.69
113.81
115.32
117.56
121.62
127.95
128.95
134.38
147.77
149.81
150.49
113.81
115.32
117.56
118.16
121.62
OH
ON
Me
Me3o
OH
ON
Me
Me3o
-
S17
2.98
3.01
1.06
2.94
1.08
1.01
1.00
0.96
0.99
2.00
2.01
1.4812
1.5990
2.0612
2.6807
2.7288
2.9484
3.0735
3.1216
4.4028
5.1866
6.2026
6.2281
6.3918
6.5390
6.5846
6.9193
6.9454
6.9748
0.96
0.99
2.00
2.01
6.2026
6.2281
6.3918
6.4199
6.5390
6.5635
6.5846
6.6112
6.9193
6.9454
6.9748
11.25
27.38
30.32
33.03
47.30
76.74
77.16
77.58
101.21
104.58
113.09
115.40
117.42
121.20
121.99
127.93
134.55
147.72
148.63
149.89
113.09
115.40
117.42
121.20
121.99
OH
ON
Me
Me
Me
3p
OH
ON
Me
Me
Me
3p
-
S18
2.93
6.56
3.07
1.02
2.77
1.03
1.02
1.00
1.01
1.01
1.90
1.4530
2.0386
2.1482
2.6972
2.9507
3.0324
3.0799
4.1689
5.2026
6.1753
6.2007
6.5234
6.5476
6.9078
6.9326
7.2450
11.30
11.90
12.17
27.75
30.67
33.06
47.53
76.74
77.16
77.58
101.47
104.41
117.32
118.23
120.30
121.28
124.19
127.79
134.88
145.34
146.53
149.87
117.32
118.23
120.30
121.28
123.62
124.19
-
S19
3.00
2.88
3.26
2.00
2.90
1.16
1.05
1.00
0.96
0.95
1.02
0.93
1.91
1.1429
1.1512
1.1657
1.1740
1.4191
2.7978
2.8051
2.9419
3.0159
3.0387
3.0615
4.3330
5.1377
6.2465
6.2722
6.3182
6.5720
6.9242
7.2447
0.96
0.95
1.02
0.93
1.91
6.2465
6.2722
6.3182
6.5720
6.5964
6.6209
6.6885
6.9242
6.9505
6.9779
7.0033
22.48
22.94
27.05
30.58
36.06
46.75
76.74
77.16
77.58
101.64
104.94
115.10
115.19
117.57
121.59
124.97
127.91
133.44
134.84
147.39
147.79
149.77
115.10
115.19
117.57
121.59
124.97
127.91
133.44
134.84
OH
ON
Me
Me3r
iPr
OH
ON
Me
Me3r
iPr
-
S20
2.77
1.79
2.93
2.57
3.10
0.96
1.00
1.83
0.93
1.85
1.4230
1.5506
2.8218
3.0056
3.8485
3.9298
5.1856
5.2662
6.2557
6.2895
6.5799
6.9152
7.2572
1.83
0.93
1.85
6.2557
6.2895
6.5799
6.6043
6.6289
6.9152
6.9391
6.9535
6.9573
6.9791
6.9829
27.52
30.75
36.22
47.44
61.28
61.35
76.74
77.16
77.58
102.09
104.87
108.58
114.77
117.84
121.78
127.94
134.58
138.29
143.65
149.68
-
S21
3.29
1.09
3.08
1.06
1.02
1.00
1.01
1.11
2.15
2.06
1.4872
1.5627
2.7562
2.8056
2.9501
3.2989
3.3483
5.1072
5.1908
6.2285
6.2551
6.5659
6.7198
6.9451
7.2505
1.01
1.11
2.15
2.06
6.2285
6.2551
6.5659
6.5904
6.6144
6.6492
6.6784
6.6909
6.7198
6.9451
6.9681
6.9888
27.18
30.42
33.29
46.93
76.74
77.16
77.58
101.50
104.92
113.65
116.95
121.45
126.12
133.87
146.45
148.14
149.60
113.65
116.95
117.88
121.45
126.12
128.15