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S1
Supporting Information
The one pot asymmetric synthesis of 3,3′-pyrrolidonyl spiroxindoles via regio- and stereoselective domino reactionSaumen Hajra,* Suhas Shivajirao Bhosale, Atanu Hazra, and Nikhil Kanaujia
Centre of Biomedical Research, Sanjay Gandhi Post-Graduate Institute of Medical Sciences Campus, Raebareli Road, Lucknow 226014, India.
List of Contents
Sci-finder substructure search data S2
X-ray crystal structure details S3-S4
References S4
1H, 13C and 19F Spectra of compounds S5-S29
HPLC chromatogram S30-S44
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2019
S2
Sci-finder substructure on February 28, 2019
structureN
N
O
1N
N
O
1'N
N
O
O
2N
N
O
OH
2'N
N
O
OO
2''
hit 14,700 11,466 434 273 248
hit for Biological
study
2972 2488 181 150 150
ref. for all (including
patent)
1987 1759 88 38 45
ref. for biological
study (including
patent)
1188 1104 43 10 34
Table 1 Optimization of the domino reaction with different metal triflates
NN
O
CO2Me
Bn
+M(OTf)nbase
THF60 °C, 3 h
Ph
(±)-4a(±)-5b
N
NO
OPh
BnTs
Ts3b
entry M(OTf)n base dr yield of (±)-5b (%)
1 In(OTf)3 KtOBu >99:1 42
2 Y(OTf)3 KtOBu >99:1 273 Fe(OTf)3 KtOBu >99:1 32
4 Mg(OTf)2 KtOBu >99:1 35
5 Zn(OTf)2 KtOBu >99:1 30
S3
X-ray crystal structure details:
Datablock for the compound 5b
The details of crystal data collection and refinement of 5b are summarized in Table S1.
CCDC 1898778 contains the supplementary crystallographic data for this paper. This data
can be obtained free of charge from The Cambridge Crystallography Data Center via
www.ccdc.cam.ac.uk/data_request/cif.
N
NTs
O Ph
O
Bn
(3R,4'S)-1-benzyl-4'-phenyl-1'-tosylspiro[indoline-3,3'-pyrrolidine]-2,2'-dione
S4
ORTEP diagram of 5b:
Reference(1) L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837.
(2) G. M. Sheldrick, Acta Crystallogr. 2008, C71, 112
(3) L. J. Farrugia, J. Appl. Crystallogr. 1997, 30, 565.
S5
1H NMR and 13C NMR Spectra of Compounds
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
sh. pm.51 mix
6.10
3.00
2.60
1.44
1.05
1.61
1.41
0.93
1.10
0.95
1.52
1.07
0.84
0.83
3.30
1.71
5.65
3.58
5.16
1.25
1.11
2.04
1.82
2.43
32.
724
3.01
33.
237
3.25
33.
779
3.78
73.
801
3.80
93.
834
3.85
13.
855
3.87
23.
979
3.99
54.
002
4.09
14.
108
4.11
74.
135
4.18
44.
202
4.21
14.
229
4.25
54.
261
4.27
24.
279
4.40
84.
424
6.45
96.
479
6.61
86.
624
6.63
66.
643
6.77
96.
784
6.80
06.
803
6.95
56.
962
6.96
46.
972
6.98
06.
983
6.99
16.
998
7.00
17.
006
7.01
97.
038
7.08
07.
083
7.09
97.
102
7.11
37.
118
7.12
97.
131
7.14
87.
150
7.16
67.
169
7.26
07.
266
7.26
97.
271
7.27
77.
290
7.29
87.
308
7.32
67.
329
7.34
57.
348
7.36
57.
440
7.44
37.
458
7.46
17.
639
7.64
47.
660
7.68
67.
691
7.70
7
1H NMR Spectrum of Compound 5a(crude reaction) (400 MHz, CDCl3)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
20.01.2016AH.183
3.00
1.98
0.99
2.00
1.98
0.93
3.97
5.08
1.73
2.82
1.91
2.52
07
4.18
424.
2115
4.22
434.
2311
4.24
064.
2592
4.50
404.
5251
4.54
584.
9382
4.96
284.
9723
4.99
015.
0128
6.40
776.
4268
6.46
176.
4798
7.07
187.
0910
7.11
027.
1624
7.18
057.
1947
7.20
957.
2255
7.24
187.
2600
7.27
907.
3251
7.33
737.
3567
7.37
507.
3936
7.43
957.
4589
8.09
988.
1200
1H NMR Spectrum of Compound 5b (400 MHz, CDCl3)
BnN
O
NTs
Ph
O
MeN
O
NTs
O
MeN
O
NTs
O
dr 1:1
S6
-20-100102030405060708090100110120130140150160170180190200210f1 (ppm)
AHC.183
20.7
74
75.6
8375
.957
76.0
0076
.273
76.3
17
108.
653
122.
435
122.
865
124.
369
125.
255
126.
177
127.
020
127.
358
127.
459
127.
529
127.
764
128.
670
128.
741
131.
738
133.
318
133.
380
142.
852
144.
509
167.
525
169.
952
13C NMR Spectrum of Compound 5b (100 MHz, CDCl3)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
AH.185 3012153.
00
1.86
0.98
1.94
2.68
3.71
0.99
3.37
1.17
1.86
0.90
1.77
2.51
4
4.13
84.
165
4.17
84.
184
4.19
34.
212
4.48
14.
499
4.50
44.
523
4.90
84.
931
4.93
64.
958
4.99
76.
311
6.33
26.
366
6.38
57.
062
7.06
77.
081
7.08
47.
100
7.10
57.
124
7.15
97.
178
7.25
97.
264
7.27
97.
298
7.30
97.
314
7.32
27.
330
7.33
57.
364
7.36
87.
371
7.38
67.
404
7.43
27.
452
7.56
97.
574
8.07
88.
082
8.09
9
1H NMR Spectrum of Compound 5d (400 MHz, CDCl3)
BnN
O
NTs
Ph
O
BnN
O
NTs
Ph
O
Br
S7
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
AHc.185 301215
21.7
65
43.5
8547
.928
48.0
27
64.5
31
76.6
8377
.000
77.3
18
111.
090
115.
973
126.
210
127.
079
127.
353
128.
024
128.
421
128.
534
128.
607
128.
873
129.
708
132.
345
132.
644
133.
781
134.
264
142.
857
145.
634
167.
839
170.
413
13C NMR Spectrum of Compound 5d (100 MHz, CDCl3)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
AH.188
3.00
2.01
1.03
2.05
2.94
3.94
1.98
1.97
0.56
1.21
2.77
1.89
2.45
3
4.08
04.
101
4.12
04.
129
4.14
94.
421
4.44
04.
444
4.46
34.
851
4.87
44.
879
4.89
84.
902
4.93
8
6.29
56.
305
6.31
66.
324
7.00
17.
006
7.02
07.
040
7.04
57.
063
7.10
07.
105
7.11
67.
121
7.12
67.
134
7.19
77.
202
7.21
67.
235
7.26
17.
306
7.30
97.
324
7.34
37.
370
7.37
67.
390
8.01
78.
037
1H NMR Spectrum of Compound 5e (400 MHz, CDCl3)
BnN
O
NTs
Ph
O
Br
BnN
O
NTs
Ph
O
Cl
S8
102030405060708090100110120130140150160170180190f1 (ppm)
AHC.188
21.7
83
43.6
3347
.947
48.0
65
64.6
27
76.6
8376
.963
77.0
0277
.319
110.
644
124.
361
126.
224
126.
997
127.
367
128.
043
128.
446
128.
551
128.
622
128.
798
128.
887
129.
719
129.
776
132.
363
133.
826
134.
278
142.
383
145.
649
167.
856
170.
518
13C NMR Spectrum of Compound 5e (100 MHz, CDCl3)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
AH.191.F
3.00
2.01
1.05
2.07
2.94
1.00
3.95
2.05
2.05
0.27
1.34
2.06
1.84
2.51
6
4.14
94.
163
4.18
24.
190
4.21
14.
492
4.51
14.
515
4.53
44.
932
4.95
64.
961
4.96
54.
984
5.00
56.
361
6.37
16.
382
6.39
36.
401
6.88
66.
893
6.90
86.
915
6.93
16.
937
7.07
17.
076
7.09
07.
109
7.11
47.
131
7.16
57.
183
7.19
57.
201
7.21
47.
220
7.25
97.
265
7.27
97.
298
7.32
77.
372
7.39
17.
409
7.43
57.
455
8.08
98.
110
1H NMR Spectrum of Compound 5f (400 MHz, CDCl3)
BnN
O
NTs
Ph
O
Cl
BnN
O
NTs
Ph
O
F
S9
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
AHC.191.F
21.7
64
43.6
5247
.967
48.1
13
64.8
5864
.878
77.0
00
110.
341
110.
421
111.
897
112.
145
116.
104
116.
336
126.
226
126.
767
126.
850
127.
313
128.
030
128.
438
128.
513
128.
592
128.
851
129.
697
132.
413
133.
957
134.
290
139.
779
139.
802
145.
616
158.
153
160.
563
167.
940
170.
666
13C NMR Spectrum of Compound 5f (100 MHz, CDCl3)
19-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
AH-191
-118
.671
F NMR Spectrum of Compound 5f (376 MHz, CDCl3)
BnN
O
NTs
Ph
O
F
BnN
O
NTs
Ph
O
F
S10
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
AH 205
3.00
3.13
1.99
0.99
2.04
2.94
0.97
5.06
1.07
2.12
0.32
1.24
2.04
1.85
2.44
3
3.78
24.
071
4.10
54.
111
4.12
54.
134
4.15
34.
423
4.44
14.
445
4.46
54.
858
4.87
04.
881
4.88
64.
910
6.27
96.
300
6.32
56.
344
6.65
06.
656
6.67
16.
677
6.97
36.
979
6.99
26.
997
7.01
17.
031
7.03
67.
055
7.08
37.
101
7.11
97.
173
7.17
87.
193
7.21
27.
260
7.28
57.
303
7.32
27.
361
7.38
18.
023
8.02
78.
044
1H NMR Spectrum of Compound 5g (400 MHz, CDCl3)
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
AHc 205
21.7
73
43.6
1948
.014
48.0
67
55.8
25
64.8
97
77.0
00
110.
218
110.
719
114.
529
126.
297
126.
502
127.
154
128.
043
128.
349
128.
456
128.
502
128.
763
129.
675
132.
755
134.
367
134.
406
137.
181
145.
514
156.
435
168.
537
170.
673
13C NMR Spectrum of Compound 5g (100 MHz, CDCl3)
BnN
O
NTs
Ph
O
OMe
BnN
O
NTs
Ph
O
OMe
S11
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
AH 209
9.00
1.13
1.13
1.11
1.14
1.13
1.19
2.22
1.02
1.01
4.29
2.45
2.17
1.63
5
4.08
34.
103
4.11
14.
131
4.30
64.
345
4.46
84.
491
4.51
14.
767
4.79
54.
819
5.05
95.
099
6.54
26.
561
6.58
96.
607
6.90
76.
926
6.99
77.
016
7.03
67.
121
7.13
87.
156
7.17
17.
189
7.21
17.
220
7.22
67.
270
7.41
17.
429
1H NMR Spectrum of Compound 5u (400 MHz, CDCl3)
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
209AHC.209 24
.46
43.7
747
.71
49.7
1
65.2
365
.27
76.6
877
.00
77.3
2
109.
8612
3.75
124.
0512
6.36
126.
6412
7.46
128.
7113
0.01
130.
2413
0.77
131.
5813
4.36
143.
75
168.
7417
1.48
13C NMR Spectrum of Compound 5u (100 MHz, CDCl3)
BnN
O
NBus
O
Br
BnN
O
NBus
O
Br
S12
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
AH 221
8.62
1.06
1.04
1.00
1.03
0.98
1.06
2.08
0.81
0.92
3.34
1.00
1.20
0.74
0.92
1.63
0
4.05
54.
075
4.08
34.
103
4.27
64.
316
4.46
54.
488
4.50
84.
746
4.77
34.
799
5.05
65.
096
6.41
26.
433
6.56
86.
586
6.91
56.
934
7.03
37.
053
7.07
37.
127
7.14
57.
163
7.18
27.
199
7.27
07.
284
7.34
17.
362
7.44
07.
460
7.56
5
1H NMR Spectrum of Compound ent-5v (400 MHz, CDCl3)
0102030405060708090100110120130140150160170180190f1 (ppm)
AH/22123.04.2016
24.4
6
43.9
047
.80
49.7
8
65.2
865
.30
76.8
4 C
DC
l377
.00
CD
Cl3
77.1
6 C
DC
l3
111.
34
116.
3612
3.03
126.
3712
6.83
127.
0912
7.29
127.
7012
8.84
130.
4013
0.69
131.
8413
2.98
133.
8713
4.88
142.
81
168.
1717
0.99
13C NMR Spectrum of Compound ent-5v (100 MHz, CDCl3)
BnN
O
NBus
O
Br
Br
BnN
O
NBus
O
Br
Br
S13
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
Atanu hazra dec 2015AH.214
9.33
3.03
1.05
1.00
0.99
0.99
1.00
0.99
1.95
1.00
0.97
1.88
3.14
1.07
0.86
1.62
3.79
4.04
4.06
4.07
4.09
4.26
4.30
4.45
4.47
4.48
4.50
4.75
4.77
4.77
4.80
5.02
5.06
6.43
6.45
6.57
6.59
6.72
6.72
6.74
6.74
6.89
6.91
6.93
6.99
7.00
7.01
7.03
7.11
7.12
7.14
7.15
7.17
7.24
7.24
7.26
7.40
7.42
1H NMR Spectrum of Compound 5w (400 MHz, CDCl3)
0102030405060708090100110120130140150160170180190f1 (ppm)
Atanu hazra dec 2015AHc.214
24.4
2
43.8
247
.72
49.7
7
55.8
5
65.2
465
.60
110.
4411
0.85
114.
7912
2.81
126.
2112
6.38
126.
7012
7.41
127.
8412
8.66
129.
9413
0.21
130.
6913
1.55
134.
4213
5.28
137.
02
156.
63
168.
7417
1.17
13C NMR Spectrum of Compound 5w (100 MHz, CDCl3)
BnN
O
NBus
O
Br
OMe
BnN
O
NBus
O
Br
OMe
S14
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
NK-Ns-spiro
2.03
1.00
1.98
1.87
0.99
3.91
5.08
1.08
0.99
1.94
1.95
4.12
264.
1630
4.18
344.
1927
4.21
204.
4604
4.48
304.
5025
4.85
434.
8807
4.89
454.
9039
4.90
914.
9323
6.34
136.
3599
6.41
726.
4350
7.00
807.
0200
7.03
887.
0944
7.11
287.
1247
7.13
157.
1427
7.15
857.
1630
7.17
327.
1778
7.18
147.
1918
7.21
147.
2600
7.29
077.
3092
7.32
777.
3789
7.38
287.
3975
7.39
988.
3309
8.35
338.
3958
8.41
83
1H NMR Spectrum of Compound 5c (400 MHz, CDCl3)
0102030405060708090100110120130140150160170180190f1 (ppm)
NKC-Ns-spiro43
.669
47.8
6848
.225
64.4
25
76.6
9977
.017
77.3
34
109.
900
123.
656
123.
884
124.
204
124.
305
124.
743
126.
220
127.
324
127.
963
128.
606
128.
903
129.
948
130.
065
132.
232
134.
095
142.
623
143.
868
151.
048
168.
916
170.
838
13C NMR Spectrum of Compound 5c (100 MHz, CDCl3)
BnN
O
NNs
O
BnN
O
NNs
O
S15
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
nmr feb 2016/12sh_bs_868
9.53
1.01
1.00
0.97
0.98
0.99
2.90
1.85
5.31
1.92
1.04
1.68
111.
6870
1.69
65
4.14
154.
1609
4.17
004.
1893
4.33
304.
3729
4.52
154.
5410
4.54
524.
5649
4.83
344.
8570
4.86
194.
8856
5.13
565.
1754
6.56
536.
5707
6.58
186.
5879
6.60
056.
9572
6.96
256.
9729
6.97
837.
2042
7.20
787.
2188
7.22
557.
2352
7.24
147.
2456
7.25
607.
2601
7.26
607.
2758
7.27
937.
2950
7.33
347.
3498
7.35
667.
3615
7.36
427.
3727
7.37
777.
4756
7.47
937.
4938
7.49
74
1H NMR Spectrum of Compound (±)-5h (400 MHz, CDCl3)
0102030405060708090100110120130140150160170180190f1 (ppm)
nmr feb 2016/13shc_bs_868
24.4
5
43.7
247
.79
49.6
6
65.2
265
.32
76.6
877
.00
77.3
2
109.
8312
2.61
123.
6912
4.08
125.
1212
6.30
127.
5112
8.69
128.
9312
9.26
129.
5712
9.95
131.
8413
1.88
134.
22
143.
76
168.
78
171.
48
13C NMR Spectrum of Compound (±)-5h (100 MHz, CDCl3)
BnN
O
NBus
O
Br
BnN
O
NBus
O
Br
S16
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
nmr jan2016/19SH BS.886.1
9.39
1.00
0.97
0.96
0.94
0.96
2.79
2.92
4.18
1.66
1.71
46
4.13
334.
1527
4.16
194.
1809
4.32
704.
3671
4.54
224.
5618
4.56
594.
5858
4.85
144.
8569
4.87
534.
8799
4.88
534.
9037
5.15
235.
1588
5.19
235.
1988
6.50
936.
5195
6.53
086.
5411
6.55
316.
5607
6.56
606.
5768
6.58
156.
5851
6.97
316.
9795
6.99
517.
0016
7.01
347.
0179
7.02
367.
0296
7.03
467.
0415
7.07
247.
0938
7.24
527.
2497
7.25
227.
2582
7.26
777.
2757
7.28
057.
2855
7.28
847.
2942
7.41
137.
4163
7.42
747.
4324
1H NMR Spectrum of Compound (±)-5i (400 MHz, CDCl3)
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
nmr jan2016/20SHc BS.886.1
24.4
3
43.8
647
.90
49.7
0
65.2
765
.65
77.0
0
110.
5911
0.66
112.
1311
2.38
116.
3611
6.60
122.
8112
6.28
126.
5612
7.67
128.
7012
8.77
129.
0512
9.30
129.
6013
1.53
132.
0013
3.88
139.
71
158.
2716
0.69
168.
2717
1.22
13C NMR Spectrum of Compound (±)-5i (100 MHz, CDCl3)
BnN
O
NBus
O
Br
F
BnN
O
NBus
O
Br
F
S17
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
SHF-Bs-5Fester-4Brazi
-118
.137
19F NMR Spectrum of Compound (±)-5i (376 MHz, CDCl3)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
nmr feb 2016/5sh_bs_900
9.23
3.00
1.23
0.95
0.97
0.97
1.00
2.86
0.97
2.96
3.23
1.74
1.68
981.
7012
3.82
813.
8366
3.85
493.
8663
3.86
954.
1183
4.13
754.
1471
4.16
624.
1881
4.29
844.
3381
4.52
514.
5453
4.54
924.
5682
4.83
474.
8374
4.85
894.
8637
4.88
675.
1173
5.15
676.
4739
6.47
706.
4954
6.49
856.
5602
6.56
576.
5785
6.58
396.
7796
6.78
316.
7891
6.80
426.
8106
6.96
836.
9848
7.00
267.
0063
7.04
337.
0644
7.08
827.
0945
7.20
517.
2167
7.22
017.
2248
7.22
757.
2411
7.25
667.
2607
7.26
617.
2750
7.33
997.
3567
7.36
297.
3693
7.37
287.
3780
7.39
027.
3938
1H NMR Spectrum of Compound (±)-5j (400 MHz, CDCl3)
BnN
O
NBus
O
Br
OMe
BnN
O
NBus
O
Br
F
S18
0102030405060708090100110120130140150160170180190200f1 (ppm)
nmr feb 2016/7shc_bs_900
24.4
5
43.8
047
.86
49.7
0
55.8
5
65.2
665
.68
77.0
0
110.
4311
0.89
114.
75
122.
6112
6.26
126.
3312
7.49
128.
6612
8.93
129.
2912
9.60
131.
8813
4.30
137.
03
156.
61
168.
7817
1.19
13C NMR Spectrum of Compound (±)-5j (100 MHz, CDCl3)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
nmr feb 2016/9sh_bs_899
9.76
3.11
1.02
0.96
0.99
0.99
1.00
0.93
1.86
1.69
1.27
3.29
1.48
1.52
1.70
19
2.43
14
4.12
914.
1484
4.15
774.
1768
4.31
604.
3557
4.52
474.
5443
4.54
824.
5679
4.83
044.
8540
4.85
894.
8825
5.12
265.
1625
6.47
536.
4952
6.55
966.
5673
6.57
296.
5867
6.59
146.
9631
6.96
776.
9744
6.99
076.
9955
7.03
277.
0537
7.06
607.
0859
7.20
217.
2182
7.22
537.
2407
7.25
547.
2599
7.26
607.
2764
7.29
537.
3147
7.31
877.
3410
7.35
827.
3634
7.37
047.
3758
7.38
007.
3867
7.39
15
1H NMR Spectrum of Compound (±)-5k (400 MHz, CDCl3)
BnN
O
NBus
O
Br
OMe
BnN
O
NBus
O
Br
Me
S19
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
nmr feb 2016/10shc_bs_899
21.1
3
24.4
8
43.7
447
.77
49.7
0
65.2
265
.35
77.0
0
109.
58
122.
5812
4.75
125.
1612
6.35
127.
4812
8.66
129.
2812
9.59
130.
3113
1.88
131.
9813
3.41
134.
3814
1.35
169.
0217
1.43
13C NMR Spectrum of Compound (±)-5k (400 MHz, CDCl3)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
nmr feb 2016/sh-bs-920sh_bs_920
8.50
1.09
1.06
1.02
1.02
1.00
2.75
2.02
6.41
1.80
0.93
1.62
991.
6918
4.14
674.
1662
4.17
534.
1949
4.32
974.
3695
4.51
884.
5392
4.54
314.
5623
4.83
294.
8571
4.86
174.
8852
5.12
585.
1657
6.55
386.
5736
6.59
477.
0082
7.01
377.
0291
7.03
707.
1931
7.20
077.
2066
7.21
327.
2190
7.22
227.
2298
7.23
237.
2452
7.26
007.
2774
7.28
097.
2961
7.32
737.
3348
7.33
707.
3403
7.47
717.
4807
7.49
59
1H NMR Spectrum of Compound (±)-5l (400 MHz, CDCl3)
BnN
O
NBus
O
Br
Me
BnN
O
NBus
O
Cl
S20
102030405060708090100110120130140150160170180190200f1 (ppm)
nmr aug 2016/11SHc-BS-9203
24.4
8
43.7
347
.79
49.7
3
65.2
665
.42
77.0
0
109.
84
123.
7112
4.09
125.
1512
6.31
127.
5312
8.64
128.
9612
9.26
129.
9813
1.30
134.
24
143.
79
168.
8217
1.51
13C NMR Spectrum of Compound (±)-5l (400 MHz, CDCl3)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
9.37
1.00
1.00
1.02
0.98
1.01
0.96
1.91
2.03
4.78
1.10
0.86
1.71
15
4.15
904.
1787
4.18
724.
2070
4.31
814.
3580
4.53
594.
5557
4.55
984.
5795
4.84
104.
8651
4.86
944.
8933
5.13
985.
1797
6.46
586.
4867
6.54
966.
5679
7.07
037.
0911
7.21
967.
2239
7.22
847.
2408
7.24
557.
2600
7.27
567.
2808
7.29
337.
3533
7.40
067.
4055
7.42
157.
4264
7.65
387.
6586
1H NMR Spectrum of Compound (±)-5m (400 MHz, CDCl3)
BnN
O
NBus
O
Cl
Br
BnN
O
NBus
O
Cl
S21
0102030405060708090100110120130140150160170180190200f1 (ppm)
nmr feb 2016/24shc_bs_919
24.4
5
43.7
947
.79
49.7
3
65.2
565
.39
77.0
0
111.
2811
6.28
126.
2812
7.15
127.
3212
7.71
128.
7312
9.08
129.
3013
0.95
132.
8913
3.74
134.
69
142.
80
168.
20
170.
99
13C NMR Spectrum of Compound (±)-5m (400 MHz, CDCl3)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
SH-BS-4F_azi+NBn
9.46
1.00
1.00
0.99
0.99
0.98
2.91
1.98
2.00
4.95
0.96
1.62
64
4.09
274.
1171
4.13
964.
2782
4.31
804.
4541
4.47
574.
4969
4.76
694.
7929
4.81
855.
0337
5.07
35
6.50
376.
5194
6.83
626.
8569
6.87
766.
9810
6.99
347.
0117
7.09
207.
1090
7.12
727.
1582
7.17
587.
1885
7.20
827.
2260
7.26
007.
4122
7.42
97
1H NMR Spectrum of Compound (±)-5n (400 MHz, CDCl3)
BnN
O
NBus
O
Cl
Br
BnN
O
NBus
O
F
S22
0102030405060708090100110120130140150160170180190200f1 (ppm)
SHC-BS-4F_azi+NBn
24.4
8
43.6
747
.71
49.9
4
65.2
265
.50
77.0
0
109.
78
115.
6111
5.82
123.
6712
4.09
125.
2912
6.34
127.
4912
8.57
128.
6212
9.58
129.
6612
9.92
134.
3214
3.81
161.
4916
3.95
168.
8817
1.60
13C NMR Spectrum of Compound (±)-5n (100 MHz, CDCl3)
-260-250-240-230-220-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40f1 (ppm)
SHF-BS-4F_azi+NBn
-113
.119
19F NMR Spectrum of Compound (±)-5n (376 MHz, CDCl3)
BnN
O
NBus
O
F
S23
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
212AH.212
8.55
1.02
1.03
1.02
0.97
1.00
1.02
1.95
0.94
1.00
4.31
1.84
1.61
4.04
4.06
4.07
4.09
4.22
4.26
4.30
4.44
4.47
4.49
4.73
4.76
4.78
5.04
5.08
6.44
6.46
6.55
6.57
6.90
6.92
7.01
7.03
7.05
7.11
7.12
7.14
7.16
7.16
7.18
7.19
7.26
7.41
7.44
1H NMR Spectrum of Compound (±)-5o (400 MHz, CDCl3)
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
212AHc.212
24.4
4
43.8
947
.74
49.7
8
65.2
765
.34
110.
8612
2.98
124.
5412
6.36
126.
7512
6.80
127.
6612
8.81
129.
1413
0.06
130.
3713
0.69
131.
8013
3.90
134.
9114
2.31
168.
1517
1.07
13C NMR Spectrum of Compound (±)-5o (100 MHz, CDCl3)
BnN
O
NBus
O
Br
Cl
BnN
O
NBus
O
Br
Cl
S24
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
213AH.213
8.34
1.18
1.05
1.25
1.20
1.00
0.80
1.39
1.46
0.78
2.86
2.96
1.64
1.58
1.64
4.05
4.07
4.09
4.29
4.33
4.47
4.50
4.52
4.77
4.80
4.82
5.07
5.11
6.46
6.47
6.48
6.49
6.58
6.60
6.92
6.95
6.97
7.04
7.06
7.08
7.15
7.17
7.19
7.21
7.26
7.28
7.45
7.46
1H NMR Spectrum of Compound (±)-5p (400 MHz, CDCl3)
0102030405060708090100110120130140150160170180190200f1 (ppm)
Atanu hazra dec 2015AHc.213
24.4
4
43.9
347
.85
49.7
8
65.3
065
.61
110.
6411
0.72
112.
1011
2.36
116.
4311
6.67
122.
9712
6.36
126.
7212
7.63
128.
8013
0.36
130.
7713
1.79
134.
0313
4.95
139.
74
158.
3216
0.74
168.
23
171.
23
13C NMR Spectrum of Compound (±)-5p (100 MHz, CDCl3)
BnN
O
NBus
O
Br
F
BnN
O
NBus
O
Br
F
S25
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
AH-213
-118
.077
19F NMR Spectrum of Compound (±)-5p (376 MHz, CDCl3)
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
sh-nk-NOS 51
1.11
1.09
1.00
1.10
1.06
1.68
0.90
1.87
1.71
1.75
2.66
0.88
0.85
1.06
2.50
0
3.64
43.
655
3.66
54.
170
4.18
24.
194
4.34
94.
359
4.36
24.
372
4.47
74.
497
4.86
44.
885
6.55
76.
566
6.61
46.
624
7.01
77.
027
7.06
37.
072
7.08
27.
107
7.11
67.
123
7.12
57.
132
7.14
27.
177
7.18
67.
195
7.20
57.
278
7.28
77.
296
7.54
47.
553
8.65
8
1H NMR Spectrum of Compound 7b (400 MHz, DMSO-d6)
BnN
O
NH
O
BnN
O
NBus
O
Br
F
S26
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
nk-unsubs. -nh-51 13 C
39.5
242
.19
42.8
249
.57
63.1
2
109.
0112
2.68
123.
9212
6.38
126.
9412
7.56
127.
9212
7.99
128.
2812
8.33
128.
6613
5.34
135.
4814
3.71
171.
7317
2.74
13C NMR Spectrum of Compound 7b (400 MHz, DMSO-d6)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)
SH-NK-5Me-nos-dep
2.93
1.00
0.96
1.00
0.98
0.96
0.98
1.97
6.14
2.05
1.06
1.00
0.93
2.30
74
2.50
00
3.63
063.
6509
3.67
154.
1348
4.15
994.
1839
4.29
804.
3181
4.34
324.
4327
4.47
294.
8255
4.86
55
6.48
996.
5096
6.55
746.
5754
6.97
736.
9972
7.01
657.
0354
7.04
887.
0680
7.08
637.
1123
7.12
997.
1475
7.17
787.
1961
7.21
487.
2638
7.28
177.
2995
7.35
918.
6079
1H NMR Spectrum of Compound 7c (400 MHz, DMSO-d6)
BnN
O
NH
O
BnN
O
NH
O
Me
S27
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
SH-NK-5Me-NOS-DEP
21.2
2
42.7
043
.35
50.0
2
63.5
9
109.
2412
5.00
126.
8612
7.40
128.
0112
8.41
128.
5312
8.75
128.
7912
9.35
132.
2113
5.88
136.
0614
1.82
172.
3817
3.16
13C NMR Spectrum of Compound 7c (100 MHz, DMSO-d6)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
nk-dep-5 Cl-L
1.00
1.00
0.81
1.24
1.00
2.03
1.02
4.12
1.16
4.25
1.03
1.01
2.50
00
3.33
523.
6231
3.64
403.
6649
4.15
534.
1804
4.20
484.
4337
4.45
404.
4822
4.52
324.
8579
4.89
816.
5425
6.56
076.
6306
6.65
167.
0408
7.05
947.
0769
7.09
577.
1238
7.14
167.
1595
7.20
387.
2220
7.24
127.
2505
7.25
557.
2717
7.27
687.
2836
7.30
227.
3203
7.73
897.
7436
8.70
87
1H NMR Spectrum of Compound 7d (400 MHz, DMSO-d6)
BnN
O
NH
O
Me
BnN
O
NH
O
Cl
S28
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
nk-dep-61
39.5
242
.88
43.4
749
.86
64.0
2
100.
14
111.
06
125.
0412
6.99
127.
5412
7.68
128.
3112
8.55
129.
0212
9.22
130.
6213
5.60
135.
8914
3.20
171.
7317
3.04
13C NMR Spectrum of Compound 7d (100 MHz, DMSO-d6)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
sh_nknos_dep65
1.08
1.04
1.07
1.05
1.10
1.99
1.03
6.24
2.08
1.13
1.00
1.04
2.50
00
3.63
143.
6519
3.67
254.
1666
4.19
234.
2162
4.40
184.
4216
4.42
804.
4477
4.47
984.
5201
4.85
854.
8987
6.55
566.
5737
6.60
176.
6123
6.62
306.
6338
7.02
197.
0284
7.05
117.
0689
7.08
237.
1014
7.12
837.
1411
7.14
627.
1525
7.16
447.
2055
7.22
377.
2431
7.28
967.
3079
7.32
637.
5657
7.57
227.
5867
7.59
328.
6926
1HNMR Spectrum of Compound 7e (400 MHz, DMSO-d6)
BnN
O
NH
O
Cl
BnN
O
NH
O
F
S29
0102030405060708090100110120130140150160170180190200f1 (ppm)
sh_nknos_dep6513C
39.5
242
.94
43.5
1
50.0
5
64.2
9
110.
4711
0.55
112.
7311
2.98
115.
5111
5.74
127.
0412
7.68
128.
3412
8.61
129.
0313
0.39
130.
4813
5.76
135.
9414
0.54
158.
1516
0.51
171.
8917
3.22
13C NMR Spectrum of Compound 7e (100 MHz, DMSO-d6)
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
NKF-5F-NH-spiro
-119
.367
19F NMR Spectrum of Compound 7e (376 MHz, CDCl3)
BnN
O
NH
O
F
BnN
O
NH
O
F
S30
HPLC Chromatograms
HPLC Chromatogram of recovered aziridine (±)-4a HPLC Chromatogram of recovered aziridine 4a
HPLC condition 4a: CHIRALCEL OJ-H, 30% iPrOH/n-Hexane, 1ml/min, 254 nm, tR = 16.644 min (major) tR = 21.331 min (minor)
S31
HPLC Chromatogram of Compound (±)-5b HPLC Chromatogram of Compound 5b
S32
HPLC Chromatogram of Compound (±)-5d HPLC Chromatogram of Compound 5d
S33
HPLC Chromatogram of Compound (±)-5e HPLC Chromatogram of Compound 5e
S34
HPLC Chromatogram of Compound (±)-5f HPLC Chromatogram of Compound 5f
S35
HPLC Chromatogram of Compound (±)-5g HPLC Chromatogram of Compound 5g
S36
HPLC Chromatogram of Compound (S)-5u (reported enantiomer) HPLC Chromatogram of Compound (R)-5u (other enantiomer)
S37
HPLC Chromatogram of Compound (R)-5v (reported enantiomer) HPLC Chromatogram of Compound (S)-5v (other enantiomer)
S38
HPLC Chromatogram of Compound (S)-5w (reported enantiomer) HPLC Chromatogram of Compound (R)-5w (other enantiomer)
S39
HPLC Chromatogram of Compound (±)-7b HPLC Chromatogram of Compound 7b
S40
HPLC Chromatogram of Compound (±)-7c HPLC Chromatogram of Compound 7c
S41
HPLC Chromatogram of Compound (±)-7d HPLC Chromatogram of Compound 7d
S42
HPLC Chromatogram of Compound (±)-7e HPLC Chromatogram of Compound 7e
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