Post on 06-Jun-2021
S1
Supporting Information
Protonated montmorillonite-mediated highly specific
isomerization of oleanolic acid esters: application to the
synthesis of Δ13(18)-CDDO-Me
Dongyin Chen,a,c Pu Zhang,a Yan Sun,a Pengfei Wang,a Can Zhang,a Lingyi Kong,a
Ji Zhang,*,b Hongbin Sun*,a and Xiaoan Wen *,a
a 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
b Department of Physical Chemistry, China Pharmaceutical University, 24 Tongjia Xiang,
Nanjing 210009, China
c Department of Medicinal Chemistry, School of Pharmacy, Nanjing Medical University, 101
Longmian Avenue, Nanjing 211166, China
jzhangcpu@126.com; hongbinsun@cpu.edu.cn; wxagj@126.com
Table of contents
1. 1H and 13C NMR data of oleanolic acid (1) and δ-oleanolic acid (2) …………………………….S2-S3
2. Copies of 1H and 13C NMR for new compounds 5d-5i and 6a-6h …………………………….S4-S31
3. Copies of 1H and 13C NMR foroleanolic acid (1) and -oleanolic acid (2) ……………….S32-S35
4. Copies of 1H and 13C NMR for new compounds 7-12 …………………………………………….S36-S47
5. Copies of 1H and 13C NMR for Δ13(18)-CDDO-Me (4) ……………………………………………….S48-S49
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2016
S2
Table 1. Chemical shifts of specific H and C atoms of oleanolic acid (1) and δ-oleanolic acid
(2)a
HOH
H
CO2H
oleanolic acid (1)
12
3 5
67
8
9
10
1112
1314
1516
1718
19 2021
22
2324
25 26
27
28
29
4
30
H
13C NMR (500 MHz, C5D5N) 1H NMR (125 MHz, C5D5N)atom δC atom δH
C-3 79.4 3β-H 3.42 (dd, J = 10.6, 5.5 Hz, 1H)C-12 123.8 12-H 5.48 (t, J = 3.3 Hz, 1H)C-13 146.1 18β-H 3.29 (dd, J = 13.8, 4.0 Hz, 1H)C-18 43.3 11-H 2.07-2.20 (m, 2H)C-28 181.4
HOH
H
CO2H
-oleanolic acid (2)
12
3 5
67
8
9
10
1112
1314
1516
1718
19 2021
22
2324
25 26
27
28
29
4
30
13C NMR (500 MHz, C5D5N) 1H NMR (125 MHz, C5D5N)atom δC atom δH
C-3 79.4 3β-H 3.46 (dd, J = 10.1, 6.0 Hz, 1H)
C-12 25.7 12-H2.84 (dd, J = 14.6, 2.0 Hz, 1H)
2.60 (d, J = 14.0 Hz, 1H)
C-13 139.2 19-H2.24-2.26 (m, 1H)1.91-1.95 (m, 1H)
C-18 130.6C-28 180.2
a In the 1H NMR spectrum, the signal due to the olefinic proton resonating at 5.48 (t, J = 3.3 Hz, 1H) is characteristic of oleanolic acid; the signals due to the allylic protons resonating at 2.84 (dd, J = 14.6, 2.0 Hz, 1H) and 2.60 (d, J = 14.0 Hz, 1H) is characteristic of δ-oleanolic acid. In the 13C NMR spectrum, the signals due to the olefinic carbons resonating at 123.8 and 146.1 is characteristic of oleanolic acid (1); the signals due to the olefinic carbons resonating at 130.6 and 139.2 is characteristic of δ-oleanolic acid (2).
S3
1H and 13C NMR data of oleanolic acid (1) and δ-oleanolic acid (2) as following:
Oleanolic acid (1). 1H NMR (500 MHz, C5D5N) δ 5.48 (t, J = 3.3 Hz, 1H), 3.42 (dd, J = 10.6, 5.5
Hz, 1H), 3.29 (dd, J = 13.8, 4.0 Hz, 1H), 2.07-2.20 (m, 2H), 2.00-2.06 (m, 1H), 1.93-1.96 (m,
3H), 1.78-1.83 (m, 4H), 1.68 (t, J = 8.9 Hz, 1H), 0.85-1.58 (m, 11H), 1.27 (s, 3H), 1.22 (s, 3H),
1.02 (s, 3H), 1.01 (s, 3H), 1.00 (s, 3H), 0.94 (s, 3H), 0.89 (s, 3H); 13C NMR (125 MHz, C5D5N) δ
181.4, 146.1, 123.8, 79.4, 57.1, 49.4, 48.0, 47.8, 43.5, 43.3, 41.1, 40.6, 40.2, 38.7, 35.5, 34.6,
34.5, 34.5, 32.2, 30.0, 29.6, 29.4, 27.4, 25.1, 25.1, 25.0, 20.1, 18.7, 17.8, 16.8.
δ-oleanolic acid (2). 1H NMR (500 MHz, C5D5N) δ 3.46 (dd, J = 10.1, 6.0 Hz, 1H), 2.84 (dd, J =
14.6, 2.0 Hz, 1H), 2.60 (d, J = 14.0 Hz, 1H), 2.52-2.55 (m, 1H), 2.24-2.26 (m, 1H), 2.18 (d, J =
13.9 Hz, 1H), 2.05 (t, J = 12.9 Hz, 1H), 1.91-1.95 (m, 1H), 1.84-1.89 (m, 2H), 0.87-1.73 (m,
15H), 1.24 (s, 3H), 1.22 (s, 3H), 1.14 (s, 3H), 1.00 (s, 3H), 0.95 (s, 3H), 0.89 (s, 3H), 0.84 (s, 3H);
13C NMR (125 MHz, C5D5N) δ 180.2, 139.2, 130.6, 79.4, 57.2, 52.5, 50.1, 46.1, 43.1, 42.8, 40.7,
40.6, 39.0, 38.7, 37.7, 36.8, 34.9, 34.2, 33.6, 30.0, 29.5, 29.1, 26.9, 25.7, 23.4, 22.6, 20.1, 19.4,
17.9, 17.7.
S4
1H NMR of 5d
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5
3.50
2.97
5.76
4.11
2.19
3.24
3.83
23.21
1.05
1.04
2.06
1.00
0.00
0.07
0.57
0.74
0.91
0.95
0.99
1.09
1.21
1.34
1.42
1.51
1.60
1.65
1.75
1.89
2.87
2.91
3.21
3.48
3.97
3.98
5.29
H
H
CO2n-Pr
HO
5d
S5
13C NMR of 5d
0102030405060708090100110120130140150160170180190200210
10.55
15.55
21.97
23.39
25.85
27.62
30.67
32.73
38.43
45.88
47.60
55.20
65.78
76.58
77.00
77.42
78.98
122.3
2
143.7
9
177.7
8H
H
CO2n-Pr
HO
5d
S6
1H NMR of 5e
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
1.06
3.51
2.44
3.14
3.89
6.83
20.76
1.03
1.02
0.97
1.00
0.01
0.08
0.72
0.90
0.99
1.18
1.23
1.34
1.48
1.60
1.87
1.90
1.94
1.95
2.85
2.89
2.96
3.19
3.21
3.23
3.24
4.90
4.92
4.94
4.96
4.98
5.29
7.28
H
H
CO2i-Pr
HO
5e
S7
13C NMR of 5e
0102030405060708090100110120130140150160170180190200210220
15.29
15.55
17.16
18.30
21.71
22.86
23.56
27.17
28.08
32.38
33.09
45.92
47.60
55.20
66.99
76.57
76.99
77.42
78.96
122.2
3
143.7
6
177.0
4
H
H
CO2i-Pr
HO
5e
S8
1H NMR of 5f
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5
0.65
3.26
3.15
6.04
4.51
3.24
1.10
3.26
25.21
1.01
1.03
2.05
1.00
0.00
0.07
0.54
0.62
0.67
0.74
0.84
0.91
0.96
1.04
1.14
1.27
1.31
1.33
1.35
1.40
1.45
1.50
1.60
2.86
2.89
2.91
3.21
3.23
3.24
4.00
4.02
4.04
5.28
7.28
H
H
CO2n-Bu
HO
5f
S9
13C NMR of 5f
0102030405060708090100110120130140150160170180190200210220230
13.68
15.27
15.55
16.97
18.31
19.21
22.98
25.84
28.08
32.74
37.00
39.31
45.87
47.60
55.20
63.95
76.58
77.00
77.42
78.97
122.3
2
143.7
8
177.7
5
H
H
CO2n-Bu
HO
5f
S10
1H NMR of 5g
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5
3.60
3.14
5.89
6.00
3.24
3.33
3.39
23.33
1.01
1.04
2.04
1.00
-0.0
10.
06
0.69
0.76
0.89
0.93
1.02
1.07
1.15
1.25
1.33
1.40
1.49
1.53
1.57
1.63
1.67
1.85
2.85
2.86
2.89
2.91
3.17
3.45
3.72
3.76
3.77
3.78
3.79
3.82
5.27
7.27
H
H
CO2i-Bu
HO
5g
S11
13C NMR of 5g
0102030405060708090100110120130140150160170180190200210220
15.2
215
.52
16.8
918
.25
19.1
222
.92
25.8
127
.62
32.4
633
.81
38.6
6
45.8
0
47.5
355
.15
70.3
2
76.5
676
.99
77.4
178
.85
122.3
3
143.7
1
177.6
4
H
H
CO2i-Bu
HO
5g
S12
1H NMR of 5h
1.95
44
2.00
71
0.96
66
2.00
98
1.00
00
0.93
26
1.16
151.
9374
10.5
62
5.18
52
7.65
41
13.3
554.
3070
2.91
23
Inte
gral
8.23
988.
2120
7.53
677.
5089
7.27
247.
2700
5.30
725.
2368
5.19
185.
1391
5.09
403.
4984
3.23
783.
2225
3.20
323.
1867
2.92
362.
8923
2.08
062.
0347
2.02
191.
9893
1.86
981.
8457
1.77
331.
7431
1.71
581.
6981
1.67
031.
6466
1.62
491.
5923
1.55
571.
5243
1.45
151.
4004
1.36
101.
3144
1.25
281.
2130
1.14
621.
1056
1.07
020.
9910
0.93
910.
9222
0.87
070.
7806
0.73
880.
7018
0.57
790.
0128
0.01
08
(ppm)0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
CDY-OA-1 H1-NMR CDCl3 300K AV-300
H
H
CO2(p-NO2-Bn)
HO
5h
S13
13C NMR of 5h
177.
1644
143.
6713
143.
5467
128.
3972
123.
6794
122.
6611
78.9
413
77.4
176
76.9
927
76.5
678
64.5
243
55.1
914
47.5
360
46.8
767
45.7
778
41.6
901
41.4
410
39.2
946
38.7
158
38.4
228
36.9
797
33.7
710
33.0
164
32.6
868
32.4
157
30.6
576
28.0
716
27.5
808
27.1
705
25.8
519
23.5
809
23.3
758
23.1
048
18.2
625
16.8
706
15.5
300
15.2
150
(ppm)0102030405060708090100110120130140150160170180190200210
CDY-OA-1 13C-NMR CDCl3 303K AV-300
H
H
CO2(p-NO2-Bn)
HO
5h
S14
1H NMR of 5i
1.44
910.
6769
2.19
03
1.01
92
2.05
92
3.32
24
1.07
04
1.00
00
1.45
302.
0377
14.2
74
7.85
663.
2383
5.52
3510
.216
5.04
813.
0155
Inte
gral
7.27
997.
2580
7.25
12
6.88
046.
8516
5.26
795.
0523
5.01
174.
9918
4.95
12
4.56
62
3.80
76
3.48
793.
2299
3.19
612.
8976
2.86
591.
9640
1.91
971.
8639
1.83
491.
8234
1.67
801.
6320
1.60
601.
5844
1.53
601.
4867
1.42
991.
3927
1.35
651.
3146
1.26
091.
2034
1.14
631.
1159
1.04
760.
9972
0.98
170.
9086
0.88
600.
7761
0.73
080.
6940
0.60
27-0
.000
0
(ppm)0.01.02.03.04.05.06.07.08.09.0
CDY-OA-2 1H-NMR CDCl3 300K AV-300
H
H
CO2(p-CH3O-Bn)
HO
5i
S15
13C NMR of 5i
177.
4427
159.
3995
143.
7079
129.
7817
128.
6169
122.
4267
113.
7750
78.9
852
77.4
248
77.0
000
76.5
751
65.6
891
55.2
499
55.2
280
47.6
239
46.6
642
45.8
877
41.6
827
41.3
897
39.2
945
38.7
378
38.4
594
37.0
162
33.8
589
33.0
823
32.7
307
32.3
424
30.6
722
28.0
935
27.6
100
27.1
998
25.8
445
23.6
395
23.3
904
23.0
241
18.3
064
16.8
999
15.5
592
15.2
662
(ppm)0102030405060708090100110120130140150160170180190200210220
CDY-OA-2 13C-NMR CDCl3 303K AV-300
H
H
CO2(p-CH3O-Bn)
HO
5i
S16
1H NMR of 6a
5.48
52
2.46
35
1.16
46
1.00
00
0.99
81
1.12
49
2.08
751.
4917
4.62
156.
9261
8.13
753.
1840
1.68
465.
3391
6.84
243.
0715
4.34
103.
9969
0.31
05
Integ
ral
7.33
337.
2927
7.25
84
5.16
525.
1489
5.12
435.
1010
5.07
675.
0601
3.24
243.
2241
3.20
683.
1882
2.74
832.
7097
2.42
522.
3783
2.21
732.
1754
1.93
051.
8869
1.83
801.
7585
1.71
521.
6450
1.62
741.
6057
1.58
051.
5335
1.48
831.
4673
1.43
071.
4214
1.39
911.
3449
1.30
761.
2936
1.28
201.
2537
1.20
151.
1732
1.13
691.
0844
1.04
040.
9766
0.95
430.
9177
0.89
470.
8624
0.84
780.
8278
0.79
260.
7583
0.72
200.
6997
0.60
890.
0000
(ppm)0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5
ZP-04-11 1H-NMR CDCL3 300K AV-300
H
H
CO2Bn
HO
6a
S17
13C NMR of 6a
176.
5710
138.
3455
136.
3969
132.
4556
128.
3532
128.
2946
127.
9723
127.
8038
122.
4927
78.9
853
77.4
249
77.0
000
76.5
751
66.2
166
66.0
334
65.9
016
55.4
771
55.3
159
51.1
403
50.7
374
48.5
030
44.3
274
41.2
726
41.0
162
38.8
477
38.8
038
38.4
448
37.3
093
36.7
819
35.8
296
34.9
065
34.5
329
33.8
589
33.4
633
33.3
461
32.9
725
32.6
136
32.3
718
32.0
934
30.3
499
29.2
877
29.1
558
28.0
716
27.9
398
27.6
174
27.3
610
27.0
460
25.9
618
25.8
666
25.1
999
24.1
743
21.6
104
21.0
536
20.8
778
18.3
138
18.1
892
17.5
006
16.6
142
16.3
285
15.8
157
15.4
787
15.3
688
14.9
000
(ppm)0102030405060708090100110120130140150160170180190200
ZP-04-11 13C-NMR CDCL3 300K AV-300
H
H
CO2Bn
HO6a
S18
1H NMR of 6b
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0
3.35
3.22
3.06
6.14
3.26
1.88
2.93
17.82
1.17
1.96
0.99
0.91
0.91
1.00
2.99
-0.0
0
0.73
0.88
0.96
1.01
1.07
1.13
1.20
1.26
1.30
1.34
1.37
1.39
1.45
1.49
2.16
2.19
2.40
2.45
2.71
2.72
2.76
3.20
3.22
3.23
3.25
3.62
3.65
3.67
7.26
H
H
CO2Me
HO6b
S19
13C NMR of 6b
0102030405060708090100110120130140150160170180190200210
15.47
16.34
17.35
18.33
21.08
21.63
24.15
25.18
27.11
28.08
32.10
34.94
37.35
41.13
48.51
55.36
76.57
76.99
77.42
79.01
127.8
8
138.2
3
177.3
7
H
H
CO2Me
HO6b
S20
1H NMR of 6c
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5
2.73
3.25
2.52
2.66
3.34
3.28
1.54
3.09
24.46
1.76
0.96
0.90
0.90
1.00
2.03
-0.0
0
0.77
0.86
0.91
0.99
1.08
1.13
1.23
1.30
1.36
1.41
1.49
1.60
1.85
2.16
2.20
2.40
2.45
2.71
2.73
2.77
3.20
3.22
3.23
3.25
4.07
4.09
4.10
4.11
4.12
4.13
4.14
4.16
4.17
4.18
7.27
H
H
CO2Et
HO6c
S21
13C NMR of 6c
0102030405060708090100110120130140150160170180190200210
14.2
615
.48
16.3
517
.63
18.3
321
.03
21.6
324
.13
25.1
927
.06
28.0
832
.16
34.9
837
.35
41.1
5
48.3
6
55.3
5
60.2
6
76.5
877
.00
77.4
378
.99
128.0
0
138.0
6
176.8
8H
H
CO2Et
HO6c
S22
1H NMR of 6d
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0
3.04
3.34
3.09
6.33
3.44
3.14
2.10
2.88
21.52
1.26
1.96
1.00
0.94
0.92
1.00
2.02
-0.00
0.74
0.83
0.88
0.94
0.99
1.07
1.13
1.21
1.29
1.34
1.40
1.43
1.46
1.65
2.17
2.20
2.40
2.45
2.71
2.73
2.77
3.20
3.22
3.23
3.25
4.00
4.03
4.05
7.26
H
H
CO2n-Pr
HO6d
S23
13C NMR of 6d
0102030405060708090100110120130140150160170180190200
10.4
2
15.3
517
.47
20.9
221
.94
27.9
632
.05
32.9
935
.78
37.2
440
.99
48.3
6
55.2
4
65.9
2
76.4
576
.87
77.2
978
.89
127.9
2
137.9
6
176.8
0
H
H
CO2n-Pr
HO6d
S24
1H NMR of 6e
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0
3.11
3.51
2.70
2.88
3.19
3.17
2.14
2.79
2.88
3.18
5.34
2.80
8.81
1.20
1.98
1.00
0.90
0.89
1.00
1.00
-0.0
0
0.77
0.88
0.99
1.07
1.15
1.23
1.30
1.39
1.46
1.51
1.60
1.84
2.11
2.39
2.44
2.71
2.72
2.76
3.20
3.22
3.23
3.25
4.96
4.98
5.00
5.02
5.04
5.06
5.08
7.26
H
H
CO2i-Pr
HO6e
S25
13C NMR of 6e
0102030405060708090100110120130140150160170180190200210
15.44
16.32
17.83
18.30
20.95
21.60
21.72
21.78
24.08
28.05
32.20
34.98
37.32
41.09
48.26
55.31
67.42
76.54
76.96
77.38
78.96
128.0
5
137.8
9
176.3
1H
H
CO2i-Pr
HO6e
S26
1H NMR of 6f
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0
2.98
3.14
2.99
6.09
1.73
1.41
3.06
2.07
2.66
23.07
1.85
1.00
0.93
0.94
1.00
2.00
0.00
0.74
0.83
0.88
0.93
0.99
1.07
1.13
1.25
1.30
1.36
1.41
1.60
2.17
2.40
2.44
2.73
2.76
3.20
3.22
3.24
3.25
4.04
4.07
4.09
7.26
H
H
CO2n-Bu
HO6f
S27
13C NMR of 6f
0102030405060708090100110120130140150160170180190200
13.6
415
.47
16.3
417
.56
18.3
419
.21
21.0
521
.64
24.1
625
.21
27.1
027
.38
28.0
830
.73
32.1
6
41.1
048
.46
55.3
6
64.2
0
76.7
276
.98
77.2
379
.00
128.0
4
138.0
7
176.8
9
H
H
CO2n-Bu
HO6f
S28
1H NMR of 6g
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5
2.92
3.26
2.79
5.04
3.12
3.15
3.22
1.50
2.86
19.30
2.99
1.01
0.93
0.90
1.00
1.98
-0.00
0.07
0.72
0.88
0.94
1.05
1.13
1.26
1.30
1.37
1.43
1.49
1.64
1.92
2.14
2.40
2.45
2.72
2.73
2.78
3.20
3.21
3.25
3.79
3.81
3.82
3.84
3.86
3.88
3.89
3.92
7.27
H
H
CO2i-Bu
HO6g
S29
13C NMR of 6g
0102030405060708090100110120130140150160170180190200210
15.44
16.31
17.56
18.30
19.20
19.27
21.02
21.61
24.15
25.18
28.05
32.13
34.91
37.30
41.01
48.50
55.31
70.65
76.55
76.98
77.40
78.94
127.9
9
138.1
0
176.7
9H
H
CO2i-Bu
HO6g
S30
1H NMR of 6h
H
H
CO2(p-NO2-Bn)
HO6h
S31
13C NMR of 6h
176.
3439
143.
6566
138.
8876
128.
6096
127.
4082
123.
7014
78.9
779
77.4
249
77.0
000
76.5
751
64.8
247
55.3
232
50.7
007
48.5
616
44.3
713
41.3
018
41.1
407
38.8
550
38.8
184
37.3
313
36.8
698
35.8
442
34.9
065
32.9
945
32.6
868
32.1
227
28.0
789
27.3
610
27.0
533
25.2
439
24.1
230
21.6
103
21.1
122
18.3
064
17.5
885
16.3
505
15.4
714
(ppm)0102030405060708090100110120130140150160170180190200210220
CDY-OA-3 13C-NMR CDCl3 303K AV-300
H
H
CO2(p-NO2-Bn)
HO6h
S32
1H NMR of 1
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
1.09
3.08
3.07
0.65
3.21
3.01
3.38
1.88
3.38
3.33
7.20
1.07
4.25
3.14
1.02
2.05
0.94
1.00
1.11
0.85
0.87
0.89
0.91
0.94
0.97
0.98
1.01
1.18
1.31
1.38
1.46
1.51
1.66
1.80
1.94
2.03
2.08
2.14
3.27
3.28
3.30
3.31
3.41
3.42
3.43
3.44
5.47
5.48
5.49
7.18
7.55
8.69
5.425.465.505.545.58
1.11
5.47
5.48
5.49
3.253.303.353.403.453.50
0.94
1.00
3.27
3.28
3.30
3.31
3.41
3.42
3.43
3.44
1.901.952.002.052.102.152.20
3.14
1.02
2.05
1.93
1.94
1.95
1.96
2.00
2.03
2.06
2.07
2.10
2.12
2.14
2.17
2.19
2.20
HOH
H
CO2H
1
H
S33
13C NMR of 1
0102030405060708090100110120130140150160170180190200210220230240
16.81
17.77
18.70
20.07
24.99
27.43
30.04
34.52
43.30
47.78
47.95
57.11
79.37
123.8
3
146.1
0
181.3
9
1618202224262830
16.81
17.77
18.70
20.07
24.99
25.03
25.09
27.43
29.36
29.60
30.04
35404550
32.21
34.46
34.52
35.51
38.67
40.23
40.64
41.05
43.30
43.46
47.78
47.95
49.41
HOH
H
CO2H
1
H
S34
1H NMR of 2
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.38
0.75
3.21
2.91
3.38
1.27
3.09
1.35
3.19
3.22
7.62
7.00
2.19
1.24
1.12
1.00
0.99
0.86
0.97
0.89
1.00
0.84
0.92
1.00
1.04
1.10
1.16
1.24
1.32
1.37
1.43
1.48
1.61
1.71
1.80
1.85
2.19
2.52
2.82
2.83
2.85
3.44
3.45
3.46
3.47
7.18
7.55
8.69
3.383.403.423.443.463.483.50
1.00
3.44
3.45
3.46
3.47
2.52.62.72.82.9
0.86
0.97
0.89
2.52
2.55
2.55
2.58
2.61
2.82
2.83
2.85
2.85
2.002.052.102.152.202.252.302.35
1.12
1.00
0.99
2.03
2.06
2.08
2.17
2.19
2.24
2.26
HOH
H
CO2H
2
S35
13C NMR of 2
0102030405060708090100110120130140150160170180190200210220
17.71
17.94
19.43
20.08
22.58
23.37
25.73
26.85
29.07
30.03
33.62
36.77
38.95
42.84
50.09
57.18
79.39
130.5
5
139.1
8
180.2
3
32343638404244464850
33.62
34.22
34.93
36.77
37.74
38.69
40.61
40.72
42.84
43.09
46.06
50.09
1618202224262830
17.71
17.94
19.43
20.08
22.58
23.37
25.73
26.85
29.07
29.53
30.03
HOH
H
CO2H
2
S36
1H NMR of 7
0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.8f1 (ppm)
2.49
3.48
4.05
8.70
3.48
2.45
3.41
1.39
0.91
0.90
2.92
1.00
0.72
190.
8291
0.85
110.
8715
0.89
240.
9302
0.95
170.
9695
1.08
981.
1385
1.20
301.
2162
1.22
261.
3220
1.38
401.
3902
1.47
461.
4948
1.51
701.
6056
1.63
651.
6496
1.65
721.
7239
1.86
84
2.03
182.
0589
2.15
372.
1594
2.17
912.
1857
2.39
532.
4234
2.71
022.
7154
2.73
982.
7447
3.56
633.
6408
3.65
933.
6680
4.47
704.
4891
4.49
764.
5098
COOMe
AcO
7H
H
S37
13C NMR of 7
0102030405060708090100110120130140150160170180190200210220
16.35
16.55
17.32
18.23
21.04
21.15
21.63
23.67
24.16
28.02
32.06
34.88
37.29
41.12
48.51
55.51
76.53
76.95
77.37
80.94
128.0
0
138.1
4
170.8
0
177.2
2
COOMe
AcO
7H
H
S38
1H NMR of 8
1.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
6.05
3.21
2.81
2.63
2.87
3.86
14.8
5
1.14
2.74
1.48
1.03
0.95
2.69
1.00
0.86
330.
8925
0.92
480.
9425
0.95
961.
0636
1.22
101.
2654
1.43
401.
5973
1.62
921.
6419
1.67
26
1.93
032.
0381
2.04
15
2.23
902.
2458
2.28
562.
2966
2.34
212.
3486
2.36
742.
5141
2.55
93
3.68
203.
6856
4.46
074.
4776
4.49
424.
5116
7.26
67
COOMe
AcO
8H
H
O
S39
13C NMR of 8
0102030405060708090100110120130140150160170180190200210220230
15.91
16.49
16.56
18.14
21.14
23.46
24.44
25.96
27.95
32.03
35.52
37.99
45.43
49.00
55.43
76.55
76.98
77.40
80.44
141.5
214
2.11
170.6
7
175.7
3
205.9
8
COOMe
AcO
8H
H
O
S40
1H NMR of 9
0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.6f1 (ppm)
3.35
2.05
4.28
3.17
3.70
2.62
7.74
3.25
11.1
9
3.17
2.05
1.51
2.78
0.95
1.00
0.81
680.
8241
0.87
260.
8801
0.93
070.
9639
0.98
601.
0120
1.30
951.
3974
1.43
781.
4647
1.47
991.
5327
1.56
191.
5909
1.62
981.
6558
1.74
551.
7533
1.84
791.
8541
1.87
381.
8797
2.05
54
2.35
432.
3749
2.38
66
3.59
403.
6225
3.66
99
4.23
004.
2422
4.50
444.
5134
4.52
764.
5363
COOMe
AcO
9H
H
OBr
S41
13C NMR of 9
0102030405060708090100110120130140150160170180190200210220
16.32
16.49
17.28
17.97
21.11
22.73
23.38
24.27
27.87
32.30
34.35
36.45
42.85
48.58
52.14
58.48
76.54
76.96
77.39
80.28
136.9
6
153.3
2
170.6
5
175.4
3
195.1
2
COOMe
AcO
9H
H
OBr
S42
1H NMR of 10
1.01.52.02.53.03.54.04.55.05.56.0f1 (ppm)
5.92
2.97
2.99
2.99
4.34
4.08
12.3
2
1.04
1.12
3.03
1.10
0.99
3.00
1.04
1.00
0.91
290.
9518
0.96
451.
0005
1.02
181.
1109
1.22
811.
2850
1.31
371.
4618
1.46
671.
4948
1.51
841.
5292
1.53
991.
5669
1.63
421.
6626
1.68
311.
7074
1.78
361.
7925
2.06
09
2.33
882.
3662
3.40
493.
4315
3.69
11
4.48
484.
4938
4.50
824.
5172
5.85
59
COOMe
AcO
10H
O
S43
13C NMR of 10
0102030405060708090100110120130140150160170180190200210220
16.71
17.91
21.09
22.86
23.91
24.09
24.62
26.21
26.45
27.96
31.98
34.07
41.23
45.08
50.07
51.00
51.70
76.54
76.96
77.38
79.75
123.9
7
137.8
6
148.4
4
170.6
5
175.7
017
6.38
191.7
9
COOMe
AcO
10H
O
S44
1H NMR of 11
0.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.8f1 (ppm)
5.88
3.04
6.03
5.95
12.9
6
1.11
1.08
2.06
1.03
3.14
1.00
0.96
231.
0998
1.13
151.
2294
1.26
321.
2747
1.28
571.
3131
1.32
221.
3505
1.45
161.
4988
1.50
881.
5412
1.55
341.
5846
1.63
631.
6666
1.68
451.
8061
1.94
372.
3436
2.38
85
2.58
642.
6114
2.61
70
3.39
663.
4410
3.70
07
5.90
21
COOMe
O
11H
O
S45
13C NMR of 11
0102030405060708090100110120130140150160170180190200210220230
19.12
21.25
22.79
24.09
24.85
26.01
26.42
26.70
31.96
34.05
41.30
45.18
46.33
47.37
50.07
51.30
51.86
76.59
77.02
77.44
125.3
3
137.7
4
148.9
6
175.1
917
5.70
191.5
4
216.1
0
COOMe
O
11H
O
S46
1H NMR of 12
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
3.88
2.60
2.93
3.63
3.38
3.14
2.80
10.5
1
1.06
1.05
1.06
1.04
1.08
3.18
1.03
1.00
0.92
770.
9505
0.95
971.
1306
1.19
961.
2270
1.26
071.
2789
1.29
241.
3022
1.31
201.
3329
1.34
781.
4444
1.49
321.
5023
1.53
941.
5840
1.64
541.
6650
1.68
201.
7094
1.72
981.
7632
1.93
78
2.33
402.
3789
2.42
492.
4752
2.79
992.
8504
3.39
073.
4351
3.65
423.
6889
5.97
97
7.26
47
8.06
90
COOMe
12H
O
NO
S47
13C NMR of 12
0102030405060708090100110120130140150160170180190200210
18.20
21.31
22.83
24.12
25.39
25.65
26.55
28.80
31.99
32.11
32.39
33.83
35.82
41.34
45.42
50.10
50.47
51.87
76.60
77.02
77.44
108.6
2
125.5
8
137.7
1
149.0
615
0.22
172.1
817
4.48
175.6
7
191.4
5
COOMe
12H
O
NO
S48
1H NMR of 4
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.97
3.07
3.15
4.18
3.60
3.78
6.19
1.62
1.23
1.19
3.53
1.03
1.00
0.95
630.
9654
1.11
561.
1807
1.20
361.
2145
1.24
071.
2745
1.28
811.
3164
1.32
481.
3800
1.51
031.
5456
1.59
281.
7582
1.79
26
2.35
122.
3615
2.39
62
3.40
023.
4446
3.47
933.
7007
6.06
24
7.26
26
8.11
42
CO2Me
H
O
O
NC
13(18)-CDDO-Me (4)
S49
13C NMR of 4
-100102030405060708090100110120130140150160170180190200210220f1 (ppm)
18.2
514
21.5
227
22.5
989
24.0
307
26.2
903
26.9
317
27.2
651
27.7
967
31.7
029
32.0
409
32.4
094
34.3
210
35.7
434
37.1
410
41.3
338
42.5
728
45.0
199
45.3
115
46.4
617
48.3
483
50.1
566
51.9
612
58.1
817
76.5
694
76.9
950
77.4
173
114.
3790
125.
3812
150.
6274
166.
4401
166.
8013
175.
4400
190.
2132
CO2Me
H
O
O
NC
13(18)-CDDO-Me (4)