Supporting Information-4 - rsc.org file1 Supporting Information-4: Scaffold diversity -oriented...
78
1 Supporting Information-4: Scaffold diversity-oriented synthesis of limonoid dimers: discovery of an axially chiral agent with in vivo anti-breast cancer activity Wan-Shan Li, ‡a Yang Yang, ‡b Jun-Jun Liu, d Li Shen,* a Zhi Shi,* b and Jun Wu* c a Marine Drugs Research Center, College of Pharmacy, Jinan University, 601 Huangpu Avenue West, Guangzhou 510632, P. R. China b Department of Cell Biology & Institute of Biomedicine, National Engineering Research Center of Genetic Medicine, Guangdong Provincial Key Laboratory of Bioengineering Medicine, College of Life Science and Technology, Jinan University, 601 Huangpu Avenue West, Guangzhou 510632, P. R. China c School of Pharmaceutical Sciences, Southern Medical University, 1838 Guangzhou Avenue North, Guangzhou 510515, P. R. China d School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, P. R. China ‡ These authors contributed equally Copies of HRESIMS, UV, IR, 1D and 2D NMR spectra of compounds 5a, and 5b Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is © the Partner Organisations 2018
Transcript of Supporting Information-4 - rsc.org file1 Supporting Information-4: Scaffold diversity -oriented...
1
Supporting Information-4:
Scaffold diversity-oriented synthesis of limonoid dimers: discovery of an axially chiral agent with in vivo anti-breast cancer activity
Wan-Shan Li,‡a Yang Yang,‡b Jun-Jun Liu,d Li Shen,*a Zhi Shi,*b and Jun Wu*c
a Marine Drugs Research Center, College of Pharmacy, Jinan University, 601 Huangpu Avenue West, Guangzhou 510632, P. R. China
b Department of Cell Biology & Institute of Biomedicine, National Engineering Research Center of Genetic Medicine, Guangdong Provincial Key Laboratory of Bioengineering Medicine, College of Life Science and Technology, Jinan University, 601 Huangpu Avenue West, Guangzhou 510632, P. R. China
c School of Pharmaceutical Sciences, Southern Medical University, 1838 Guangzhou Avenue North, Guangzhou 510515, P. R. China
d School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, P. R. China
‡ These authors contributed equally
Copies of HRESIMS, UV, IR, 1D and 2D NMR spectra of compounds 5a, and 5b
Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2018
2
Table of Contents: (Page)
1. HR-ESIMS for compound 5a·································································3-4 2. UV spectrum for compound 5a in CH3CN······································································5 3. IR spectrum for compound 5a·····················································································6 4. 1H NMR (400 MHz) spectrum of compound 5a in CDCl3·································7-10
5. 13C NMR (100 MHz) spectrum of compound 5a in CDCl3 ································11-15
6. DEPT135 (100 MHz) spectrum of compound 5a in CDCl3 ·······························16-20 7. 1H-1H COSY (400 MHz) spectrum of compound 5a in CDCl3 ···························21-22 8. HSQC (400 MHz) spectrum of compound 5a in CDCl3 ···································23-27 9. HMBC (400 MHz) spectrum of compound 5a in CDCl3 ···································28-34 10. NOESY (400 MHz) spectrum of compound 5a in CDCl3 ································35-39 11. HR-ESIMS for compound 5b·································································40-41 12. UV spectrum for compound 5b in CH3CN····································································42 13. IR spectrum for compound 5b···················································································43 14. 1H NMR (400 MHz) spectrum of compound 5b in CDCl3·································44-47
15. 13C NMR (100 MHz) spectrum of compound 5b in CDCl3 ································48-52
16. DEPT135 (100 MHz) spectrum of compound 5b in CDCl3 ·······························53-56 17. 1H-1H COSY (400 MHz) spectrum of compound 5b in CDCl3 ···························57-59 18. HSQC (400 MHz) spectrum of compound 5b in CDCl3 ···································60-64 19. HMBC (400 MHz) spectrum of compound 5b in CDCl3 ··································65-72 20. NOESY (400 MHz) spectrum of compound 5b in CDCl3 ································73-76 21. IR spectrum for compound 2a···················································································77 22. IR spectrum for compound 2b···················································································78
3
HR-ESIMS for compound 5a
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
4
HR-ESIMS for compound 5a
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
UV spectrum for compound 5a in CH3CN
5
IR spectrum for compound 5a
6
7
1H NMR (400 MHz) spectrum of compound 5a in CDCl3
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
8
1H NMR (400 MHz) spectrum of compound 5a in CDCl3
H-2
1/H
-21'
H
-23/
H-2
3'
H-2
2/H
-22'
H-1
7/H
-17'
H-6
/H-6
'
H-3
/H-3
'
H3-
31/H
3-31
'
30-O
H/3
0'-O
H
2-O
H/2
'-OH
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
9
1H NMR (400 MHz) spectrum of compound 5a in CDCl3
H-3
3/H
-33'
H
3-37
/ H3-
37'
H-9
/ H-9
'
Hβ-
11/Hβ-
11'
Hα-
11/Hα-
11'
H-5
/H-5
' H
a-29
/Ha-
29'
Hb-
29/H
b-29
'
6-O
H/6
'-OH
Acetone
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
Hβ-
12/Hβ-
12'
H3-
19/H
3-19
'
H3-
35/H
3-35
' H
3-34
/H3-
34'
H3-
28/H
3-28
'
H3-
38/H
3-38
' H
3-39
/H3-
39'
H3-
18/H
3-18
' Hα-
12/Hα-
12'
1H NMR (400 MHz) spectrum of compound 5a in CDCl3
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
13C NMR (100 MHz) spectrum of compound 5a in CDCl3
11
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
12
13C NMR (100 MHz) spectrum of compound 5a in CDCl3
C-3
0/C
-30'
C-3
2/C
-32'
C-7
/C-7
' C
-36/
C-3
6'
C-1
6/C
-16'
C-2
3/C
-23'
C
-21/
C-2
1'
C-1
4/C
-14'
C-8
/C-8
'
C-2
0/C
-20'
C-2
2/C
-22'
C-1
5/C
-15'
C-1
/C-1
' C
-3/C
-3'
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
13
13C NMR (100 MHz) spectrum of compound 5a in CDCl3
C-1
7/ C
-17'
C-2
/C-2
'
C-6
/C-6
'
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
14
13C NMR (100 MHz) spectrum of compound 5a in CDCl3
C-1
3/C
-13'
C-3
3/C
-33'
C-1
2/C
-12'
C-3
7/C
-37'
C-3
1/C
-31'
C-1
0/C
-10'
C-9
/C-9
'
C-5
/C-5
'
C-4
/C-4
'
C-2
9/C
-29'
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
15
13C NMR (100 MHz) spectrum of compound 5a in CDCl3
C-3
4/C
-34'
C-3
9/C
-39'
C-2
8/C
-28'
C-3
8/C
-38'
C
-11/
C-1
1' C-3
5/C
-35'
C-1
8/C
-18'
C-1
9/C
-19'
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
16
DEPT135 (100 MHz) spectrum of compound 5a in CDCl3
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
17
DEPT135 (100 MHz) spectrum of compound 5a in CDCl3
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
18
DEPT135 (100 MHz) spectrum of compound 5a in CDCl3
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
19
DEPT135 (100 MHz) spectrum of compound 5a in CDCl3
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
20
DEPT135 (100 MHz) spectrum of compound 5a in CDCl3
1'
2'3'
4'
5'6'7'
8'
9'10'
11' 12'
13'
14'15'
16'
17'
18'19'
20' 21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
1415
16
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OH OH
MeOO
O
Me
H
HO HH
3637
38
39
OMe
Me
OMe
Me36'37'38'
39'
O32
33
34
35Me
Me
MeMe O
32'
33'35'
34'
1H-1H COSY (400 MHz) spectrum of compound 5a in CDCl3
21
1H-1H COSY (400 MHz) spectrum of compound 5a in CDCl3
22
HSQC (400 MHz) spectrum of compound 5a in CDCl3
23
24
HSQC (400 MHz) spectrum of compound 5a in CDCl3
25
HSQC (400 MHz) spectrum of compound 5a in CDCl3
26
HSQC (400 MHz) spectrum of compound 5a in CDCl3
27
HSQC (400 MHz) spectrum of compound 5a in CDCl3
HMBC (400 MHz) spectrum of compound 5a in CDCl3
28
HMBC (400 MHz) spectrum of compound 5a in CDCl3
29
HMBC (400 MHz) spectrum of compound 5a in CDCl3
30
HMBC (400 MHz) spectrum of compound 5a in CDCl3
31
HMBC (400 MHz) spectrum of compound 5a in CDCl3
32
HMBC (400 MHz) spectrum of compound 5a in CDCl3
33
HMBC (400 MHz) spectrum of compound 5a in CDCl3
34
NOESY (400 MHz) spectrum of compound 5a in CDCl3
35
NOESY (400 MHz) spectrum of compound 5a in CDCl3
36
NOESY (400 MHz) spectrum of compound 5a in CDCl3
37
NOESY (400 MHz) spectrum of compound 5a in CDCl3
38
NOESY (400 MHz) spectrum of compound 5a in CDCl3
39
40
HR-ESIMS for compound 5b
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
HR-ESIMS for compound 5b
41
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
UV spectrum for compound 5b in CH3CN
42
IR spectrum for compound 5b
43
44
1H NMR (400 MHz) spectrum of compound 5b in CDCl3
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
45
1H NMR (400 MHz) spectrum of compound 5b in CDCl3
H-2
1/H
-21'
H
-23/
H-2
3'
H-2
2/H
-22'
H-1
7/H
-17'
H-6
/H-6
' H-3
/H-3
'
H3-
31/H
3-31
'
30-O
H/3
0'-O
H 1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
46
1H NMR (400 MHz) spectrum of compound 5b in CDCl3
H-3
3/H
-33'
H3-
37/ H
3-37
' H
-9/ H
-9'
Hα-
11/Hα-
11'
H-5
/H-5
' H
a-29
/Ha-
29'
Hb-
29/H
b-29
'
6-O
H/6
'-OH
2-O
H/2
'-OH
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
47
1H NMR (400 MHz) spectrum of compound 5b in CDCl3
Hβ-
12/Hβ-
12'
H3-
19/H
3-19
'
H3-
35/H
3-35
'
H3-
34/H
3-34
'
H3-
28/H
3-28
'
H3-
38/H
3-38
' H
3-39
/H3-
39'
H3-
18/H
3-18
' Hα-
12/ Hα-
12'
Hβ-
11/Hβ-
11'
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
13C NMR (100 MHz) spectrum of compound 5b in CDCl3
48
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
49
13C NMR (100 MHz) spectrum of compound 5b in CDCl3
C-3
0/C
-30'
C-3
2/C
-32'
C-7
/C-7
' C
-36/
C-3
6'
C-1
6/C
-16'
C-2
3/C
-23'
C
-21/
C-2
1'
C-1
4/C
-14'
C-8
/C-8
'
C-2
0/C
-20'
C-2
2/C
-22'
C-1
5/C
-15'
C-1
/C-1
' C
-3/C
-3'
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
50
13C NMR (100 MHz) spectrum of compound 5b in CDCl3
C-1
7/ C
-17'
C-2
/C-2
'
C-6
/C-6
'
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
51
13C NMR (100 MHz) spectrum of compound 5b in CDCl3
C-1
3/C
-13'
C-3
3/C
-33'
C-1
2/C
-12'
C-3
7/C
-37'
C-3
1/C
-31'
C-1
0/C
-10'
C-9
/C-9
'
C-5
/C-5
'
C-4
/C-4
'
C-2
9/C
-29'
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
52
13C NMR (100 MHz) spectrum of compound 5b in CDCl3
C-3
4/C
-34'
C-3
9/C
-39'
C-2
8/C
-28'
C-3
8/C
-38'
C-1
1/C
-11'
C-3
5/C
-35'
C-1
8/C
-18'
C-1
9/C
-19'
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
DEPT135 (100 MHz) spectrum of compound 5b in CDCl3
53
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
54
DEPT135 (100 MHz) spectrum of compound 5b in CDCl3
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
55
DEPT135 (100 MHz) spectrum of compound 5b in CDCl3
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
56
DEPT135 (100 MHz) spectrum of compound 5b in CDCl3
1'
2'3'
4'
5'6' 7'
8'
9' 10'
11'12'
13'
14'15'
16'
17'
18' 19'
20'21'
22'23'
28'
29'
30'
31'
1
23
4
567
8
910
11 12
13
14
1516
17
1819
20 21
2223
28
29
30
31
O
MeO
O
O
Me
OH OH
H
MeOO
O
Me
H
HO H
O
MeO
O
O
Me
OHHO
OMeO
O
Me
H
OHH H
O
Me Me
36
3738
39 O
Me Me36'
37'38'
39'
O32
33
34
35Me
Me
MeMeO
32'
33' 35'34'
1H-1H COSY (400 MHz) spectrum of compound 5b in CDCl3
57
1H-1H COSY (400 MHz) spectrum of compound 5b in CDCl3
58
59
1H-1H COSY (400 MHz) spectrum of compound 5b in CDCl3
H-6/H-6'
H-5
/H-5
'
6-O
H/6
'-OH
HSQC (400 MHz) spectrum of compound 5b in CDCl3
60
HSQC (400 MHz) spectrum of compound 5b in CDCl3
61
HSQC (400 MHz) spectrum of compound 5b in CDCl3
62
63
HSQC (400 MHz) spectrum of compound 5b in CDCl3
64
HSQC (400 MHz) spectrum of compound 5b in CDCl3
HMBC (400 MHz) spectrum of compound 5b in CDCl3
65
HMBC (400 MHz) spectrum of compound 5b in CDCl3
66
HMBC (400 MHz) spectrum of compound 5b in CDCl3
67
HMBC (400 MHz) spectrum of compound 5b in CDCl3
68
HMBC (400 MHz) spectrum of compound 5b in CDCl3
69
70
HMBC (400 MHz) spectrum of compound 5b in CDCl3
71
HMBC (400 MHz) spectrum of compound 5b in CDCl3
72
HMBC (400 MHz) spectrum of compound 5b in CDCl3
NOESY (400 MHz) spectrum of compound 5b in CDCl3
73
NOESY (400 MHz) spectrum of compound 5b in CDCl3
74
NOESY (400 MHz) spectrum of compound 5b in CDCl3
75
NOESY (400 MHz) spectrum of compound 5b in CDCl3
76
IR spectrum for compound 2a
77
IR spectrum for compound 2b
78
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