Supporting Information for

Design and synthesis of 2-phenylnaphtalenoids and 2-

phenylbenzofuranoids as DNA topoisomerase inhibitors and

antitumor agents

Huilin Hao,a Wang Chen,a Jing Zhu,b Chunhua Lua and Yuemao Shen*,a,b

a
Key Laboratory of Chemical Biology (Ministry of Education), School of Pharmaceutical Sciences, Shandong

University, Jinan, Shandong 250012, P. R. China

b
State Key Laboratory of Microbial Technology, School of Life Sciences, Shandong University, Jinan, Shandong

250100, P. R. China

* Corresponding author. Tel.: +86 0531 88382108

E-mail address: yshen@sdu.edu.cn. (Yuemao Shen)

Experimental and analytical data

Figure S1. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 2a

 -0.00
8.30
7.78

7.65
7.63
7.26
7.13

7.09
7.08

5.40

1.74

1.39
1.28
1.26
7.11

12.30
1.00

2.08
1.09

1.05
1.00

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 0.0
f1 (ppm)

Figure S2. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 2a
154.47

136.43
136.22

130.81
128.34
125.58

109.41
117.79

83.94
77.27
77.06
76.84
76.73

24.92

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

f1 (ppm)
Figure S3. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 2b

-0.00
8.57

8.07
8.05
7.83

7.60

7.26

3.98
1.00

1.01
0.98
2.07
1.01

3.05

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 0.0
f1 (ppm)

Figure S4. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 2b
166.90

136.45
130.21
126.40
122.64

77.34
77.02
76.70

52.33

-0.00

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S5. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 2c

7.37
7.35
6.89
6.87
6.68
6.68

3.86

1.29
1.00

1.02
1.00
0.98

3.15

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 0.0
f1 (ppm)

Figure S6. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 2c
 156.26
150.80

129.24
128.52

108.41
102.60
112.78
111.43

77.28
77.07
76.86

55.87
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)

Figure S7. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 2d

8.48

8.24
8.23
7.58
7.57

6.92
1.00
1.08

1.06

1.06

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 0.0
f1 (ppm)
Figure S8. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 2d

158.29

144.52

131.91
129.03

120.14

109.24
116.50
111.38

77.26
77.04
76.83

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)

Figure S9. 1H NMR (400 MHz, DMSO-d6, r.t.) spectrum for 3a

 190
1.00 10.65

180
10.5

170
1.05 9.77

9.5

160
155.94
155.47 7.85

9.0

150
7.76
130.16 7.74

8.5
7.70
1.07

140
127.22 7.70
3.04

8.0
125.35 7.68
124.95 1.03
7.67
1.01

130
124.82

7.5
7.15
124.77
7.13
3.07
119.56 7.12

120
7.0
118.11 7.11
116.21 7.10

6.5
108.93 7.09

110
6.0

100
5.5

f1 (ppm)
f1 (ppm)

90
5.0

80
4.5

70
4.0

60
3.5

3.34

40.65
3.0

50
40.44

Figure S10. 13C NMR (100 MHz, DMSO-d6, r.t.) spectrum for 3a
40.23 2.50
2.5

40.02

40
39.81
39.60
2.0

39.39

30
1.5

20
1.0

10
0.5

0
-0.00
0.0
Figure S11. HR ESIMS spectrum for 3a
Figure S12. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 3b

-0.00
7.88
7.79
7.77
7.73
7.71
7.63
7.62
7.26

7.15

6.92
6.91

6.02

1.25
7.11
1.00
1.02
0.98
0.99

2.90
0.98
0.97

2.01

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 0.0
f1 (ppm)

Figure S13. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 3b
153.33

148.18
146.96

136.18
135.55
133.53
130.08

125.24
120.71

109.32
108.67
107.75
101.18
118.18

77.25
77.04
76.83

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S14. HR ESIMS spectrum for 3b

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Figure S15. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 3c
8.64

8.10
8.04
8.01
7.93
7.81
7.80
7.30
7.26
7.03
7.01

4.02
4.01
3.98
1.00

0.99
0.94
1.16
1.09
1.07
1.03
1.04
1.06

3.32
2.81
3.01

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 0.0
f1 (ppm)

Figure S16. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 3c
 180
170
167.27

160
149.30

150
149.08

140.77

140
130.84
128.24

130
126.32
124.92
119.90

120
111.51
110.52

110
100

Figure S17. HR ESIMS spectrum for 3c

90
f1 (ppm)
77.27

80
77.06
76.85

70
60

56.03
52.28
50
40
30
20
10
0
Figure S18. 1H NMR (400 MHz, acetone-d6 and DMSO-d6, r.t.) spectrum for 3d
 210
205.71

13.5

200
0.78

190
12.5

180
11.5

170
167.67

160
10.5
149.84

150
149.64

9.5
140.39

140
131.53
8.64
129.83
1.00 8.64

130
126.13

8.5
124.63 1.06
1.09 8.06
2.13
1.07
119.68 7.94

120
112.27 1.05

7.5
1.06 7.40
111.01 1.06 7.12
7.11

f1 (ppm)
f1 (ppm)

110 100
6.5

90
5.5

80
70
4.5

3.04 3.95

60
3.10 3.88
55.47
55.40
3.5

50
39.77
39.50
2.07

40
39.22
2.5

2.06
29.62 2.06
29.50 2.06

30
29.37 2.05
1.5

29.24
29.11

20
28.98
28.86
Figure S19. 13C NMR (100 MHz, acetone-d6 and DMSO-d6, r.t.) spectrum for 3d
0.5

10
0.00

0
Figure S20. HR ESIMS spectrum for 3d

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Figure S21. 1H NMR (400 MHz, acetone-d6 and DMSO-d6, r.t.) spectrum for 3e

8.58

8.25
8.07
8.02
7.93
7.41
7.39
7.13
7.12

3.95
3.88

3.15

2.52
2.51
2.07
2.07
2.07
2.06
2.06

0.00
1.00

1.03
4.33
1.06

1.06
1.04
0.87
1.07

3.04
3.14

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 0.0
f1 (ppm)

Figure S22. 13C NMR (100 MHz, Acetone-d6 and DMSO-d6, r.t.) spectrum for 3e
206.44

168.71

150.35
150.05

140.22

132.14
128.38
125.15
120.15

112.86
111.54

56.08
56.02

40.24
40.10
39.96
39.83
30.16
30.03
29.90
29.78
29.65
29.52

-0.00

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S23. HR ESIMS spectrum for 3e

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Figure S24. 1H NMR (400 MHz, DMSO-d6, r.t.) spectrum for 3f
9.39
9.27

8.62
8.14

7.98
7.96
7.85
7.83
7.29
7.15
7.13
6.94
6.92

3.94
3.93

3.40

2.52
2.52
2.52
2.51
2.51
1.99

1.18
1.01
1.02

1.00

2.04
1.05
1.01
1.05

1.04
1.03
1.05

3.03

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 0.0
f1 (ppm)

Figure S25. 13C NMR (100 MHz, DMSO-d6, r.t.) spectrum for 3f
 170
166.86

160
146.43

150
146.32

140.88

140
136.06

130.72

130
126.76
124.09

118.73

120
116.85
114.99

110
100

Figure S26. HR ESIMS spectrum for 3f

90
f1 (ppm)
70
60 80

52.66
50

40.64
40.43
40.22
40

40.01
39.80
39.59
30

39.38
20
10
0
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Figure S27. 1H NMR (400 MHz, DMSO-d6, r.t.) spectrum for 3g

 190
10.0
9.5

180
9.29
1.86
9.18

9.0

170
167.93
1.00 8.59

8.5
8.14

160
2.04
1.05 7.99

8.0
146.32 1.03 7.96

150
146.28 1.03 7.84
7.82
7.25

7.5
140.58
1.01 7.16

140
135.93 1.01 7.14

7.0
130.69 1.03 6.92

130
127.98 6.89
124.10

6.5
118.75

120
116.73

6.0
114.87

110
5.5

100
5.0

f1 (ppm)
f1 (ppm)

90
4.5

80
4.0

70
3.5 3.57
3.42

60
3.0

2.52
40.61 2.52

50
2.51
2.5

40.40

Figure S28. 13C NMR (100 MHz, DMSO-d6, r.t.) spectrum for 3g
40.20 2.51
39.99 2.09

40
2.0

39.78
39.57
39.36

30
1.5

20
1.0
0.5

10
0.0

0
Figure S29. HR ESIMS spectrum for 3g

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Figure S30. 1H NMR (400 MHz, DMSO-d6, r.t.) spectrum for 3h

-0.00
9.19
9.09

8.47

7.96
7.79

7.45

6.89
6.87

3.34

2.51
2.51
2.50
2.50
2.50
7.11
0.95
0.95

1.02

2.02
2.04
1.03
1.04

0.99
0.98
1.00
1.00

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 0.0
f1 (ppm)

Figure S31. 13C NMR (100 MHz, DMSO-d6, r.t.) spectrum for 3h
168.42

146.25
146.16

139.83
135.14
131.31
128.00
124.09
118.66
116.65
114.76

40.64
40.44
40.23
40.02
39.81
39.60
39.39

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S32. HR ESIMS spectrum for 3h

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Figure S33. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 4a

-0.00
7.43
7.41
7.41
7.39
7.36
7.26
7.02
6.94
6.93
6.87
6.87
6.86

4.00
3.94
3.87
3.86
2.10
1.00
0.99
1.08
1.95

3.06
3.02
3.20

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 0.0
f1 (ppm)

Figure S34. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 4a
156.78
156.06

149.75
149.53
149.19

130.03

123.64

107.99
103.21
100.22
117.89

111.35

77.25
77.04
76.83

56.01
55.92

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

f1 (ppm)
Figure S35. HR ESIMS spectrum for 4a

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Figure S36. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 4b

-0.00
7.79
7.78
7.76
7.76
7.36
7.26

6.98
6.98
6.96
6.95
6.87
6.86
6.84
6.83
6.82
6.82

3.86
3.85

1.55
1.97

1.00
0.96
2.04
1.96

6.08

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 0.0
f1 (ppm)

Figure S37. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 4b
 190
180
170
159.98
156.89

160
156.05

149.77

150
140
130.07

130
126.36
123.46

120
114.26
112.28
111.37

110
103.25

Figure S38. HR ESIMS spectrum for 4b

99.87

100
f1 (ppm)
90
77.33

80
77.22
77.01
76.69
70
60

55.93
55.37
50
40
30
20
10
0
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Figure S39. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 4c

 9.0

190
180
8.5
7.44
7.42
7.39

170
8.0
7.38
7.36
1.05
159.98 7.34

160
1.44

7.5
156.12 7.32
1.04
7.25
149.95

150
1.00 7.04

7.0
0.99 7.03
1.00 6.96

140
0.95 6.91

6.5
131.87 6.90
129.85 6.90

130
129.74 6.89

6.0
6.88
114.45 6.87

120
113.10

5.5
111.62
110.12

110
5.0
103.38
101.81

100
100.01

4.5

f1 (ppm)
f1 (ppm)

90
2.95 3.89

4.0
77.34 2.99 3.85

80
77.02
76.71

3.5

70
3.0

60
55.94
55.40

Figure S40. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 4c
2.5

50
2.0

40
1.55
1.5

30
1.25
1.0

20
0.5

10
0
-0.00 -0.00
0.0
Figure S41. HR ESIMS spectrum for 4c

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Figure S42. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 4d

-0.00
8.66
8.66
8.65
8.16

7.63
7.61
7.59
7.45
7.43
7.26

7.06
7.06
6.97
6.96
6.94
6.94

3.87

1.25
8.11

7.11
7.11
1.00

1.00
1.04

1.04
1.03

1.03
1.02
1.04

3.03

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 0.0
f1 (ppm)

Figure S43. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 4d
156.42
153.88
150.22
148.82

132.25
130.17
129.81
129.25

103.70
103.56
119.59

111.90

77.33
77.01
76.69

55.92

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S44. HR ESIMS spectrum for 4d

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Figure S45. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 4e

-0.00
7.85
7.82
7.45

7.39
7.26
7.04
7.03
6.96
6.91
6.90
6.88
6.87

4.74

3.86

1.63
2.05

2.07
1.00
1.00
1.00
1.03

2.03

3.01

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 0.0
f1 (ppm)

Figure S46. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 4e
 180
170
156.48

160
156.12

149.96

150
141.18

140
129.96
129.77

130
127.35
125.05

120
113.04
111.59

110
103.37
101.52

100

Figure S47. HR ESIMS spectrum for 4e

90
f1 (ppm)
77.34

80
77.02
76.70

70
65.07
60

55.94
50
40
30
20
10
0
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Figure S48. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 4f

-0.00
8.47
8.46
8.18
7.58

7.46
7.37
7.27
7.01
6.98
6.97

4.01
3.96
3.92

2.18

1.58
1.00
1.03

1.05
1.03
1.04

1.06
1.07

3.03
3.08

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 0.0
f1 (ppm)

Figure S49. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 4f
159.33
157.50
150.41
149.32
144.30

129.94

108.10
100.25
119.75
118.57
116.90
111.36
111.22

77.26
77.05
76.84

56.09
56.06

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

f1 (ppm)
Figure S50. HR ESIMS spectrum for 4f

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Figure S51. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 4g

-0.00
8.47
8.46
8.16

7.80
7.54
7.26
7.02
7.02
7.00
6.99
6.98
6.98

3.88

1.56
1.00
1.04

2.07
1.06

3.03

3.08

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 0.0
f1 (ppm)

Figure S52. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 4g
 170
160.86
159.48

160
157.54

150
144.35

140
130.00

130
126.89

119.65

120
116.86
114.51
111.17

110
100.01
100.00

100
99.92

Figure S53. HR ESIMS spectrum for 4g

90
77.51

f1 (ppm)
80
77.34
77.02
76.71

70
60
55.45
50
40
30
20
10
0

0.00
 Instrument impact HD 1819696.00309

4g_BB7_01_2190.d
Bruker Compass DataAnalysis 4.2 printed: 6/5/2015 6:11:41 PM by: BDAL@DE Page 1 of 1

Figure S54. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 4h

 170
10.0
160.10

9.5
159.14

160
157.62

9.0

150
8.51
144.42 1.00 8.50

8.5
1.01

140
130.48 8.23
7.46

8.0
130.15 8.20
1.04 7.41
129.61

130
1.16 7.40

7.5
120.18 1.90 7.37
117.87 1.05 7.26
7.13

120
117.31 1.04

7.0
115.50 7.12
111.46 6.99
6.99

110
6.5
110.65
6.99
6.98
101.95
6.97

6.0

100
6.96
6.96

5.5
6.96

90
5.0
77.34

80
f1 (ppm)
f1 (ppm)
77.02

4.5
76.71

70
4.0
3.05 3.91

60
3.5
55.47

50
3.0

Figure S55. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 4h
2.5

40
2.0

30
1.56
1.5

20
1.0

10
0.5

0
-0.00
-0.00
0.0
Figure S56. HR ESIMS spectrum for 4h

Instrument impact HD 1819696.00309

4h_BB8_01_2191.d
Bruker Compass DataAnalysis 4.2 printed: 6/11/2015 10:25:27 PM by: BDAL@DE Page 1 of 1
Figure S57. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 4i

-0.00
8.74
8.74
8.73
8.58
8.57

8.27
8.18
7.68
7.65

7.32
7.26

1.56

1.25
1.00
1.01
2.15
1.04

2.14

1.04

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 0.0
f1 (ppm)

Figure S58. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 4i
157.73
156.44

148.88
144.70

130.65
130.21
129.09

103.93
121.11
117.87

111.85

77.33
77.01
76.70

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S59. HR ESIMS spectrum for 4i

Instrument impact HD 1819696.00309

4i_BC1_01_2192.d
Bruker Compass DataAnalysis 4.2 printed: 6/11/2015 10:26:06 PM by: BDAL@DE Page 1 of 1
Figure S60. 1H NMR (400 MHz, DMSO-d6, r.t.) spectrum for 4j

-0.00
8.61
8.60
8.22
8.20

7.86
7.61
7.50
7.48

5.35
5.34
5.32

4.59
4.57

3.34

2.51
2.51
2.50
2.50
2.09
1.00

1.05
2.05
1.06
1.06
2.07

1.06

2.06

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 0.0
f1 (ppm)

Figure S61. 13C NMR (100 MHz, DMSO-d6, r.t.) spectrum for 4j
 170
159.08

160
157.54

150
145.04
144.44

140
130.06

130
127.52
125.43

120
117.80

112.40

110
102.64

100

Figure S62. HR ESIMS spectrum for 4j

90
f1 (ppm)
70 80
62.98
60
50

40.65
40.44
40.24
40.03
40

39.82
39.61
39.40
30
20
10
0
 Instrument impact HD 1819696.00309

4j_BC2_01_2193.d
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Figure S63. 1H NMR (400 MHz, acetone-d6, r.t.) spectrum for 5a

-0.00
8.89

8.47
8.35
7.77

7.56
7.55

7.08
7.01
7.00

3.07

2.09
2.06
2.06
1.00

1.06
1.02

1.06
1.13
1.03

1.09
1.09

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 0.0
f1 (ppm)

Figure S64. 13C NMR (100 MHz, acetone-d6, r.t.) spectrum for 5a
205.50

151.90
150.80
146.93
146.82
145.23

129.98
120.89

107.79
104.25
115.25
113.65
113.60

90.32

29.38
29.25
29.13
29.00
28.87
28.74
28.61

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S65. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 6a

-0.00
7.38
7.37
7.35
7.35
7.31
7.29
7.28
7.26

6.95
6.86
6.77
6.74

6.01

1.58

1.25
2.07
0.96
1.00
1.06
2.05

2.08

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 0.0
f1 (ppm)

Figure S66. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 6a
 170
160
156.87

151.63

150
148.14

140
130.25

130
119.17

120
112.49

108.72

110
105.69
105.47
101.35

100
100.09

Figure S67. HR ESIMS spectrum for 6a

90
f1 (ppm)
77.34

80
77.02
76.71

70
60
50
40

29.73
30
20
10
0

0.00
 Instrument impact HD 1819696.00309

6a_BD5_01_2204.d
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Figure S68. 1H NMR (400 MHz, acetone-d6, r.t.) spectrum for 5b

-0.00
8.71

8.09

7.74
7.34
7.32

6.99
6.99
6.96
6.94
6.80
6.79
6.78
6.77

2.97
2.94

2.09
2.06
2.06
2.05
2.05
2.04
0.85

0.88

2.03

1.00

1.01
2.94
1.03

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 0.0
f1 (ppm)

Figure S69. 13C NMR (100 MHz, acetone-d6, r.t.) spectrum for 5b
205.28
205.07

158.10
156.94
153.55
149.09

130.48
126.32
122.33

105.27
115.74

110.84

99.25

29.50
29.31
29.12
28.93
28.73
28.54
28.35

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S70. HR ESIMS spectrum for 5b

Instrument impact HD 1819696.00309

5b_BC4_01_2195.d
Bruker Compass DataAnalysis 4.2 printed: 6/11/2015 10:28:05 PM by: BDAL@DE Page 1 of 1
Figure S71. 1H NMR (400 MHz, acetone-d6, r.t.) spectrum for 5c

-0.00
-0.00
8.55

8.15

7.37
7.32
7.28
7.10
7.03
6.88
6.85
6.85
6.83

2.95

2.05
2.05
0.98

0.95

2.94
1.05
1.15
1.00
2.05

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 0.0
f1 (ppm)

Figure S72. 13C NMR (100 MHz, acetone-d6, r.t.) spectrum for 5c
 210
205.76

190
170
156.38
153.38
149.31

150
131.83
129.99
129.85

130
116.13

111.42
111.07

Figure S73. HR ESIMS spectrum for 5c

110
105.49
103.35
101.39

f1 (ppm)
90
78.28

80
77.95
77.63
70
60
50

29.89
40

29.69
29.50
29.31
30

29.12
28.92
20

28.73
10
0
-10
 Instrument impact HD 1819696.00309

5c_BC5_01_2196.d
Bruker Compass DataAnalysis 4.2 printed: 6/5/2015 6:24:24 PM by: BDAL@DE Page 1 of 1

Figure S74. 1H NMR (400 MHz, CDCl3 and acetone-d6, r.t.) spectrum for 5d
 9.0

170
1.00 8.63
158.63

8.5
8.18

160
158.18
154.22 1.92
8.16
153.47

8.0
8.15

150
7.69
1.04 7.65

7.5
137.02 0.97 7.34

140
135.13 0.99 7.17
134.87 0.95 7.01

7.0
134.16 0.97 7.01

130
127.37 6.87
123.93 6.87

6.5
6.85
119.41

120
6.85
116.24

6.0
110.74

110
108.58

5.5

100
5.0

90
83.18
83.06

4.5
82.86

f1 (ppm)
f1 (ppm)

80
82.53

4.0

70
3.5

60
3.0

45.52
45.31

50
45.10 2.58
2.5

44.90
44.69 2.16

40
44.48
2.0

44.27

30
1.5

1.25

20
1.0

Figure S75. 13C NMR (100 MHz, CDCl3 and acetone-d6, r.t.) spectrum for 5d

10
0.5

0
-0.00
0.0
Figure S76. HR ESIMS spectrum for 5d

Instrument impact HD 1819696.00309

5d_BC6_01_2197.d
Bruker Compass DataAnalysis 4.2 printed: 6/11/2015 10:28:36 PM by: BDAL@DE Page 1 of 1
Figure S77. 1H NMR (400 MHz, acetone-d6, r.t.) spectrum for 5e

8.12

7.87
7.85
7.46
7.36

7.02
6.85
6.84
6.82
6.81

4.70
4.68
4.30
4.28
4.26
0.86
2.04

2.07
1.01
1.00
0.98
1.01

0.83
2.11

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 0.0
f1 (ppm)

Figure S78. 13C NMR (100 MHz, acetone-d6, r.t.) spectrum for 5e
206.12
205.92

157.38
154.57
150.23
144.12
131.09

127.96
127.86
127.43
125.41

106.40
102.06
114.01
112.00

64.38

30.41
30.22
30.03
29.83
29.64
29.45
29.26

0.00

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S79. HR ESIMS spectrum for 5e

Instrument impact HD 1819696.00309

5e_BC7_01_2198.d
Bruker Compass DataAnalysis 4.2 printed: 6/11/2015 10:29:03 PM by: BDAL@DE Page 1 of 1
Figure S80. 1H NMR (400 MHz, acetone-d6, r.t.) spectrum for 5f
8.54
8.50

8.20

7.76
7.75

7.40
7.29

7.01
6.99

2.91

2.10
2.08
2.07

0.01
0.86
0.81
0.78
0.97

0.95

0.95
1.00
0.97

1.00

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 0.0
f1 (ppm)

Figure S81. 13C NMR (100 MHz, acetone-d6, r.t.) spectrum for 5f
 210
205.39

200
190
180
170
159.78

160
157.36

147.14

150
145.61
144.38

140
130.32

130
119.38
117.79

120
116.66

Figure S82. HR ESIMS spectrum for 5f

115.87
112.28
111.28

f1 (ppm)
99.90

110 100
90
80
70
60
50

29.36
40

29.23
29.11
30

28.98
28.85
28.72
20

28.59
10
0
 Instrument impact HD 1819696.00309

5f_BC8_01_2199.d
Bruker Compass DataAnalysis 4.2 printed: 6/5/2015 6:27:18 PM by: BDAL@DE Page 1 of 1

Figure S83. 1H NMR (400 MHz, DMSO-d6, r.t.) spectrum for 6f

 170
10.0
9.5

160
1.00 9.27
156.18
0.98 9.15

9.0
147.77

150
146.65
146.01

8.5
145.01
7.21

140
8.0
7.19
130.29 7.15

130
7.14

7.5
2.00 7.13
122.28 1.00 7.12

120
7.0
116.50 1.00 6.85
1.02
112.36 1.00 6.68

6.5

110
111.03 1.00 6.68
6.54
104.12
6.53

6.0
99.54 6.52

100
6.51

5.5

90
5.0
1.99 4.81

f1 (ppm)
f1 (ppm)

80
4.5

70
4.0

60
3.5
3.34
3.0

50
40.66
40.45 2.51
40.24 2.50
2.5

40.03
Figure S84. 13C NMR (100 MHz, DMSO-d6, r.t.) spectrum for 6f 2.50

40
39.82 2.09
39.61
2.0

39.41

30
1.5

20
1.0

10
0.5

-0.00
0.0

0
Figure S85. HR ESIMS spectrum for 6f

Instrument impact HD 1819696.00309

6f_BD6_01_2205.d
Bruker Compass DataAnalysis 4.2 printed: 6/5/2015 6:31:03 PM by: BDAL@DE Page 1 of 1
Figure S86. 1H NMR (400 MHz, acetone-d6, r.t.) spectrum for 5g

-0.00
8.69
8.59
8.58

8.24
7.81
7.79

7.35
6.98
6.97
6.96
6.95

2.86
2.83
2.09
2.07
2.06
2.05
2.05
2.04
0.81
0.96

1.00

1.02
2.07
0.92
1.05
1.00

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 0.0
f1 (ppm)

Figure S87. 13C NMR (100 MHz, acetone-d6, r.t.) spectrum for 5g
205.40
205.21

159.18
157.99
157.53

144.53

130.50
130.29
129.89
120.01

102.21
116.87
116.62
111.88
111.61

29.50
29.30

28.92
28.73
28.53
28.34
29.11

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S88. HR ESIMS spectrum for 5g

Instrument impact HD 1819696.00309

5g_BD1_01_2200.d
Bruker Compass DataAnalysis 4.2 printed: 6/5/2015 6:27:54 PM by: BDAL@DE Page 1 of 1
Figure S89. 1H NMR (400 MHz, CDCl3, r.t.) spectrum for 6g
9.67

7.53
7.51
7.35
7.33
7.31
7.29
7.28
7.25
6.86
6.86
6.82
6.82
6.80
6.80
6.64
6.63
6.62
6.61

3.33

2.50

2.12

1.79
0.89

1.00
1.00
3.22

0.92
1.04
1.03

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 0.0
f1 (ppm)

Figure S90. 13C NMR (100 MHz, CDCl3, r.t.) spectrum for 6g
 170
158.27

160
156.25
151.29

150
147.68

140
131.48
130.60

130
129.76

117.58
116.41

120
116.07

111.61

110
110.92
102.40

100

Figure S91. HR ESIMS spectrum for 6g

90
f1 (ppm)
70
60
50 80

40.65
40.44
40.23
40.03
40

39.82
39.61
39.40
30
20
10
0
 Instrument impact HD 1819696.00309

6g_BD7_01_2206.d
Bruker Compass DataAnalysis 4.2 printed: 6/5/2015 6:31:49 PM by: BDAL@DE Page 1 of 1
Figure S92. 1H NMR (400 MHz, acetone-d6, r.t.) spectrum for 5h

-0.00
-0.00
8.69
8.59
8.59

8.24
7.81
7.79

7.35
6.97
6.95

2.85
2.85
2.82
2.09
2.09
2.06
2.06
2.05
2.05
2.04
0.79
0.91

0.99

0.99

3.06
1.08

1.00

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 0.0
f1 (ppm)

Figure S93. 13C NMR (100 MHz, acetone-d6, r.t.) spectrum for 5h
210.36
210.16

164.40
163.18
162.74

149.75

135.71
135.49
135.10
125.20

122.07
121.84

107.41
117.09
116.80

34.68
34.49
34.30
34.10
33.91
33.72
33.53

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
f1 (ppm)
Figure S94. HR ESIMS spectrum for 5h

Instrument impact HD 1819696.00309

5h_BD2_01_2201.d
Bruker Compass DataAnalysis 4.2 printed: 6/19/2015 6:09:47 PM by: BDAL@DE Page 1 of 1
Figure S95. 1H NMR (400 MHz, DMSO-d6, r.t.) spectrum for 6h
9.61

7.27
7.25
7.22
7.10

6.77
6.76
6.72
6.60
6.58

4.86

3.33

2.51
0.90

3.89
0.97

0.94
0.91
1.00

1.99

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 0.0
f1 (ppm)

Figure S96. 13C NMR (100 MHz, DMSO-d6, r.t.) spectrum for 6h
 170
160
158.21
155.42

150
148.03
145.24

140
131.88
130.48

130
129.91

115.98

120
115.83
113.51
111.41

110
111.34
104.23
102.03

100

Figure S97. HR ESIMS spectrum for 6h

90
f1 (ppm)
70
60
50 80

40.66
40.45
40.24
40.03
40

39.82
39.61
39.40
30
20
10
0
 Instrument impact HD 1819696.00309

6h_BD8_01_2207.d
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Figure S98. 1H NMR (400 MHz, DMSO-d6, r.t.) spectrum for 5i

 7.24

170
7.22

8.0
7.11
7.09

160
7.07
156.25

7.5
1.03 7.05
1.07 7.04
149.51 1.05 6.99

150
147.93 2.02 6.97

7.0
145.14
1.00 6.71

140
2.05
6.58

6.5
131.15 6.56
129.98 6.56

130
129.84 6.54

6.0
6.54
114.60
113.21

120
112.78

5.5
111.20
109.95 1.97 5.22

110
5.0
104.22
101.29 2.03 4.83

100
4.5

90
4.0

f1 (ppm)
f1 (ppm)

80
3.5
3.31

70
3.0

60
2.50
2.50
2.5

2.50

50
40.67
40.46
40.25
2.0

40.04
Figure S99. 13C NMR (100 MHz, DMSO-d6, r.t.) spectrum for 5i

40
39.83
39.62
1.5

39.42

30
1.0

20
0.5

10
-0.00
0.0

0
Figure S100. HR ESIMS spectrum for 5i

Instrument impact HD 1819696.00309

5i_BD3_01_2202.d
Bruker Compass DataAnalysis 4.2 printed: 6/5/2015 6:29:12 PM by: BDAL@DE Page 1 of 1
 9.0

170
8.5

160
155.46
7.81

8.0
148.05

150
1.98 7.79
145.25
7.42
143.39

7.5
1.98

140
1.01 7.25
0.97 7.14
129.98

7.0
6.73
129.15

130
0.98 6.72
127.39 1.00 6.60
124.62 6.60

6.5
6.58

120
6.57
113.42

6.0
111.32

110
104.22

5.5
101.70 5.26
1.01 5.24

100
5.23

5.0
1.94 4.85

90
2.01 4.54

4.5
4.53

f1 (ppm)
f1 (ppm)

80
4.0

70
3.5
63.09 3.32

60
3.0
2.51

50
40.67 2.5 2.50
40.46 2.50
40.25
40.04 2.09
Figure S101. 1H NMR (400 MHz, DMSO-d6, r.t.) spectrum for 5j

40
Figure S102. 13C NMR (100 MHz, DMSO-d6, r.t.) spectrum for 5j
2.0

39.83
39.62
39.42

30
1.5

20
1.0
0.5

10
-0.00
0.0

0
Figure S103. HR ESIMS spectrum for 5j

Instrument impact HD 1819696.00309

5j_BD4_01_2203.d
Bruker Compass DataAnalysis 4.2 printed: 6/5/2015 6:29:42 PM by: BDAL@DE Page 1 of 1