Synthetic studies towards putative yuremamine using an

iterative C(sp3)-H arylation strategy

Matthew B. Calvert and Jonathan Sperry*

School of Chemical Sciences, University of Auckland, 23 Symonds St., Auckland, New Zealand

j.sperry@auckland.ac.nz

SUPPORTING INFORMATION

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2016

Contents Page 1H NMR of 10 (400 MHz, CDCl3) …………………………………………………........................ 1

13C NMR of 10 (100 MHz, CDCl3) ………………………………………………………............... 2

1H NMR of 12 (400 MHz, CDCl3) ………………………………………………………………… 3

13C NMR of 12 (100 MHz, CDCl3) ………………………………………………………............... 4

NOESY spectrum of 12…………………………………………………………………………….. 5 1H NMR of 16 (400 MHz, CDCl3) …………………………………………………….................... 6

13C NMR of 16 (100 MHz, CDCl3) ……………………………………………………………....... 7

NOESY spectrum of 16…………………………………………………………………………….. 8 1H NMR of 17 (400 MHz, CDCl3) …………………………………………………….................... 9

13C NMR of 17 (100 MHz, CDCl3) ………………………………………………………………... 10

NOESY spectrum of 17…………………………………………………………………………….. 11 1H NMR of 19 (400 MHz, CDCl3) ………………………………………………………………… 12

13C NMR of 19 (100 MHz, CDCl3) ………………………………………………………………... 13

NOESY spectrum of 19…………………………………………………………………………….. 14 1H NMR of 20 (400 MHz, CDCl3) ……………………………………………………………….... 15

13C NMR of 20 (100 MHz, CDCl3) ………………………………………………………………... 16

NOESY spectrum of 20…………………………………………………………………………….. 17 1H NMR of 21 (500 MHz, CDCl3) ………………………………………………………………… 18

13C NMR of 21 (125 MHz, CDCl3) ……………………………………………………………....... 19

NOESY spectrum of 21…………………………………………………………………………….. 20 1H NMR of 24 (400 MHz, CDCl3) ………………………………………………………………… 21

1H NMR of 25 (400 MHz, CDCl3) ………………………………………………………………… 22

13C NMR of 25 (100 MHz, CDCl3) ………………………………………………………………... 23

1H NMR of 31 (400 MHz, CDCl3) ………………………………………………………………… 24

1H NMR of 35(400 MHz, CDCl3) …………………………………………………………………. 25

13C NMR of 35 (100 MHz, CDCl3) ………………………………………………………………... 26

1H NMR of 36 (400 MHz, CDCl3) ………………………………………………………………… 27

13C NMR of 36 (100 MHz, CDCl3) ……………………………………………………………....... 28

1H NMR of 37 (500 MHz, CDCl3) …………………………………………………………………. 29

13C NMR of 37(125 MHz, CDCl3) ……………………………………………………………......... 30

NOESY spectrum of 37……………………………………………………………………………... 31

COSY spectrum of 37……………………………………………………………………………….. 32 1H NMR of 39 (500 MHz, CDCl3) …………………………………………………………………. 33

13C NMR of 39 (125 MHz, CDCl3) …………………………………………………........................ 34

1H NMR of 38 (500 MHz, CDCl3) ……………………………………………………. …………... 35

13C NMR of 38(125 MHz, CDCl3) ……………………………………………………...................... 36

NOESY spectrum of 38…………………………………………………………………………….... 37 1H NMR of 40 (400 MHz, CDCl3) ……………………………………………………….................. 38

13C NMR of 40(100 MHz, CDCl3) …………………………………………………………….......... 39

1H NMR of 41 (400 MHz, CDCl3) ………………………………………………………………….. 40

13C NMR of 41 (100 MHz, CDCl3) ……………………………………………………………......... 41

1H NMR of 43 (400 MHz, CDCl3) ……………………………………………………...................... 42

13C NMR of 43(100 MHz, CDCl3) …………………………………………………………….......... 43

1H NMR of 44 (400 MHz, CDCl3) …………………………………………………................. ……. 44

13C NMR of 44(100 MHz, CDCl3) …………………………………………………………….......... 45

1H NMR of 45 (500 MHz, CDCl3) ………………………………………………………………….. 46

13C NMR of 45 (125 MHz, CDCl3) ……………………………………………………………......... 47

1H NMR of 47 (400 MHz, CDCl3) ………………………………………………………………….. 48

13C NMR of 47(100 MHz, CDCl3) …………………………………………………………….......... 49

1H NMR of 48 (400 MHz, CDCl3) ………………………………………………………………….. 50

13C NMR of 48(100 MHz, CDCl3) …………………………………………………………….......... 51

NOESY spectrum of 48……………………………………………………………………………… 52 1H NMR of 49 (500 MHz, CDCl3) ……………………………………………………………. ……. 53

13C NMR of 49(125 MHz, CDCl3) …………………………………………………………………... 54

NOESY spectrum of 49………………………………………………………………………………. 55 1H NMR of 50 (500 MHz, CDCl3) …………………………………………………………..... …….. 56

13C NMR of 50 (125 MHz, CDCl3) …………………………………………………………….......... 57

NOESY spectrum of 50………………………………………………………………………………. 58

 

O

HN

N

1

 

 

O

HN

N

2

 

 

3

 

4

HN

N

HH

O

OMe

MeO

HH

5

 

6

 

7

HNH

N

H

O

OMOM

MOMO

8

 

9

 

10

HNH N

H

OMOM

O

MOMO

OMOMMOMO

H

11

 

 

12

 

 

13

HNH

N

H

O

OMe

OMeMeO

14

 

 

15

 

16

HHN

N

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OMe

O

MeO

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OMe

MeO

MeO

OMe

17

 

18

 

19

HNH N

H

OMOM

O

MeO

H

MeO

OMe

OMOM

20

SpinWorks 2.5: protonstdri CDCl3 /nmr/400 mcal049 53

PPM 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

0.

999

6.

148

1.

031

1.

768

0.

688

0.

793

9.

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file: E:\NMR backup\NMR backup\400\20130701-MBC117.7V\1\fid expt: <zg30>transmitter freq.: 400.132101 MHztime domain size: 32768 pointswidth: 8169.93 Hz = 20.418093 ppm = 0.249327 Hz/ptnumber of scans: 16

freq. of 0 ppm: 400.130010 MHzprocessed size: 16384 complex pointsLB: 0.000 GB: 0.0000Hz/cm: 176.005 ppm/cm: 0.43987

4.

3343

4.

3149

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3030

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7613

1.

4557

1.

4032

21

 

22

 

23

SpinWorks 2.5: protonstdri CDCl3 /nmr/400 mcal049 4

PPM 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8 0.4 -0.0

0.

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file: N:\data\mcal049\nmr\20130910-MBC140.1-1\1\fid expt: <zg30>transmitter freq.: 400.132101 MHztime domain size: 32768 pointswidth: 8169.93 Hz = 20.418093 ppm = 0.249327 Hz/ptnumber of scans: 16

freq. of 0 ppm: 400.130010 MHzprocessed size: 16384 complex pointsLB: 0.000 GB: 0.0000Hz/cm: 128.105 ppm/cm: 0.32016

7.

2284

7.

2125

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2103

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7.

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1372

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2.

8110

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24

 

25

 

26

 

27

 

28

 

N HN

O

N

OMOM

MOMO

29

 

N HN

O

N

OMOM

MOMO

30

NOESY

N

H

RH

OMOM

OMOM

31

N

H

RH

OMOM

OMOM

H

H

H

32

 

 

33

 

34

 

 

35

 

36

N

H

RH

OMe

H

H

HOMe

MeO

37

 

38

 

39

 

40

 

41

 

N

NHCOCF3

O

42

 

N

NHCOCF3

O

43

 

44

 

45

 

46

 

47

 

48

 

49

 

50

 

51

N

H

RH

OMOM

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MeOMOM

52

 

   

53

 

54

N

H

RH

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OMOM

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55

 

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OMOMMOMO

OMeMeO

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56

 

 

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57

N

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58