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1

Electronic Supplementary Information (ESI)

Modular synthesis of polyene side chain analogues of the potent

macrolide antibiotic etnangien by a flexible coupling strategy

based on hetero-bis-metallated alkenes†

Mario Altendorfer,a Aruna Raja,b Florenz Sasse,b Herbert Irschikc and Dirk Menchea,d,*

a University of Heidelberg, Department of Organic Chemistry, INF 270, D-69120 Heidelberg,

Germany, EU.

b Helmholtz Centre for Infection Research, Department of Chemical Biology, Inhoffenstr. 7, 38124

Braunschweig, Germany, EU.

c Helmholtz Centre for Infection Research, Research Group Microbial Drugs, Inhoffenstr. 7, 38124

Braunschweig, Germany, EU.

d University of Bonn, Kekulé-Department of Organic Chemistry and Biochemistry, Gerhard-Domagk-

Str. 1, D-53121 Bonn, Germany, EU.

E-mail: dirk.menche@uni-bonn.de

Contents

Copies of 1H and 13C NMR spectra.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

2

c081120dmma.23_001001r

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

Chemical Shift (ppm)

Bu3Sn OH

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

16a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

3

c081120dmma.23.003.001.1r.esp

144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

Bu3Sn OH

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

16a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

4

c110408dmma.375_II_001001r

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

Chemical Shift (ppm)

Bu3Sn OH

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

16b

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

5

a110404dmma375_2_002001r

152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

Bu3Sn OH

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

16b

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

6

b081117dmma.28_001001r

6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

Chemical Shift (ppm)

Bu3SnOH

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

16c

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

7

b081117dmma.28_002001r

145 140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5

Chemical Shift (ppm)

Bu3SnOH

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

16c

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

8

d080725dmma.2_001001r

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

Chemical Shift (ppm)

Bu3Sn OH

solvent: CDCl3 nucleus: 1H frequency: 500.130 MHz

16d

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

9

d080725dmma.2.003.001.1r.esp

144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

OHBu3Sn

solvent: CDCl3 nucleus: 13C frequency: 125.78 MHz

16d

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

10

b101210dmma.308-III_002001r

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

Chemical Shift (ppm)

Bu3Sn OH

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

16e

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

11

b101210dmma.308-III.001.001.1r.esp

144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

OHBu3Sn

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

16e

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

12

c101214dmma.309-II_002000fid

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

Chemical Shift (ppm)

Bu3Sn OH

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

16f

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

13

c101214dmma.309-II.001.esp

144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

Bu3Sn OH

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

16f

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

14

c081107dmma.0_002001r

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

Chemical Shift (ppm)

Bu3Sn O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

12a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

15

c081107dmma.0.001.001.1r.esp

192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

Bu3Sn O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

12a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

16

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

Chemical Shift (ppm)

Bu3Sn O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

12b

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

17

a110404dmma377.002.001.1r.esp

192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

Bu3Sn O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

12b

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

18

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

Chemical Shift (ppm)

Bu3Sn O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

12d

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

19

b080729dmma.5.001.001.1r.esp

200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

Bu3Sn O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

12d

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

20

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

Chemical Shift (ppm)

Bu3Sn O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

12e

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

21

a110331dmma317_1.002.001.1r.esp

200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

OBu3Sn

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

12e

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

22

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

Chemical Shift (ppm)

Bu3Sn O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

12f

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

23

a110331dmma318_1.002.001.1r.esp

200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

Bu3Sn O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

12f

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

24

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

Chemical Shift (ppm)

Bu3SnB

O

O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

5

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

25

C0030595.001.001.1r.esp

144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

Bu3SnB

O

O

solvent: CDCl3 nucleus: 13C frequency: 100.61 MHz

5

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

26

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

Chemical Shift (ppm)

B

O

OBu3Sn

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

6a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

27

c081110dmma.55.003.001.1r.esp

152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

B

O

OBu3Sn

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

6a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

28

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

Chemical Shift (ppm)

B

O

OBu3Sn

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

6b

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

29

c080826dmma.3.001.001.1r.esp

152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

B

O

OBu3Sn

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

6b

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

30

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

Chemical Shift (ppm)

Bu3SnB

O

O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

6c

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

31

c110217dmma.357.001.001.1r.esp

152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

Bu3SnB

O

O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

6c

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

32

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

Chemical Shift (ppm)

Bu3SnB

O

O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

6d

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

33

a111124dmma365_1.002.001.1r.esp

152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

Bu3SnB

O

O

solvent: CDCl3 nucleus: 13C

frequency: 75.48 MHz

6d

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

34

b100128dmma.125.002.001.1r.esp

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

Chemical Shift (ppm)

O O

OMe

TBS

solvent: CDCl3 nucleus: 1H

frequency: 300.132 MHz

43

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

35

b100128dmma.125.001.001.1r.esp

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O O

OMe

TBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

43

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

36

c100804dmma.257.002.001.1r.esp

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

Chemical Shift (ppm)

O OH

TBS

solvent: CDCl3 nucleus: 1H

frequency: 300.132 MHz

44

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

37

c100804dmma.257.001.001.1r.esp

105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5

Chemical Shift (ppm)

O OH

TBS

solvent: CDCl3 nucleus: 13C

frequency: 75.48 MHz

44

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

38

md068.010.001.1r.esp

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 -0.5

Chemical Shift (ppm)

O O

TBS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

19a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

39

200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O O

TBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

19a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

40

b100128dmma.174.002.001.1r.esp

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

Chemical Shift (ppm)

O OH

TMS

TBS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

21a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

41

b100128dmma.174.001.001.1r.esp

110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5

Chemical Shift (ppm)

O OH

TMS

TBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

21a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

42

c091021dmma.152-R.001.esp

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

Chemical Shift (ppm)

O O

O

CF3

OMePh

TBS

TMS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

45

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

43

c091021dmma.153-S.001.esp

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

Chemical Shift (ppm)

O O

O

CF3

PhOMe

TBS

TMS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

46

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

44

c100804dmbe.06.002.001.1r.esp

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

Chemical Shift (ppm)

O OTBS

TMS

TBS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

47

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

45

c100804dmbe.06.001.001.1r.esp

110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5

Chemical Shift (ppm)

O OTBS

TMS

TBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

47

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

46

c100809dmbe.09.002.001.1r.esp

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

Chemical Shift (ppm)

O OTBS

H

TBS

solvent: CDCl3 nucleus: 1H

frequency: 300.132 MHz

48

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

47

c100809dmbe.09.001.001.1r.esp

90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5

Chemical Shift (ppm)

O OTBS

H

TBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

48

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

48

a111114dmma180.001.001.1r.esp

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

Chemical Shift (ppm)

O OTBS

I

TBS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

8a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

49

a111114dmma180.002.001.1r.esp

152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O OTBS

I

TBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

8a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

50

d090828dmma.129 = 130im winscp.010.001.1r.esp

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

Chemical Shift (ppm)

O O

OMeMeO

49

solvent: CDCl3 nucleus: 1H frequency: 500.130 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

51

d090828dmma.129 = 130im winscp.012.001.1r.esp

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

O O

OMeMeO

solvent: CDCl3 nucleus: 13C

frequency: 125.76 MHz

49

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

52

b090901dmma.130II.001.001.1r.esp

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

Chemical Shift (ppm)

O OH

MeO

50

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

53

b090901dmma.130II.003.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

O OH

MeO

50

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

54

c090902dmma.131.001.001.1r.esp

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

Chemical Shift (ppm)

O O

MeO

19b

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

55

c090902dmma.131.003.001.1r.esp

200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

O O

MeO

19b

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

56

c090907dmma.135-I.002.001.1r.esp

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

Chemical Shift (ppm)

O OH

MeO

TMS

21b

solvent: CDCl3 nucleus: 1H

frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

57

c090907dmma.135-I.001.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O OH

MeO

TMS

21b

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

58

b091006dmma.142_R.001.001.1r.esp

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

Chemical Shift (ppm)

O O

O

CF3

OMePh

MeO

TMS

51

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

59

b091006dmma.143_S.001.001.1r.esp

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

Chemical Shift (ppm)

O O

O

CF3

PhOMe

MeO

TMS

52

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

60

b091210dmma.164.002.001.1r.esp

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

Chemical Shift (ppm)

O OTBS

MeO

TMS

53

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

61

b091210dmma.164.001.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O OTBS

MeO

TMS

53

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

62

b091209dmma.165.001.001.1r.esp

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

Chemical Shift (ppm)

O OTBS

MeO

H

54

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

63

b091209dmma.165.003.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O OTBS

MeO

H

54

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

64

a111116dmma180_I.001.001.1r.esp

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

Chemical Shift (ppm)

O OTBS

IMeO

8b

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

65

a111116dmma180_I.002.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O OTBS

IMeO

8b

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

66

a120210dmma314_3.001.001.1r.esp

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

Chemical Shift (ppm)

O OH

MeO

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

22

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

67

a120210dmma314_3.002.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0

Chemical Shift (ppm)

O OH

MeO

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

22

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

68

c110117dmma.325_R.001.001.1r.esp

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

Chemical Shift (ppm)

O O

O

PhOMe

CF3

MeO

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

55

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

69

c110117dmma.326_S.001.001.1r.esp

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

Chemical Shift (ppm)

O O

O

CF3

PhOMe

MeO

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

56

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

70

a110805dmma438.001.001.1r.esp

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

Chemical Shift (ppm)

O OTBS

MeO

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

57

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

71

a110805dmma438.002.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0

Chemical Shift (ppm)

O OTBS

MeO

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

57

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

72

a110808dmma444.001.001.1r.esp

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

Chemical Shift (ppm)

O O

SnBu3MeO

TBS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

58

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

73

a110808dmma444.002.001.1r.esp

152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0

Chemical Shift (ppm)

O O

SnBu3MeO

TBS

solvent: CDCl3 nucleus: 13C

frequency: 75.48 MHz

58

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

74

a111115dmma445.001.001.1r.esp

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 -0.5

Chemical Shift (ppm)

O O

IMeO

TBS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

7

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

75

a111115dmma445.002.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0

Chemical Shift (ppm)

O O

IMeO

TBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

7

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

76

b081119dmma.51_001001r

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

Chemical Shift (ppm)

OMe

O

O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

24

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

77

b081119dmma.51_002001r

200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24

Chemical Shift (ppm)

OMe

O

O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

24

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

78

b090514dmae.001.001.001.1r.esp

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0

Chemical Shift (ppm)

OMe

O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

59

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

79

b090514dmae.001.002.001.1r.esp

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24

Chemical Shift (ppm)

OMe

O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

59

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

80

c080926dmma.9_002001r

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

Chemical Shift (ppm)

OMe

O

O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

26

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

81

c080926dmma.9_001001r

192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24

Chemical Shift (ppm)

OMe

O

O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

26

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

82

c090616dmae.09.002.001.1r.esp

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0

Chemical Shift (ppm)

OMe

O

OH

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

27

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

83

d081024dmnb.25_012001r

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24

Chemical Shift (ppm)

OMe

O

OH

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

27

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

84

c090309dmma.R.001.001.1r.esp

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5

Chemical Shift (ppm)

OMe

O

O O

MeOCF3

Ph

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

60

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

85

c090309dmma.S.001.001.1r.esp

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0

Chemical Shift (ppm)

OMe

O

O O

F3C OMePh

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

61

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

86

c090616dmae.10.001.001.1r.esp

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

Chemical Shift (ppm)

OMe

O

OTBS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

62

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

87

c090616dmae.10.002.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

OMe

O

OTBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

62

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

88

c090616dmae.12.002.001.1r.esp

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

Chemical Shift (ppm)

OMe

O

OTBS

O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

63

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

89

c081022dmnb.26_003001r

192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

OMe

O

OTBS

O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

63

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

90

AE015_me.010.001.1r.esp

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

Chemical Shift (ppm)

OMe

O

OTBS

I

10

E/Z = 7:1

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

91

c081111dmma.57.003.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0

Chemical Shift (ppm)

OMe

O

OTBS

I

10

E/Z = 7:1

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

92

c081112dmma.58.001.001.1r.esp

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

Chemical Shift (ppm)

OMe

O

OH

I

solvent: CDCl3 nucleus: 1H

frequency: 300.132 MHz

28

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

93

c081112dmma.58.003.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

OMe

O

OH

I

solvent: CDCl3 nucleus: 13C

frequency: 75.48 MHz

28

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

94

c101006dmma.JS01.002.001.1r.esp

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

Chemical Shift (ppm)

OEt

O

O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

64

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

95

c100909dmma.266.001.001.1r.esp

192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

OEt

O

O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

64

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

96

c101008dmma.JS02.002.001.1r.esp

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

Chemical Shift (ppm)

O

OEt

OH

solvent: CDCl3 nucleus: 1H

frequency: 300.132 MHz

32

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

97

c101008dmma.JS02.001.001.1r.esp

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16

Chemical Shift (ppm)

O

OEt

OH

solvent: CDCl3 nucleus: 13C

frequency: 75.48 MHz

32

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

98

c101025dmma.JS06.001.001.1r.esp

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

Chemical Shift (ppm)

O

OEt

OO

PhCF3

OCH3

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

65

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

99

c101025dmma.JS09.001.001.1r.esp

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

Chemical Shift (ppm)

O

OEt

OO

PhOCH3

CF3

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

66

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

100

c101011dmma.JS03.002.001.1r.esp

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

Chemical Shift (ppm)

O

OEt

OTBS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

67

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

101

c101011dmma.JS03.004.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O

OEt

OTBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

67

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

102

me_majs04.60010.001.1r.esp

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

Chemical Shift (ppm)

O

OH

OTBS

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

68

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

103

c101011dmma.JS04.004.001.1r.esp

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O

OH

OTBS

solvent: CDCl3 nucleus: 13C

frequency: 75.48 MHz

68

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

104

c101026dmma.JS08.002.001.1r.esp

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

Chemical Shift (ppm)

O

OMe

OTBS

solvent: CDCl3 nucleus: 1H

frequency: 300.132 MHz

33

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

105

c101026dmma.JS08.001.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0

Chemical Shift (ppm)

O

OMe

OTBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

33

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

106

c101025dmma.JS13.002.001.1r.esp

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

Chemical Shift (ppm)

O

OMe

OTBS

O

solvent: CDCl3 nucleus: 1H

frequency: 300.132 MHz

69

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

107

c101025dmma.JS13.001.001.1r.esp

192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O

OMe

OTBS

O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

69

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

108

a111019dmma474.001.001.1r.esp

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

Chemical Shift (ppm)

I

OTBS

OMe

O

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

18 9

E/Z = 8:1

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

109

a111019dmma474.002.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

I

OTBS

OMe

O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

18 9

E/Z = 8:1

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

110

me_ab016II.60010.001.1r.esp

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

Chemical Shift (ppm)

OTBS

O

OMeBO

O

37a

solvent: CDCl3 nucleus: 1H frequency: 600.130 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

111

c090710dmma.108.001.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

OTBS

O

OMeBO

O

37a

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

112

c090710dmma.109.002.001.1r.esp

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

Chemical Shift (ppm)

OTBS

O

OMeBO

O

37b

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

113

c090710dmma.109.001.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0

Chemical Shift (ppm)

OTBS

O

OMeBO

O

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

37b

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

114

me_ab017.60010.001.1r.esp

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

Chemical Shift (ppm)

OTBS

O

OMe

OTBSO

TBS

38a

solvent: CDCl3 nucleus: 1H frequency: 600.130 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

115

me_ab017.60011.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

OTBS

O

OMe

OTBSO

TBS

solvent: CDCl3 nucleus: 13C frequency: 150.90 MHz

38a

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

116

c100331dmma.205.001.001.1r.esp

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

Chemical Shift (ppm)

OTBS

O

OMe

O OTBS

TBS

38b

solvent: CDCl3 nucleus: 1H frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

117

c100331dmma.205.002.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

OTBS

O

OMe

O OTBS

TBS

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

38b

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

118

d100331dmab.018.001.001.1r.esp

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

Chemical Shift (ppm)

OTBS

O

OMe

OTBSO

OMe

39a

solvent: CDCl3 nucleus: 1H frequency: 500.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

119

d100331dmab.018.002.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

OTBS

O

OMe

OTBSO

OMe

39a

solvent: CDCl3 nucleus: 13C frequency: 125.76 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

120

me_ma204.60010.001.1r.esp

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

Chemical Shift (ppm)

O OTBS OTBS

OMe

O

OMe

39b

solvent: CDCl3 nucleus: 1H frequency: 600.130 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

121

me_ma204.60011.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O OTBS OTBS

OMe

O

OMe

39b

solvent: CDCl3 nucleus: 13C frequency: 150.90 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

122

d110923dmma.467.002.001.1r.esp

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

Chemical Shift (ppm)

OH

O

OMe

OHOH

4a

solvent: CDCl3 nucleus: 1H frequency: 500.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

123

d110923dmma.467.001.001.1r.esp

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

Chemical Shift (ppm)

OH

O

OMe

OHOH

4a

solvent: CDCl3 nucleus: 13C frequency: 125.76 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

124

d110923dmma.468.002.001.1r.esp

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

Chemical Shift (ppm)

OH OH OH

OMe

O

4b

solvent: CDCl3 nucleus: 1H

frequency: 500.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

125

d110923dmma.468.001.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16

Chemical Shift (ppm)

OH OH OH

OMe

O

4b

solvent: CDCl3 nucleus: 13C frequency: 125.76 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

126

me_ma460.60010.001.1r.esp

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

Chemical Shift (ppm)

OH

O

OMe

OHO

OMe

4c

solvent: CDCl3 nucleus: 1H frequency: 399.982 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

127

me_ma460.60016.001.1r.esp

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0

Chemical Shift (ppm)

OH

O

OMe

OHO

OMe

4c

solvent: CDCl3 nucleus: 13C frequency: 150.90 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

128

me_ma207.60010.001.1r.esp

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

Chemical Shift (ppm)

O OH OH

OMe

O

OMe

4d

solvent: CDCl3 nucleus: 1H frequency: 300.13 2MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

129

me_ma305.60012.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16

Chemical Shift (ppm)

O OH OH

OMe

O

OMe

4d

solvent: CDCl3 nucleus: 13C frequency: 150.90 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

130

a110505dmma395.001.001.1r.esp

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

Chemical Shift (ppm)

OMe

O

OTBS

B

O

O

40

solvent: CDCl3 nucleus: 1H

frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

131

a110505dmma395.002.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

OMe

O

OTBS

B

O

O

40

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

132

me_ma419.60010.001.1r.esp

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

Chemical Shift (ppm)

BO

O

OOPMB TBS

42

solvent: CDCl3 nucleus: 1H

frequency: 300.132 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

133

me_ma419.60012.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

BO

O

OOPMB TBS

42

solvent: CDCl3 nucleus: 13C frequency: 75.48 MHz

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

134

me_ma463.60010.001.1r.esp

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

Chemical Shift (ppm)

O

O

OMe

OO

TBS TBS

OMe

solvent: CDCl3 nucleus: 1H frequency: 600.130 MHz

41

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

135

me_ma463.60012.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

O

O

OMe

OO

TBS TBS

OMe

solvent: CDCl3 nucleus: 13C frequency: 150.90 MHz

41

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

136

me_ma476.60010.001.1r.esp

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

Chemical Shift (ppm)

OH

O

OMe

OHO

OMe

solvent: CDCl3 nucleus: 1H

frequency: 600.130 MHz

3

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

137

me_ma476.60011.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16

Chemical Shift (ppm)

OH

O

OMe

OHO

OMe

solvent: CDCl3 nucleus: 13C frequency: 150.90 MHz

3

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

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