Asymmetric organocatalytic synthesis of tertiary azomethyl … · 2017. 3. 7. · 1 Asymmetric...

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Asymmetricorganocatalyticsynthesisoftertiaryazomethylalcohols:keyintermediatestowardsazoxycompoundsandα-hydroxy-β-aminoestersJoséA.Carmona,aGonzalodeGonzalo,bInmaculadaSerrano,b,AnaM.Crespo-Peña,aMichalŠimek,aDavidMonge,*,bRosarioFernández*,bandJoséM.Lassaletta*,a

InstitutodeInvestigacionesQuímicas(CSIC-US),C/AméricoVespucio49,

41092Sevilla(Spain),andDepartamentodeQuímicaOrgánica,

UniversidaddeSevilla,C/Prof.GarcíaGonzález,1,41012Sevilla(Spain)

dmonge@us.es; ffernan@us.es;jmlassa@iiq.csic.es

CONTENTS 1.NMRSpectra.......................................................................................................................................2

2.GCChromatograms...........................................................................................................................38

3.HPLCChromatograms.......................................................................................................................40

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2017

2

1.NMRSpectra:1HNMR(CDCl3,500MHz)ofVIII:

13CNMR(CDCl3,125MHz)ofVIII:

3

1HNMR(CD3OD,500MHz)of9a:

13CNMR(CD3OD,125MHz)of9a:

4

1HNMR(CD3OD,500MHz)of10a:

13CNMR(CD3OD,125MHz)of10a:

5

1HNMR(CDCl3,400MHz)ofIX:

13CNMR(CDCl3,100MHz)ofIX:

6

1HNMR(CDCl3,500MHz)ofX:

13CNMR(CDCl3,125MHz)ofX:

7

1HNMR(CDCl3,500MHz)ofXI:

13CNMR(CDCl3,125MHz)ofXI:

8

1HNMR(CDCl3,400MHz)ofXII:

13CNMR(CDCl3,100MHz)ofXII:

O

OBz

HN

BzO

BzO

OBz

HN

S

XII

CF3

CF3

9

1HNMR(CDCl3,300MHz)ofXIII:

13CNMR(CDCl3,75MHz)ofXIII:

O

OPiv

HN

PivO

PivO

OPiv

HN

S

XIII

CF3

CF3

10

1HNMR(CDCl3,400MHz)of[(S)-3a]:

13CNMR(CDCl3,100MHz)of[(S)-3a]:

11

1HNMR(CDCl3,400MHz)of[(S)-3b]:

13CNMR(CDCl3,100MHz)of[(S)-3b]:

12

1HNMR(CDCl3,300MHz)of[(S)-3c]:

13CNMR(CDCl3,125MHz)of[(S)-3c]:

13

1HNMR(CDCl3,400MHz)of[(S)-3d]:

13CNMR(CDCl3,100MHz)of[(S)-3d]:

14

1HNMR(CDCl3,300MHz)of[(S)-3e]:

13CNMR(CDCl3,75MHz)of[(S)-3e]:

15

1HNMR(CDCl3,400MHz)of[(S)-3f]:

13CNMR(CDCl3,100MHz)of[(S)-3f]:

16

1HNMR(CDCl3,400MHz)of[(S)-3g]:

13CNMR(CDCl3,100MHz)of[(S)-3g]:

17

1HNMR(CDCl3,400MHz)of[(S)-4a]:

13CNMR(CDCl3,100MHz)of[(S)-4a]:

18

1HNMR(CDCl3,500MHz)of[(S)-4b]:

13CNMR(CDCl3,125MHz)of[(S)-4b]:

19

1HNMR(CDCl3,300MHz)of[(S)-4c]:

13CNMR(CDCl3,125MHz)of[(S)-4c]:

20

1HNMR(CDCl3,400MHz)of[(S)-4d]:

13CNMR(CDCl3,100MHz)of[(S)-4d]:

21

1HNMR(CDCl3,300MHz)of[(S)-4e]:

13CNMR(CDCl3,75MHz)of[(S)-4e]:

22

1HNMR(CDCl3,400MHz)of[(S)-4f]:

13CNMR(CDCl3,100MHz)of[(S)-4f]:

23

1HNMR(CDCl3,400MHz)of[(R)-4h]:

13CNMR(CDCl3,100MHz)of[(R)-4h]:

24

1HNMR(CDCl3,400MHz)of[(R)-4i]:

13CNMR(CDCl3,100MHz)of[(R)-4i]:

25

1HNMR(CDCl3,400MHz)of[(R)-4j]:

13CNMR(CDCl3,100MHz)of[(R)-4j]:

26

1HNMR(CDCl3,300MHz)of[(R)-4k]:

13CNMR(CDCl3,75MHz)of[(R)-4k]:

27

1HNMR(CDCl3,300MHz)of[(R)-4l]:

13CNMR(CDCl3,75MHz)of[(R)-4l]:

28

1HNMR(CDCl3,300MHz)of[(S)-5a]:

13CNMR(CDCl3,75MHz)of[(S)-5a]:

29

1HNMR(CDCl3,300MHz)of[(S)-5c]:

13CNMR(CDCl3,75MHz)of[(S)-5c]:

30

1HNMR(CDCl3,300MHz)of[(S)-5d]:

13CNMR(CDCl3,75MHz)of[(S)-5d]:

31

1HNMR(CDCl3,300MHz)of[(S)-5e]:

13CNMR(CDCl3,75MHz)of[(S)-5e]:

32

1HNMR(CDCl3,400MHz)of[(S)-5f]:

13CNMR(CDCl3,100MHz)of[(S)-5f]:

33

1HNMR(CDCl3,300MHz)of[(R)-5h]:

13CNMR(CDCl3,75MHz)of[(R)-5h]:

34

1HNMR(CDCl3,300MHz)of[(R)-5i]:

13CNMR(CDCl3,75MHz)of[(R)-5i]:

35

1HNMR(CDCl3,400MHz)of[(R)-5j]:

13CNMR(CDCl3,100MHz)of[(R)-5j]:

36

1HNMR(CDCl3,300MHz)of[(R)-5k]:

13CNMR(CDCl3,75MHz)of[(R)-5k]:

37

1HNMR(CDCl3,300MHz)of[(R)-5l]:

13CNMR(CDCl3,75MHz)of[(R)-5l]:

38

2.GCChromatogramsGCconditionsfor3a:ChrompackCP7500,cyclodextrin-β,225mx0.25mmx0.25μm,Heasmobilephase

39

GC conditions for (S)-3b: Chrompack CP7500, cyclodextrin-β, 225m x 0.25 mm x 0.25 µm, He as mobile phase

40

3.HPLCChromatograms HPLCconditionsfor(S)-3c:ChiralpakAD-Hcolumn[hexane/i-PrOH(98:2)1mL/min]

HPLCconditionsfor(S)-3e:ChiralpakOJ-Hcolumn[hexane/iPrOH(98:2)1mL/min]

41

HPLCconditionsfor(S)-4a:ChiralpakAD-Hcolumn[hexane/i-PrOH(98:2)1mL/min]

HPLCconditionsfor(S)-4b:ChiralpakOJcolumn[hexane/i-PrOH(98:2)1mL/min]

42

HPLCconditionsfor(S)-4c:ChiralpakAD-Hcolumn[hexane/i-PrOH(98:2)1mL/min]

HPLCconditionsfor(S)-4d:ChiralpakAD-Hcolumn[hexane/i-PrOH(80:20)1mL/min]

43

HPLCconditionsfor(S)-4e:ChiralpakOJ-Hcolumn[hexane/iPrOH(98:2)1mL/min]

HPLCconditionsfor(S)-4f:ChiralpakAD-Hcolumn[hexane/i-PrOH(80:20)1mL/min]

44

HPLCconditionsfor(S)-4g:ChiralpakAD-Hcolumn[hexane/i-PrOH(80:20)1mL/min]

HPLCconditionsfor(R)-4h:ChiralpakAD-Hcolumn[hexane/i-PrOH(80:20)1mL/min]

45

HPLCconditionsfor(R)-4i:ChiralpakAD-Hcolumn[hexane/i-PrOH(80:20)1mL/min]

HPLCconditionsfor(R)-4j:ChiralpakAD-Hcolumn[hexane/i-PrOH(80:20)1mL/min]

46

HPLCconditionsfor(R)-4k:ChiralpakAD-Hcolumn[hexane/iPrOH(98:2)1mL/min]

HPLCconditionsfor(R)-4l:ChiralpakAD-Hcolumn[hexane/iPrOH(80:20)1mL/min]

47

HPLCconditionsfor(S)-5a:ChiralpakAD-Hcolumn[hexane/iPrOH(80:20)1mL/min]

HPLCconditionsfor(S)-5c:ChiralpakAD-Hcolumn[hexane/iPrOH(80:20)1mL/min]

48

HPLCconditionsfor(S)-5d:ChiralpakAD-Hcolumn[hexane/iPrOH(80:20)1mL/min]

HPLCconditionsfor(S)-5e:ChiralpakOJ-Hcolumn[hexane/iPrOH(90:10)1mL/min]

49

HPLCconditionsfor(S)-5f:ChiralpakAD-Hcolumn[hexane/iPrOH(80:20)1mL/min]

HPLCconditionsfor(R)-5h:ChiralpakAD-Hcolumn[hexane/iPrOH(80:20)1mL/min]

50

HPLCconditionsfor(R)-5i:ChiralpakIBcolumn[hexane/iPrOH(90:10)1mL/min]

HPLCconditionsfor(R)-5j:ChiralpakAD-Hcolumn[hexane/iPrOH(80:20)1mL/min]

51

HPLCconditionsfor(R)-5k:ChiralpakIAcolumn[hexane/iPrOH(80:20)1mL/min]

HPLCconditionsfor(R)-5l:ChiralpakAD-Hcolumn[hexane/iPrOH(80:20)1mL/min]