Supporting Information - Semantic Scholar€¦ · 1 Supporting Information Titanium mediated...

1

Supporting Information

Titanium mediated olefination of aldehydes with α-haloacetates: an exceptionally stereoselective and general approach to (Z)-α-haloacrylates

John Kallikat Augustine,* a Agnes Bombrun,b Srinivasa Venkatachaliah,a Anandh Jothia

aSyngene International Ltd., Biocon Park, Plot Nos. 2 & 3, Bommasandra IV Phase, Jigani Link

Road, Bangalore - 560 099, India.

bCovance Central Laboratory Services, 7 Rue Moise-Marcinhes, 1217 Meyrin, Geneva, Switzerland.

[email protected]

Table of contents

Table of contents.………………………………………………….... 1 1H NMR, 13C NMR, HPLC and IR reports for 1aE…….………… 2-5 1H NMR, 13C NMR, HPLC and IR reports for 1a-1q…….………… 6-73 1H NMR, 13C NMR, HPLC and IR reports for 2a-2j……….………. 74-113 1H NMR, 13C NMR, HPLC and IR reports for 3a-3i……….………. 114-149 1H NMR, 13C NMR, HPLC and IR reports for 4a-4j……….………. 150-189 1H NMR, 13C NMR reports for 5 …………………….……….……. 190-191

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013

2

(E)-isomer (1aE): 1H NMR (400 MHz) in DMSO-d6

Br

BrCOOMe

H

1aE

delta 7.54 ppm


3

13C NMR (100 MHz) in CDCl3 (1aE)

Br

BrCOOMe

1aE

(E)


4

IR data (1aE)

Br

BrCOOMe

1aE

(E)


5

HPLC data (1aE)

Br

BrCOOMe

1aE

(E)


6

(Z)-isomer (1a): 1H NMR (400 MHz) in DMSO-d6

Br

COOMe

Br

H

1a

delta 8.25 ppm


7

13C NMR (100 MHz) in CDCl3 (1a)


8

IR spectrum (1a)


9

HPLC data (1a)


10

1H NMR (400 MHz) in CDCl3 (1b)


11

13C NMR (100 MHz) in CDCl3 (1b)


12

IR spectrum (1b)


13

HPLC data (1b)


14

1H NMR (400 MHz) in CDCl3 (1c)

Br

O

O(Z)

(1c)N


15

13C NMR (100 MHz) in CDCl3 (1c)

Br

O

O(Z)

(1c)N


16

IR spectrum (1c)

Br

O

O(Z)

(1c)N


17

HPLC data (1c)

Br

O

O(Z)

(1c)N


18

1H NMR (400 MHz) in DMSO-d6 (1d)

Br

O

O

O

O

(Z)

(1d)


19

13C NMR (100 MHz) in CDCl3 (1d)

Br

O

O

O

O

(Z)

(1d)


20

IR spectrum (1d)

Br

O

O

O

O

(Z)

(1d)


21

HPLC data (1d)

Br

O

O

O

O

(Z)

(1d)


22

1H NMR (400 MHz) in CDCl3 (1e)

Br

O

O

Br

Cl(Z)

(1e)


23

13C NMR (100 MHz) in CDCl3 (1e)

Br

O

O

Br

Cl(Z)

(1e)


24

IR spectrum (1e)

Br

O

O

Br

Cl(Z)

(1e)


25

HPLC data (1e)

Br

O

O

Br

Cl(Z)

(1e)


26

1H NMR (400 MHz) in CDCl3 (1f)


27

13C NMR (100 MHz) in CDCl3 (1f)


28

IR spectrum (1f)


29

HPLC data (1f)


30

1H NMR (400 MHz) in CDCl3 (1g)

O

O

BrNC

(Z)

(1g)


31

13C NMR (100 MHz) in CDCl3 (1g)

O

O

BrNC

(Z)

(1g)


32

IR spectrum (1g)

O

O

BrNC

(Z)

(1g)


33

HPLC data (1g)

O

O

BrNC

(Z)

(1g)


34

1H NMR (400 MHz) in CDCl3 (1h)

O

O

Br

(Z)

(1h)


35

13C NMR (100 MHz) in CDCl3 (1h)

O

O

Br

(Z)

(1h)


36

IR spectrum (1h)

O

O

Br

(Z)

(1h)


37

HPLC data (1h)

O

O

Br

(Z)

(1h)


38

1H NMR (400 MHz) in DMSO-d6 (1i)

( Z )

(1i)N

Br

COOMe


39

13C NMR (100 MHz) in DMSO-d6 (1i)

( Z )

(1i)N

Br

COOMe


40

IR spectrum (1i)

( Z )

(1i)N

Br

COOMe


41

HPLC data (1i)

( Z )

(1i)N

Br

COOMe


42

1H NMR (400 MHz) in CDCl3 (1j)

NBr

O

O

F

F

( Z)

(1j)

F


43

13C NMR (100 MHz) in CDCl3 (1j)

NBr

O

O

F

F

( Z)

(1j)

F


44

IR spectrum (1j)

NBr

O

O

F

F

( Z)

(1j)

F


45

HPLC data (1j)

NBr

O

O

F

F

( Z)

(1j)

F


46

1H NMR (400 MHz) in CDCl3 (1k)

(1k)Br

COOMeSBr

(Z)


47

13C NMR (100 MHz) in CDCl3 (1k)

(1k)Br

COOMeSBr

(Z)


48

IR spectrum (1k)

(1k)Br

COOMeSBr

(Z)


49

HPLC data (1k)

(1k)Br

COOMeSBr

(Z)


50

1H NMR (400 MHz) in CDCl3 (1l)

(Z)

(1l)Br

COOMeO


51

13C NMR (100 MHz) in CDCl3 (1l)

(Z)

(1l)Br

COOMeO


52

IR spectrum (1l)

(Z)

(1l)Br

COOMeO


53

HPLC data (1l)

(Z)

(1l)Br

COOMeO


54

1H NMR (400 MHz) in CDCl3 (1m)

( Z )

Br

O

O

(1m)


55

13C NMR (100 MHz) in CDCl3 (1m)

( Z )

Br

O

O

(1m)


56

IR spectrum (1m)

( Z )

Br

O

O

(1m)


57

HPLC data (1m)

( Z )

Br

O

O

(1m)


58

1H NMR (400 MHz) in CDCl3 (1n)

( Z )

Br

O

O

(1n)


59

13C NMR (100 MHz) in CDCl3 (1n)

( Z )

Br

O

O

(1n)


60

IR spectrum (1n)

( Z )

Br

O

O

(1n)


61

HPLC data (1n)

( Z )

Br

O

O

(1n)


62

1H NMR (400 MHz) in CDCl3 (1o)

( Z )

Br

O

O

(1o)


63

13C NMR (100 MHz) in CDCl3 (1o)

( Z )

Br

O

O

(1o)


64

IR spectrum (1o)

( Z )

Br

O

O

(1o)


65

HPLC data (1o)

( Z )

Br

O

O

(1o)


66

1H NMR (400 MHz) in CDCl3 (1p)

( Z )

Br

O

OOMe

(1p)


67

13C NMR (100 MHz) in CDCl3 (1p)

( Z )

Br

O

OOMe

(1p)


68

IR spectrum (1p)

( Z )

Br

O

OOMe

(1p)


69

HPLC data (1p)

( Z )

Br

O

OOMe

(1p)


70

1H NMR (400 MHz) in DMSO-d6 (1q)

Br

OH

O

O(Z)

(1q)


71

13C NMR (100 MHz) in DMSO-d6 (1q)

Br

OH

O

O(Z)

(1q)


72

IR spectrum (1q)

Br

OH

O

O(Z)

(1q)


73

HPLC data (1q)

Br

OH

O

O(Z)

(1q)


74

1H NMR (400 MHz) in DMSO-d6 (2a)

ClO

O(Z)

(2a)


75

13C NMR (100 MHz) in DMSO-d6 (2a)

ClO

O(Z)

(2a)


76

IR spectrum (2a)

ClO

O(Z)

(2a)


77

HPLC data (2a)

ClO

O(Z)

(2a)


78

1H NMR (400 MHz) in DMSO-d6 (2b)

ClO

O(Z)

Br(2b)


79

13C NMR (100 MHz) in DMSO-d6 (2b)

ClO

O(Z)

Br(2b)


80

IR spectrum (2b)

ClO

O(Z)

Br(2b)


81

HPLC data (2b)

ClO

O(Z)

Br(2b)


82

1H NMR (400 MHz) in DMSO-d6 (2c)

O

O

O

Cl

(Z)

(2c)


83

13C NMR (100 MHz) in DMSO-d6 (2c)

O

O

O

Cl

(Z)

(2c)


84

IR spectrum (2c)

O

O

O

Cl

(Z)

(2c)


85

HPLC data (2c)

O

O

O

Cl

(Z)

(2c)


86

1H NMR (400 MHz) in CDCl3 (2d)

NCCl

O

O(Z)

(2d)


87


NCCl

O

O(Z)

(2d)


88

IR spectrum (2d)

NCCl

O

O(Z)

(2d)


89

HPLC data (2d)

NCCl

O

O(Z)

(2d)


90


O

O

Cl

F

FF

(Z)NO2

(2e)


91


O

O

Cl

F

FF

(Z)NO2

(2e)


92

IR spectrum (2e)

O

O

Cl

F

FF

(Z)NO2

(2e)


93

HPLC data (2e)

O

O

Cl

F

FF

(Z)NO2

(2e)


94

1H NMR (400 MHz) in DMSO-d6 (2f)

OO

O

Cl

(Z)

(2f)


95

13C NMR (100 MHz) in DMSO-d6 (2f)

OO

O

Cl

(Z)

(2f)


96

IR spectrum (2f)

OO

O

Cl

(Z)

(2f)


97

HPLC data (2f)

OO

O

Cl

(Z)

(2f)


98

1H NMR (400 MHz) in DMSO-d6 (2g)

NO

O

O

Cl

(Z)

(2g)


99

13C NMR (100 MHz) in DMSO-d6 (2g)

NO

O

O

Cl

(Z)

(2g)


100

IR spectrum (2g)

NO

O

O

Cl

(Z)

(2g)


101

HPLC data (2g)

NO

O

O

Cl

(Z)

(2g)


102


O

O

ClO2N

(Z)

(2h)


103


O

O

ClO2N

(Z)

(2h)


104

IR spectrum (2h)

O

O

ClO2N

(Z)

(2h)


105

HPLC data (2h)

O

O

ClO2N

(Z)

(2h)


106

1H NMR (400 MHz) in CDCl3 (2i)

O

O

Cl

(Z)

(2i)


107

13C NMR (100 MHz) in CDCl3 (2i)

O

O

Cl

(Z)

(2i)


108

IR spectrum (2i)

O

O

Cl

(Z)

(2i)


109

HPLC data (2i)

O

O

Cl

(Z)

(2i)


110


O

O

Cl

(Z)

(2j)


111


O

O

Cl

(Z)

(2j)


112

IR spectrum (2j)

O

O

Cl

(Z)

(2j)


113

HPLC data (2j)

O

O

Cl

(Z)

(2j)


114

1H NMR (400 MHz) in CDCl3 (3a)

F

O

O(Z)

(3a)


115

13C NMR (100 MHz) in CDCl3 (3a)

F

O

O(Z)

(3a)


116

IR spectrum (3a)

F

O

O(Z)

(3a)


117

HPLC data (3a)

F

O

O(Z)

(3a)


118


BrF

O

O(Z)

(3b)


119

13C NMR (100 MHz) in CDCl3 (3b)

BrF

O

O(Z)

(3b)


120

IR spectrum (3b)

BrF

O

O(Z)

(3b)


121

HPLC data (3b)

BrF

O

O(Z)

(3b)


122


OF

O

O(Z)

(3c)


123


OF

O

O(Z)

(3c)


124

IR spectrum (3c)

OF

O

O(Z)

(3c)


125

HPLC data (3c)

OF

O

O(Z)

(3c)


126


NCF

O

O(Z)

(3d)


127


NCF

O

O(Z)

(3d)


128

IR spectrum (3d)

NCF

O

O(Z)

(3d)


129

HPLC data (3d)

NCF

O

O(Z)

(3d)


130


NO2

F

F

FF

O

O(Z)

(3e)


131


NO2

F

F

FF

O

O(Z)

(3e)


132

IR spectrum (3e)

NO2

F

F

FF

O

O(Z)

(3e)


133

HPLC data (3e)

NO2

F

F

FF

O

O(Z)

(3e)


134


O

F

O

O

(Z)

(3f )


135


O

F

O

O

(Z)

(3f )


136

IR spectrum (3f)

O

F

O

O

(Z)

(3f )


137

HPLC spectrum (3f)

O

F

O

O

(Z)

(3f )


138


NOF

O

O(Z)

(3g)


139


NOF

O

O(Z)

(3g)


140

IR spectrum (3g)

NOF

O

O(Z)

(3g)


141

HPLC data (3g)

NOF

O

O(Z)

(3g)


142


FO

O

O2N

(Z)

(3h)


143


F

O

O

O2N

(Z)

(3h)


144

IR spectrum (3h)

FO

O

O2N

(Z)

(3h)


145

HPLC data (3h)

F

O

O

O2N

(Z)

(3h)


146


F

O

O(Z)

(3i)


147


F

O

O(Z)

(3i)


148

IR spectrum (3i)

F

O

O(Z)

(3i)


149

HPLC data (3i)

F

O

O(Z)

(3i)


150

1H NMR (400 MHz) in CDCl3 (4a)

I

O

O

(Z)

4a


151

13c NMR (100 MHz) in CDCl3 (4a)

I

O

O

(Z)

4a


152

IR spectrum (4a)

I

O

O

(Z)

4a


153

HPLC spectrum (4a)

I

O

O

(Z)

4a


154


IO

O(Z)

Br 4b


155

13c NMR (100 MHz) in CDCl3 (4b)

IO

O(Z)

Br 4b


156

IR spectrum (4b)

IO

O(Z)

Br 4b


157

HPLC data (4b)

IO

O(Z)

Br 4b


158


IO

O(Z)

O 4c


159


IO

O(Z)

O 4c


160

IR spectrum (4c)


161

HPLC data (4c)

IO

O(Z)

O 4c


162


IO

O(Z)

CN 4d


163


IO

O(Z)

CN 4d


164

IR spectrum (4d)

IO

O(Z)

CN 4d


165

HPLC data (4d)

IO

O(Z)

CN 4d


166


4eI

O

O(Z)

FF

F

NO2


167


4eI

O

O(Z)

FF

F

NO2


168

IR spectrum (4e)

4eI

O

O(Z)

FF

F

NO2


169

HPLC data (4e)

4eI

O

O(Z)

FF

F

NO2


170


4f

OI O

O(Z)


171


4f

OI O

O(Z)


172

IR spectrum (4f)

4f

OI O

O(Z)


173

HPLC data (4f)

4f

OI O

O(Z)


174



175



176

IR spectrum (4g)


177

HPLC data (4g)


178

1H NMR (400 MHz) in DMSO-d6 (4h)


179

13C NMR (100 MHz) in DMSO-d6 (4h)


180

IR spectrum (4h)


181

HPLC data (4h)


182


4iI

O

O(Z)


183


4iI

O

O(Z)


184

IR spectrum (4i)

4iI

O

O(Z)


185

HPLC data (4i)

4iI

O

O(Z)


186


4jI

O

O(Z)


187


4jI

O

O(Z)


188

IR spectrum (4j)

4jI

O

O(Z)


189

HPLC data (4j)

4jI

O

O(Z)


190

1H NMR (400 MHz) in CDCl3 (5)

O

OO

O

(5)


191

13C NMR (100 MHz) in CDCl3 (5)

**************************

O

OO

O

(5)


Supporting Information - Semantic Scholar€¦ · 1 Supporting Information Titanium mediated...

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