1

Binaphthyl-Based Chiral Bifunctional Organocatalysts for Water Mediated Asymmetric List-Lerner-Barbas Aldol Reactions

Veeramanoharan Ashokkumar, Chinnadurai Chithirai kuma, Ayyanar Siva

Supramolecular and Organometallic Chemistry Lab, School of Chemistry, Madurai Kamaraj University,

Madurai 625 021, Tamil Nadu, India.

E-mail: drasiva@gmail.com

Supporting Information

Table of Contents

S. NO Contents Page no.

1 NMR & Mass spectrum of intermediates, organocatatalysts 17, 18 and aldol products

2-25

2 HPLC chromatograms of aldol products 26-62

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

2

Figure S1: 1H NMR Spectrum of compound 14.

Figure S2: 13C NMR Spectrum of compound 14.

3

Figure S3: ESI-Mass Spectrum of compound 14.

Figure S4: 1H NMR Spectrum of compound 15.

4

Figure S5: 13C NMR Spectrum of compound 15.

Figure S6: ESI-Mass Spectrum of compound 15.

5

Figure S7: 1H NMR Spectrum of organocatalyst (17a).

Figure S8: 13C NMR Spectrum of organocatalyst (17a).

6

Figure S9: ESI-Mass Spectrum of organocatalyst (17a).

Figure S10: 1H NMR Spectrum of organocatalyst (17b).

7

Figure S11: 13C NMR Spectrum of organocatalyst (17b).

Figure S12: ESI-Mass Spectrum of organocatalyst (17b).

8

Figure S13: 1H NMR Spectrum of aldol product 7a.

Figure S14: 13C NMR Spectrum of aldol product 7a.

9

Figure S15: 1H NMR Spectrum of aldol product 7b.

Figure S16: 13C NMR Spectrum of aldol product 7b.

10

Figure S17: 1H NMR Spectrum of aldol product 7c.

Figure S18: 13C NMR Spectrum of aldol product 7c.

11

Figure S19: 1H NMR Spectrum of aldol product 7d.

Figure S20: 13C NMR Spectrum of aldol product 7d.

12

Figure S21: 1H NMR Spectrum of aldol product 7e.

Figure S22: 13C NMR Spectrum of aldol product 7e.

13

Figure S23: 1H NMR Spectrum of aldol product 7f.

Figure S24: 13C NMR Spectrum of aldol product 7f.

14

Figure S25: 1H NMR Spectrum of aldol product 7g.

Figure S26: 13C NMR Spectrum of aldol product 7g.

15

Figure S27: 1H NMR Spectrum of aldol product 7h.

Figure S28: 13C NMR Spectrum of aldol product 7h.

16

Figure S29: 1H NMR Spectrum of aldol product 9a.

Figure S30: 13C NMR Spectrum of aldol product 9a.

17

Figure S31: 1H NMR Spectrum of aldol product 9b.

Figure S32: 13C NMR Spectrum of aldol product 9b.

18

Figure S33: 1H NMR Spectrum of aldol product 9c.

Figure S34: 13C NMR Spectrum of aldol product 9c.

19

Figure S35: 1H NMR Spectrum of aldol product 10a.

Figure S36: 13C NMR Spectrum of aldol product 10a.

20

Figure S37: 1H NMR Spectrum of aldol product 10b.

Figure S38: 13C NMR Spectrum of aldol product 10b.

21

Figure S39: 1H NMR Spectrum of aldol product 10c.

Figure S40: 13C NMR Spectrum of aldol product 10c.

22

Figure S41: 1H NMR Spectrum of aldol product 11a.

Figure S42: 13C NMR Spectrum of aldol product 11a.

23

Figure S43: 1H NMR Spectrum of aldol product 11d.

Figure S44: 13C NMR Spectrum of aldol product 11d.

24

Figure S45: 1H NMR Spectrum of aldol product 11e.

Figure S46: 13C NMR Spectrum of aldol product 11e.

25

Figure S47: 1H NMR Spectrum of aldol product 11f.

Figure S48: 13C NMR Spectrum of aldol product 11f.

26

Figure S49: HPLC chromatogram of (7) Racemic mixture.

Figure S50: HPLC chromatogram of (7a) in the presence organocatalyst (17a), CH3COOH

(2 mol%) and H2O in 0 °C condition.

27

Figure S51: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S52: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and CH3OH in 0 °C condition.

28

Figure S53: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and CH3CH2OH in 0 °C condition.

Figure S54: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and DMF in 0 °C condition.

29

Figure S55: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and 1,4-Dioxane in 0 °C condition.

Figure S56: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and CH3OH + H2O in 0 °C condition.

30

Figure S57: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and DMF + H2O in 0 °C condition.

Figure S58: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and 1,4-Dioxane + H2O in 0 °C condition.

31

Figure S59: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S60: HPLC chromatogram of (7a) in the presence organocatalyst (17b), PhCOOH (2 mol%) and H2O in 0 °C condition.

32

Figure S61: HPLC chromatogram of (7a) in the presence organocatalyst (17b), PhCOOH (10 mol%) and H2O in 0 °C condition.

Figure S62: HPLC chromatogram of (7a) in the presence organocatalyst (17b), HCOOH (2 mol%) and H2O in 0 °C condition.

33

Figure S63: HPLC chromatogram of (7a) in the presence organocatalyst (17b), HCOOH (10 mol%) and H2O in 0 °C condition.

Figure S64: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

34

Figure S65: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (10 mol%) and H2O in 0 °C condition.

Figure S66: HPLC chromatogram of (7a) in the presence organocatalyst (17b), Oxalic acid (2 mol%) and H2O in 0 °C condition.

35

Figure S67: HPLC chromatogram of (7a) in the presence organocatalyst (17b), Oxalic acid (10 mol%) and H2O in 0 °C condition.

Figure S68: HPLC chromatogram of (7a) in the presence organocatalyst (17b, 1 mol%), CH3COOH (2 mol%) and H2O in 30 °C condition.

36

Figure S69: HPLC chromatogram of (7a) in the presence organocatalyst (17b, 1 mol%), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S70: HPLC chromatogram of (7a) in the presence organocatalyst (17b, 1 mol%), CH3COOH (2 mol%) and H2O in 60 °C condition.

37

Figure S71: HPLC chromatogram of (7a) in the presence organocatalyst (17b, 1 mol%), CH3COOH (2 mol%) and H2O in −20 °C condition.

Figure S72: HPLC chromatogram of (7a) in the presence organocatalyst (17b, 5 mol%), CH3COOH (2 mol%) and H2O in 0 °C condition.

38

Figure S73: HPLC chromatogram of (7a) in the presence organocatalyst (17b, 10 mol%), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S74: HPLC chromatogram of (7a) in the presence organocatalyst (17b, 20 mol%), CH3COOH (2 mol%) and H2O in 0 °C condition.

39

Figure S75: HPLC chromatogram of (7a) Racemic mixture.

Figure S76: HPLC chromatogram of (7a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

40

Figure S77: HPLC chromatogram of (8a) in the presence organocatalyst (18b), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S78: HPLC chromatogram of (7b) Racemic mixture.

41

Figure S79: HPLC chromatogram of (7b) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S80: HPLC chromatogram of (8b) in the presence organocatalyst (18b), CH3COOH (2 mol%) and H2O in 0 °C condition.

42

Figure S81: HPLC chromatogram of (7c) Racemic mixture.

Figure S82: HPLC chromatogram of (7c) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

43

Figure S83: HPLC chromatogram of (8c) in the presence organocatalyst (18b), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S84: HPLC chromatogram of (7d) Racemic mixture.

44

Figure S85: HPLC chromatogram of (7d) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S86: HPLC chromatogram of (8d) in the presence organocatalyst (18b), CH3COOH (2 mol%) and H2O in 0 °C condition.

45

Figure S87: HPLC chromatogram of (7e) in the presence organocatalyst (17b), CH3COOH (2 mole%) and H2O in 0 °C conditions.

Figure S88: HPLC chromatogram of (8e) in the presence organocatalyst (18b), CH3COOH

(2 mol%) and H2O in 0 °C condition.

46

Figure S89: HPLC chromatogram of (7f) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S90: HPLC chromatogram of (8f) in the presence organocatalyst (18b), CH3COOH (2 mol%) and H2O in 0 °C condition.

47

Figure S91: HPLC chromatogram of (7g) Racemic mixture.

Figure S92: HPLC chromatogram of (7g) in the presence organocatalyst (17b), CH3COOH

(2 mol%) and H2O in 0 °C condition.

48

Figure S93: HPLC chromatogram of (8g) in the presence organocatalyst (18b), CH3COOH

(2 mol%) and H2O in 0 °C condition.

Figure S94: HPLC chromatogram of (7h) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

49

Figure S95: HPLC chromatogram of (8h) in the presence organocatalyst (18b), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S96: HPLC chromatogram of (9a) Racemic mixture.

50

Figure S97: HPLC chromatogram of (9a) in the presence organocatalyst (17a), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S98: HPLC chromatogram of (9a) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

51

Figure S99: HPLC chromatogram of (9b) Racemic mixture.

Figure S100: HPLC chromatogram of (9b) in the presence organocatalyst (17a), CH3COOH

(2 mol%) and H2O in 0 °C condition.

52

Figure S101: HPLC chromatogram of (9b) in the presence organocatalyst (17b), CH3COOH

(2 mol%) and H2O in 0 °C condition.

Figure S102: HPLC chromatogram of (9c) Racemic mixture.

53

Figure S103: HPLC chromatogram of (9c) in the presence organocatalyst (17a), CH3COOH

(2 mol%) and H2O in 0 °C condition.

Figure S104: HPLC chromatogram of (9c) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

54

Figure S105: HPLC chromatogram of (10a) in the presence organocatalyst (17a), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S106: HPLC chromatogram of (10a) in the presence organocatalyst (17b),

CH3COOH (2 mol%) and H2O in 0 °C condition.

55

Figure S107: HPLC chromatogram of (10b) in the presence organocatalyst (17a),

CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S108: HPLC chromatogram of (10b) in the presence organocatalyst (17b),

CH3COOH (2 mol%) and H2O in 0 °C condition.

56

Figure S109: HPLC chromatogram of (10c) in the presence organocatalyst (17a), CH3COOH

(2 mol%) and H2O in 0 °C condition.

Figure S110: HPLC chromatogram of (10c) in the presence organocatalyst (17b), CH3COOH (2 mol%) and H2O in 0 °C condition.

57

Figure S111: HPLC chromatogram of (11a) in the presence organocatalyst (17a), CH3COOH

(2 mol%) and H2O in 0 °C condition.

Figure S112: HPLC chromatogram of (11a) in the presence organocatalyst (17b),CH3COOH (2 mol%) and H2O in 0 °C condition.

58

Figure S113: HPLC chromatogram of (12a) in the presence organocatalyst (18a), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S114: HPLC chromatogram of (12a) in the presence organocatalyst (18b),

CH3COOH (2 mol%) and H2O in 0 °C condition.

59

Figure S115: HPLC chromatogram of (11d) in the presence organocatalyst (18a), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S116: HPLC chromatogram of (11d) in the presence organocatalyst (18b), CH3COOH (2

mol%) and H2O in 0 °C condition.

60

Figure S114: HPLC chromatogram of (11e) in the presence organocatalyst (18a), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S118: HPLC chromatogram of (11e) in the presence organocatalyst (18b), CH3COOH (2 mol%) and H2O in 0 °C condition.

61

Figure S119: HPLC chromatogram of (11f) in the presence organocatalyst (17a), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S120: HPLC chromatogram of (11f) in the presence organocatalyst (17b), CH3COOH

(2 mol%) and H2O in 0 °C condition.

62

Figure S121: HPLC chromatogram of (12f) in the presence organocatalyst (18a), CH3COOH (2 mol%) and H2O in 0 °C condition.

Figure S122: HPLC chromatogram of (12f) in the presence organocatalyst (18b), CH3COOH (2 mol%) and H2O in 0 °C condition.