S1  

Highly Enantioselective Synthesis of Naphthoquinones and

Pyranonaphthoquinones Catalyzed by Bifunctional Chiral Bis-Squaramides

Nagaraju Molletia and Vinod K. Singh*,a,b

aDepartment of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal–462 066, India

bDepartment of Chemistry, Indian Institute of Technology, Kanpur–208 016, India.

Fax: +91-512-2597436; E-mail: vinodks@iitk.ac.in

Supporting information

Table of contents:

X-ray Crystallographic Data of 4d S2- S3

1H, 13C NMR Spectra and HPLC graph S4-S57

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2015

S2  

Fig. S1. Molecular structure of 4d shown with 50% ellipsoidal probability. (CCDC 1030663)

Table S1.Crystal data and structure refinement for 4d.

Empirical formula C26 H18 Cl N O5

Formula weight 459.86

Temperature 296 K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P2(1)

Unit cell dimensions a = 8.5053 (3) Å = 90.000°.

b = 18.3634 (5) Å = 106.636(2)°.

c = 14.5843 (4) Å = 90.000°.

Volume 2182.52 (12) Å3

Z 4

Density (calculated) 1.400 Mg/m3

Absorption coefficient 0.214 mm-1

S3  

F(000) 952

Crystal size 0.0043 x 0.0032 x 0.0028 mm3

Theta range for data collection 1.457 to 28.011°.

Index ranges -11<=h<=11, 0<=k<=24, -19<=l<=19

Reflections collected 10341

Independent reflections 5399 [R(int) = 0.0219]

Completeness to theta = 28.011° 99.0 %

Absorption correction Multi-scan

Data / restraints / parameters 5399 / 1 / 597

Goodness-of-fit on F2 1.230

Final R indices [I>2sigma(I)] R1 = 0.0438, wR2 = 0.1062

R indices (all data) R1 = 0.0329, wR2 = 0.0939

Absolute structure parameter 0.07(6)

S4  

 

500 MHz 1H NMR spectra of compound 4a in CDCl3

 

125 MHz 13C NMR spectra of compound 4a in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

O

N

O

O

OAc

O

N

O

O

OAc

S5  

HPLC graph of compound 4a (racemic)

HPLC graph of compound 4a (enantioenriched)

O

N

O

O

OAc

S6  

 

400 MHz 1H NMR spectra of compound 4b in CDCl3

 

100 MHz 13C NMR spectra of compound 4b in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S7  

HPLC graph of compound 4b (racemic)

HPLC graph of compound 4b (enantioenriched)

S8  

  

400 MHz 1H NMR spectra of compound 4c in CDCl3

  

100 MHz 13C NMR spectra of compound 4c in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

O

N

O

O

OAc

CH3

O

N

O

O

OAc

CH3

S9  

HPLC graph of compound 4c (racemic)

HPLC graph of compound 4c (enantioenriched)

O

N

O

O

OAc

CH3

S10  

 

400 MHz 1H NMR spectra of compound 4d in CDCl3

  

100 MHz 13C NMR spectra of compound 4d in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

O

N

O

O

OAc

Cl

O

N

O

O

OAc

Cl

S11  

HPLC graph of compound 4d (racemic)

HPLC graph of compound 4d (enantioenriched)

O

N

O

O

OAc

Cl

O

N

O

O

OAc

Cl

S12  

 

400 MHz 1H NMR spectra of compound 4e in CDCl3

 

100 MHz 13C NMR spectra of compound 4e in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S13  

HPLC graph of compound 4e (racemic)

HPLC graph of compound 4e (enantioenriched)

S14  

 

400 MHz 1H NMR spectra of compound 4f in CDCl3 

 

 100 MHz 13C NMR spectra of compound 4f in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S15  

HPLC graph of compound 4f (racemic)

HPLC graph of compound 4f (enantioenriched)

O

N

O

O

OAc

Cl

S16  

  

400 MHz 1H NMR spectra of compound 4g in CDCl3 

 

100 MHz 13C NMR spectra of compound 4g in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S17  

HPLC graph of compound 4g (racemic)

HPLC graph of compound 4g (enantioenriched)

S18  

 

400 MHz 1H NMR spectra of compound 4h in CDCl3

 

400 MHz 13C NMR spectra of compound 4h in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S19  

HPLC graph of compound 4h (racemic)

HPLC graph of compound 4h (enantioenriched)

O

N

O

O

OAc

NO2

S20  

 

400 MHz 1H NMR spectra of compound 4i in CDCl3 

100 MHz 13C NMR spectra of compound 4i in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

O

N

O

O

OAc

CN

O

N

O

O

OAc

CN

S21  

HPLC graph of compound 4i (racemic)

HPLC graph of compound 4i (enantioenriched)

O

N

O

O

OAc

CN

O

N

O

O

OAc

CN

S22  

 

500 MHz 1H NMR spectra of compound 4j in CDCl3 

  

125 MHz 13C NMR spectra of compound 4j in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S23  

HPLC graph of compound 4j (racemic)

HPLC graph of compound 4j (enantioenriched)

S24  

 

500 MHz 1H NMR spectra of compound 4k in CDCl3 

0102030405060708090100110120130140150160170180190200210f1 (ppm)

20.4

8

36.1

6

41.1

5

101.

03

108.

3110

8.83

121.

4212

1.47

122.

1612

6.48

130.

73

134.

2013

7.38

139.

83

146.

4314

7.77

148.

8015

0.99

152.

62

167.

71

178.

39

184.

31

198.

97

 

 125 MHz 13C NMR spectra of compound 4k in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

S25  

HPLC graph of compound 4k (racemic)

HPLC graph of compound 4k (enantioenriched)

S26  

 

400 MHz 1H NMR spectra of compound 4l in CDCl3 

 

100 MHz 13C NMR spectra of compound 4l in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S27  

HPLC graph of compound 4l (racemic)

HPLC graph of compound 4l (enantioenriched)

S28  

 

400 MHz 1H NMR spectra of compound 4m in CDCl3 

 

100 MHz 13C NMR spectra of compound 4m in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S29  

HPLC graph of compound 4m (racemic)

HPLC graph of compound 4m (enantioenriched)

S30  

 

400 MHz 1H NMR spectra of compound 4n in CDCl3 

 

100 MHz 13C NMR spectra of compound 4n in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200210f1 (ppm)

S31  

HPLC graph of compound 4n (racemic)

HPLC graph of compound 4n (enantioenriched)

S32  

 

400 MHz 1H NMR spectra of compound 4n in CDCl3 

  

100 MHz 13C NMR spectra of compound 4n in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S33  

HPLC graph of compound of 4n (racemic)

HPLC graph of compound of 4n (enantioenriched)

S34  

 

400 MHz 1H NMR spectra of compound 9a in CDCl3 

 

100 MHz 13C NMR spectra of compound 9a in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S35  

HPLC graph of compound 9a (racemic)

HPLC graph of compound 9a (enantioenriched)

S36  

 

400 MHz 1H NMR spectra of compound 9b in CDCl3 

 

100 MHz 13C NMR spectra of compound 9b in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S37  

HPLC graph of compound 9b (racemic)

HPLC graph of compound 9b (enantioenriched)

S38  

 

500 MHz 1H NMR spectra of compound 9c in CDCl3 

 

125 MHz 13C NMR spectra of compound 9c in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S39  

HPLC graph of compound 9c (racemic)

HPLC graph of compound 9c (enantioenriched)

S40  

 

500 MHz 1H NMR spectra of compound 10a in CDCl3 

 

125 MHz 13C NMR spectra of compound 10a in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S41  

HPLC graph of compound 10a (racemic)

HPLC graph of compound 10a (enantioenriched)

S42  

 

400 MHz 1H NMR spectra of compound 11a in CDCl3 

 

100 MHz 13C NMR spectra of compound 11a in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200210f1 (ppm)

S43  

HPLC graph of compound 11a (racemic)

HPLC graph of compound 11a (enantioenriched)

S44  

 

500 MHz 1H NMR spectra of compound 12a in CDCl3 

  

125 MHz 13C NMR spectra of compound 12a in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190f1 (ppm)

S45  

HPLC graph of compound 12a (racemic)

HPLC graph of compound 12a (enantioenriched)

S46  

 

500 MHz 1H NMR spectra of compound 12b in CDCl3 

  

125 MHz 13C NMR spectra of compound 12b in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S47  

HPLC graph of compound 12b (racemic)

HPLC graph of compound 12b (enantioenriched)

S48  

 

500 MHz 1H NMR spectra of compound 12c in CDCl3 

  

125 MHz 13C NMR spectra of compound 12c in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

0102030405060708090100110120130140150160170180190f1 (ppm)

O

O

ON

CH3

O

O

ON

CH3

S49  

HPLC graph of compound 12c (racemic)

HPLC graph of compound 12c (enantioenriched)

O

O

ON

CH3

O

O

ON

CH3

S50  

 

500 MHz 1H NMR spectra of compound 12d in CDCl3 

  

125 MHz 13C NMR spectra of compound 12d in CDCl3 

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190f1 (ppm)

O

O

ON

Cl

O

O

ON

Cl

S51  

HPLC graph of compound 12d (racemic)

HPLC graph of compound 12d (enantioenriched)

O

O

ON

Cl

O

O

ON

Cl

S52  

 

500 MHz 1H NMR spectra of compound 12e in CDCl3 

 

125 MHz 13C NMR spectra of compound 12e in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190f1 (ppm)

S53  

HPLC Graph of compound 12e (racemic)

HPLC Graph of compound 12e (enantioenriched)

S54  

 

500 MHz 1H NMR spectra of compound 12g in CDCl3 

  

125 MHz 13C NMR spectra of compound 12g in CDCl3 

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

S55  

HPLC graph of compound 12g (racemic)

HPLC graph of compound 12g (enantioenriched)

O

O

ON

Cl

S56  

1.10

1.03

1.02

1.00

4.85

1.24

1.93

0.98

0.96

0.93

0.90

0.92

2.26

2.27

2.28

2.29

2.29

2.31

2.82

2.82

2.83

2.83

2.84

2.85

4.25

4.26

4.26

4.27

5.43

5.43

5.44

5.45

7.12

7.13

7.13

7.14

7.18

7.19

7.19

7.22

7.58

7.61

7.75

7.99

8.12

8.13

8.59

8.59

700 MHz 1H NMR spectra of compound 13a in CDCl3 37

.80

39.0

2

76.8

877

.06

77.2

480

.40

117.

8912

0.23

123.

3612

6.36

128.

5213

0.39

135.

0813

7.13

143.

00

149.

46

157.

88

163.

58

178.

2217

9.20

  

175 MHz 13C NMR spectra of compound 13a in CDCl3 

 

S57  

 

 

HPLC graph of compound 13a (racemic)

 

HPLC graph of compound 13a (enantioenriched)