S1

Supplementary Material for

The Synthesis, Structural Characterisation and Chemoselective Manipulation of Certain Functionalized Cyclic Sulfates Derived from Chiral, Non-Racemic and

Polysubstituted Bicyclo[2.2.2]octane-2,3-diols

Martin G. Banwell,a,* Antony L. Crisp,b BoRa Lee,b Ping Lan,a

Hannah Bollard,b Jas S. Ward,b and Anthony C. Willisb

aInstitute for Advanced and Applied Chemical Synthesis, Jinan University,

Guangzhou, 510632, China

and

bResearch School of Chemistry, Institute of Advanced Studies,

The Australian National University, Canberra, ACT 2601, Australia

CONTENTS Page

1. Plots Derived from the X-ray Analyses of Compounds 13, 16, 17, 18, 23, 25, 33, 40 and

42……………………………….………………………………………………………...S2

2. 1H and 13C{1H} NMR Spectra for Compounds 12 (1H NMR spectrum only), 13-18, 19,

20, (1H NMR spectrum only), 21/22 (mixture), 23-26, 28/29 (mixture), 30, 31/32

(mixture), 33, 34, 41, sulfite precursors to 42 (mixture) and 42 ………..…….……….S11

*Corresponding author. Email: mgb@rsc.anu.edu.au

10.1071/CH21140_ACAustralian Journal of Chemistry

S2

Figure S1: Plot arising from the single-crystal X-ray analysis of compound 13 – thermal ellipsoids at 50% probability (crystal grown by slow evaporation of a sample dissolved in

dichloromethane/hexane) (CCDC 2082646).

S3

Figure S2: Plot arising from the single-crystal X-ray analysis of compound 16 – thermal ellipsoids at 50% probability (crystal grown by slow evaporation of a sample dissolved in

dichloromethane/hexane) (CCDC 2082647).

S4

Figure S3: Plot arising from the single-crystal X-ray analysis of compound 17 – thermal ellipsoids at 50% probability (crystal grown by slow evaporation of a sample dissolved in

dichloromethane/hexane) (CCDC 2082648).

S5

Figure S4: Plot arising from the single-crystal X-ray analysis of compound 18 – thermal ellipsoids at 50% probability (crystal grown by slow evaporation of a sample dissolved in

dichloromethane/hexane) (CCDC 2082649).

S6

Figure S5: Plot arising from the single-crystal X-ray analysis of compound 23 – thermal ellipsoids at 50% probability (crystal grown by slow evaporation of a sample dissolved in

dichloromethane/ethyl acetate) (CCDC 2082650).

S7

Figure S6: Plot arising from the single-crystal X-ray analysis of compound 25 – thermal ellipsoids at 50% probability (crystal grown by slow evaporation of a sample dissolved in

dichloromethane/hexane/ethyl acetate/chloroform) (CCDC 2082651).

S8

Figure S7: Plot arising from the single-crystal X-ray analysis of compound 33 – thermal ellipsoids at 50% probability (crystal grown by slow evaporation of a sample dissolved in

dichloromethane/hexane/ethyl acetate) (CCDC 2082652).

S9

Figure S8: Plot arising from the single-crystal X-ray analysis of compound 40 – thermal

ellipsoids at 30% probability (crystal grown by slow evaporation of a sample dissolved in hexane/ethyl acetate) (CCDC 2082653).

S10

Figure S9: Plot arising from the single-crystal X-ray analysis of compound 42 – thermal ellipsoids at 50% probability (crystal grown by slow evaporation of a sample dissolved in

dichloromethane/ hexane) (CCDC 2082654).

S11

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0

f1 (ppm)

OO

O

400 MHz 1H NMR spectrum

of compound 12 (recorded in CDCl3)

CHCl3

S12

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

OO

O

400 MHz 1H NMR spectrum

of compound 13 (recorded in CDCl3)

CHCl3

S13

0102030405060708090100110120130140150160170180190200f1 (ppm)

19.0

22.5

25.2

25.7

36.7

39.0

41.1

42.2

49.2

77.4

79.1

83.4

109.4

130.2

135.9

OO

O

100 MHz 13C NMR spectrum

of compound 13 (recorded in CDCl3)

CDCl3

S14

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

400 MHz 1H NMR spectrum

of compound 14 (recorded in CDCl3)

OHOH

O

CHCl3

S15

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

18.5

25.4

36.8

39.6

43.3

43.7

53.4

70.7

74.3

131.1

136.9

220.1

125 MHz 13C NMR spectrum

of compound 14 (recorded in CDCl3)

OHOH

O

CDCl3

S16

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0

f1 (ppm)

OHOH

MeO

400 MHz 1H NMR spectrum of compound 15

(recorded in CDCl3)

CHCl3

S17

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

14.4

21.1

21.8

26.5

31.6

34.7

35.3

37.9

48.8

56.7

70.3

74.0

85.4

OHOH

MeO

100 MHz 13C NMR spectrum

of compound 15 (recorded in CDCl3)

CDCl3

S18

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

f1 (ppm)

OO

MeO

S O

:

400 MHz 1H NMR spectrum

of compound 16 (recorded in CDCl3)

CHCl3

S19

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.0

20.4

21.7

26.1

31.5

32.1

34.6

37.9

47.1

56.8

81.6

84.6

86.2

OO

MeO

S O

:

100 MHz 13C NMR spectrum

of compound 16 (recorded in CDCl3)

CDCl3

S20

0.0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0

f1 (ppm)

OO

MeO

S:O

400 MHz 1H NMR spectrum

of compound 17 (recorded in CDCl3)

CHCl3

S21

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

14.0

20.5

22.0

26.3

32.3

32.5

34.9

38.1

46.6

56.9

84.9

86.5

90.9

OO

MeO

S:O

100 MHz 13C NMR spectrum

of compound 17 (recorded in CDCl3)

CDCl3

S22

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

OO

MeO

SO

O

400 MHz 1H NMR spectrum

of compound 18 (recorded in CDCl3)

CHCl3

S23

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

13.8

20.1

21.3

26.3

31.1

31.3

34.6

36.4

46.2

56.7

81.3

84.7

85.4

OO

MeO

SO

O

100 MHz 13C NMR spectrum

of compound 18 (recorded in CDCl3)

CDCl3

S24

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

OO

SO

O

400 MHz 1H NMR spectrum

of compound 19

(recorded in CDCl3)

CHCl3

H2O

Grease

silicone

grease

S25

-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

400 MHz 1H NMR spectrum

of compound 20 (recorded in CDCl3)

OHOH

O

CHCl3

S26

-20-100102030405060708090100110120130140150160170180190200210220f1 (ppm)

14.5

21.0

21.7

23.8

35.5

36.5

36.8

39.6

51.2

68.6

72.1

221.2

100 MHz 13C NMR spectrum

of compound 20 (recorded in CDCl3)

OHOH

O

CDCl3

S27

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

400 MHz 1H NMR spectrum

of compounds 21 and 22 (1:2 dr) (recorded in CDCl3)

OO

22

S O

+

21

:

O

OO

S:O

O

CHCl3

S28

-20-100102030405060708090100110120130140150160170180190200210220230240f1 (ppm)

14.0

14.2

21.0

21.2

21.3

21.8

23.5

23.7

33.4

34.4

35.1

35.3

35.6

36.0

39.7

49.7

49.8

79.7

84.0

84.9

89.0

218.7

219.1

100 MHz 13C NMR spectrum

of compounds 21 and 22 (1:2 dr)

(recorded in CDCl3)

OO

22

S O

+

21

:

O

OO

S:O

O

CDCl3

S29

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

OO

SO

O

O

400 MHz 1H NMR spectrum

of compound 23 (recorded in CDCl3)

CHCl3

S30

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

13.8

20.7

20.9

23.4

32.9

33.8

35.4

39.1

48.6

79.4

83.3

217.7

OO

SO

O

O

100 MHz 13C NMR spectrum

of compound 23 (recorded in CDCl3)

CDCl3

S31

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

CHCl3

silicone

grease

OO

HO

SO

O

400 MHz 1H NMR spectrum

of compound 24 (recorded in CDCl3)

S32

-100102030405060708090100110120130140150160170180190200210220f1 (ppm)

12.9

19.9

21.5

25.7

31.7

33.9

35.8

36.1

49.8

74.5

80.7

84.5

OO

HO

SO

O

100 MHz 13C NMR spectrum

of compound 24 (recorded in CDCl3)

CDCl3

S33

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

OO

HO

SO

O

400 MHz 1H NMR spectrum

of compound 25 (recorded in CDCl3)

CHCl3

S34

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

13.9

20.3

21.6

26.3

31.1

34.6

36.5

37.8

46.6

75.5

81.2

85.3

OO

HO

SO

O

100 MHz 13C NMR spectrum

of compound 25 (recorded in CDCl3)

CDCl3

S35

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

OO

O

SO

O

S

SMe

400 MHz 1H NMR spectrum

of compound 26 (recorded in CDCl3)

CHCl3

H2O

S36

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

13.8

19.5

20.4

21.4

26.7

30.9

34.1

34.5

36.5

46.4

80.7

84.8

86.5

215.4

OO

O

SO

O

S

SMe

100 MHz 13C NMR spectrum

of compound 26 (recorded in CDCl3)

CDCl3

S37

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

28

O

OO S

O

:

29

O

OO S:

+

O

400 MHz 1H NMR spectrum

of compounds 28 and 29 (1:1 dr)

(recorded in CDCl3)

CHCl3

S38

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

19.2

19.3

24.4

24.6

32.1

33.7

38.9

39.0

40.1

40.6

40.6

41.8

42.3

49.2

49.9

80.8

84.9

85.1

90.0

131.5

131.8

138.4

138.6

220.1

220.3

28

O

OO S

O

:

29

O

OO S:

+

O

75 MHz 13C NMR spectrum

of compounds 28 and 29 (1:1 dr)

(recorded in CDCl3)

CDCl3

S39

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

O

OHOH

400 MHz 1H NMR spectrum

of compound 30 (recorded in CDCl3)

CHCl3

S40

-100102030405060708090100110120130140150160170180190200210220230240f1 (ppm)

18.9

22.0

23.5

26.5

30.4

37.0

38.0

39.2

46.9

69.2

74.2

223.9

O

OHOH

100 MHz 13C NMR spectrum

of compound 30 (recorded in CDCl3)

CDCl3

S41

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

CHCl3

32

O

OO S

O

:

31

O

OO S:

+

O

400 MHz 1H NMR spectrum

of compounds 31 and 32 (1:1 dr) (recorded in CDCl3)

S42

-100102030405060708090100110120130140150160170180190200210220230240250f1 (ppm)

17.3

17.6

21.7

21.8

22.8

22.9

25.5

25.7

29.7

30.2

34.0

34.1

35.7

36.1

38.8

39.1

46.0

46.2

80.7

84.8

85.5

90.2

220.9

221.1

32

O

OO S

O

:

31

O

OO S:

+

O

100 MHz 13C NMR spectrum

of compounds 31 and 32 (1:1 dr)

(recorded in CDCl3)

CDCl3

S43

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

OO S

O

O

O

400 MHz 1H NMR spectrum

of compound 33 (recorded in CDCl3)

CHCl3

S44

-40-30-20-100102030405060708090100110120130140150160170180190200210220230240f1 (ppm)

16.9

21.4

22.6

24.9

29.5

33.5

35.3

38.6

45.6

81.0

85.0

219.6

OO S

O

O

O

100 MHz 13C NMR spectrum

of compound 33 (recorded in CDCl3)

CDCl3

S45

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

OO S

O

O

OHH

400 MHz 1H NMR spectrum

of compound 34 (recorded in CDCl3)

CHCl3

S46

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

16.7

22.4

25.8

26.0

32.1

32.2

34.8

37.3

41.6

75.9

82.6

86.2

OO S

O

O

OHH

100 MHz 13C NMR spectrum

of compound 34 (recorded in CDCl3)

CDCl3

S47

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0

f1 (ppm)

400 MHz 1H NMR spectrum

of compound 41 (3.6:1 dr) (recorded in CDCl3)

CHCl3

OHOH

S48

-100102030405060708090100110120130140150160170180190200

f1 (ppm)

19.1

23.0

23.8

26.9

33.0

33.8

34.4

37.0

38.6

45.1

46.9

73.0

75.6

OHOH

100 MHz 13C NMR spectrum

of compound 41 (3.6:1 dr) (recorded in CDCl3)

CDCl3

S49

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0

f1 (ppm)

CHCl3

OOSO

400 MHz 1H NMR spectrum

of the sulfite precursors to compound 42 (mixture of 4 diastereomers) (recorded in CDCl3)

S50

-100102030405060708090100110120130140150160170180190200f1 (ppm)

19.1

19.3

21.8

22.0

23.6

23.9

26.4

27.1

32.6

32.8

33.2

33.2

34.9

35.3

38.3

38.6

42.1

42.3

43.4

44.2

47.8

48.0

85.6

86.0

90.3

90.9

OOSO

100 MHz 13C NMR spectrum

of the sulfite precursors to compound 42 (mixture of 4 diastereomers) (recorded in CDCl3)

CDCl3

S51

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0

f1 (ppm)

OOSO

O

400 MHz 1H NMR spectrum

of compound 42 (4:1 dr) (recorded in CDCl3)

CHCl3

S52

-100102030405060708090100110120130140150160170180190200f1 (ppm)

18.8

21.9

23.2

26.1

32.7

33.0

34.0

35.2

38.5

43.0

46.5

85.8

86.1

OOSO

O

100 MHz 13C NMR spectrum

of compound 42 (4:1 dr) (recorded in CDCl3)

CDCl3