S1

Supporting Information

Highly sulphated cellulose: A versatile, reusable and selective desilylating agent for deprotection of alcoholic TBDMS ethers

Soma Shekar Dachavarama, Narsimha R. Penthalaa, Julie L. Calahanb, Eric J. Munsonb, Peter A. Crooksa*

aDepartment of Pharmaceutical Sciences College of Pharmacy, University of Arkansas for Medical Sciences, Little Rock, AR 72205, USA.bDepartment of Pharmaceuticals Sciences, University of Kentucky, Lexington, KY, 40536, USA

Table of Contents

General Information ……………………………………………………………………….…........................... S1 Characterization data………………………………………………………………………..…………………………. S2-S7IR- spectra of cellulose sulphate and cellulose sulphate sodium ………………………………….. S8Solid state NMR spectra of cellulose sulphate sodium and CSA...……….….…………………….. S91 H Spectra of cellulose sulphate sodium ….………………………………………………………………….. S1013C NMR Spectra of cellulose sulphate sodium ….…………………………………………………………. S111 H, 13C NMR Spectra of compound 3c, 3d, 3f, 3g, 3h, 3i,3j, 3k, 3l, 4l, 5d, 5e, 5f, 6f………………………..…………..…............................................................................. S12-S391 H Spectra of recovered cellulose sulphate sodium ….………………………………………….. S-4013C NMR Spectra of recovered cellulose sulphate sodium ….…………………………………. S-41References………………………………………………………………………………….………………………………….. S42

General Information

Solvents were dried by standard procedures. All commercially available alcohols and phenols were purchased from the Sigma

Aldrich Company. Thin-layer chromatography was performed on silica gel plates and chromatographic spots were visualized by

using UV light and staining with anisaldehyde charring solution. 1H NMR and 13C NMR spectral analyses were recorded on a Varian

400 MHz spectrometer equipped with a Linux workstation running on vNMRj software and the chemical shifts are based on the

internal standard TMS peak at δ = 0.00 ppm for proton NMR and the CDCl3 peak at δ = 77.23 ppm (t) for carbon NMR. For cellulose

sulphate sodium both 1H NMR and 13C NMR were recorded in D2O. IR spectra were obtained on a Thermo Scientific Nicolet iS 50

FT-IR instrument. Silyl ethers were prepared from phenols\alcohols using a standard procedure1 (TBDMS chloride, imidazole,

DCM). TBDMS ethers 3k, 5e, 5f were synthesized by the Barbier allylation procedure2. TBDMS ethers 3a-3j and 5a-5d were

prepared from commercially available phenols/alcohols. Compound 3l was prepared by the reduction of methyl 8-(4-

chlorophenyl)-1, 4-dioxaspiro[4.5]dec-7-ene-7-carboxylate using lithium aluminum hydride (LAH) as reducing agent to afford 4l.

Compound 4l was converted to its TBDMS ether by reaction with TBDMS chloride and imidazole in DCM.1 TBDMS ethers 3a3, 3b4

3e5, 5a5, 5b6, 5c5 are known compounds and the characterization data for these ethers complied with the literature reported

data. The desilylated products 4a7, 4b8, 4c9, 4d,10 4e11, 4f12, 4g13, 4h14, 4i,15 4j,16 4k17, 6a6, 6b18, 6c19, 6d20, 6e21 are known

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2018

S2

compounds, and their characterization data complied with the literature reported data. Characterization data for the new

compounds 3c, 3d, 3f, 3g, 3h, 3i, 3j, 3k, 3l, 4l, 5d, 5e, 5f and 6f are provided below.

Characterization data for new compounds

O

NaO3SOHO

n

OSO3Na

O

HO

OSO3Na

OSO3NaOO

123

4 56

HS-cellulose sulphate sodium salt

HS-Cellulose sulphate (H2SO4 method) sodium salt: The compound was obtained as a white solid; 1H-NMR (D2O, 400 MHz): δ

4.56 (d, J = 16.0 Hz, 1H, H1), 4.37 (m, 1H, H6), 4.0-3.49 (m, 3H, H3, H6, H4), 3.36 (s, 1H, H5) ppm; 13C-NMR (D2O, 100 MHz): δ 104.8

(C-1), 80.7, 77.2, 76.4, 75.4 (C-2 to C-5), 62.3 (C-6) ppm. Sulphur combustion analysis calcd for the 2,6-disubstited cellulose

sulphate, empirical formula C6H8S2O11Na2: 17.51%. Found: 15.42% (88.06% of theoretical), FT-IR: 3332, 2896, 1427, 1053, 663,

557 cm-1.

NOTE: Sulphur combustion analysis calcd for 2,6-disubstituted cellulose sulphate, empirical formula C6H8S2O11Na2: 17.51%.

Found: 15.42% (88.06% of theoretical); sulphur combustion analysis calcd for 6-monosubstituted cellulose sulphate, empirical

formula C6H9SO8Na: 12.14%. Found: 15.42% (27.01 % greater than theoretical); sulphur combustion analysis calcd for 2,3,6-

trisubstituted cellulose sulphate, empirical formula C6H7S3O14Na2: 20.54%. Found: 15.42% (24.92% less than theoretical). These

data indicate that the sulphated cellulose product is predominantly the 2,6-disulphated cellulose rather than the 2,3,6-

trisubstituted or 6-monosulphated cellulose.

Cellulose sulphate (chlorosulphonic acid method): Sulphur content calcd for the empirical formula C6H7S3O14Na3: 20.54%. Found:

0.42%; sulphur content: 2.04% of theoretical; FT-IR: 3331, 2891, 1315, 1201, 1159, 1023, 895, 558, and 433 cm-1.

Tert-butyl(4-ethoxyphenethoxy)dimethylsilane (3c)

O

OSi

Colourless liquid, Yield: (95%), 1H NMR (400 MHz, CDCl3): δ 7.15 (d, J = 8.0 Hz, 2H, Ar-H), 6.82 (t, J = 8.0, 4.0 Hz, 2H. Ar-H), 4.01 (q,

J = 8.0 Hz, 2H, -OCH2), 3.76 (t, J = 7.43, 7.04 Hz, 2H, -OCH2), 2.74 (t, J = 8.0, 4.0 Hz, 2H, -CH2), 1.40 (t, J = 8.0 Hz, 3H, -CH3), 0.88 (s,

9H, t-Bu), -0.01 (s, 6H, (CH3)2-Si) ppm; 13C-NMR (CDCl3, 100 MHz): δ 157.3, 131.0, 130.0, 114.2, 64.8, 63.3, 38.7, 25.9, 18.3, 14.8, -

5.4 ppm; ESI-MS (m/z): 281.0447 (M+H)+.

Tert-butyl (4-methoxy-3-methylphenethoxy) dimethylsilane (3d)

S3

O

OSi

Colourless liquid, Yield: (95%), 1H NMR (400 MHz, CDCl3): δ 7.00-6.98 (m, 2H, Ar-H), 6.73 (t, J= 8.0 Hz, 1H, Ar-H), 3.80 (s, 3H, -

OCH3), 3.75 (t, J = 4 Hz, 2H, -OCH2 ), 2.74 (t, J = 8 Hz, 2H, -CH2), 2.20 (s, 3H, Ar-CH3), 0.89 (s, 9H, t-Bu), 0.01 (s, 6H, (CH3)2-Si) ppm;

13C-NMR (CDCl3, 100 MHz): δ 156.1, 131.5, 130.6, 127.0, 126.2, 109.7, 64.9, 55.3, 38.7, 25.9, 18.35, 16.1, -5.3 ppm; ESI-MS(m/z):

281.0610 (M+H)+, 304.0410 (M+Na)+.

Tert-butyldimethyl (3, 4, 5-trimethoxyphenethoxy)silane (3f)

OO

O OSi

Colourless liquid, Yield: (85%), 1H NMR (400 MHz, CDCl3): δ 6.43 (s, 2H, Ar-H), 3.84 (s, 6H, 2 x -OCH3), 3.82-3.78 (m, 5H, -OCH3 and

–OCH2), 2.75 (t, J = 8.0 Hz, 4.0 Hz, 2H, CH2), 0.87 (s, 9H, t-Bu), -0.01 (s, 6H, (CH3)2-Si ) ppm; 13C NMR (100 MHz, CDCl3): δ 152.9,

136.3, 135.1, 106.0, 64.4, 60.7, 55.9, 39.8, 25.8, 18.2, -5.4 ppm; ESI-MS (m/z): 327.0410 (M+H)+, 349.0256 (M+Na)+.

Tert-butyl ((3, 4-dichlorobenzyl) oxy)dimethylsilane (3g)

ClCl

OSi

Colourless liquid, Yield: (85%), 1H NMR (400 MHz, CDCl3): δ 7.42 -7.41 (m, 1H, Ar-H), 7.39 (d, J = 8.2 Hz, 1H, Ar-H), 7.16-7.13 (m,

1H, Ar-H), 4.68 (s, 2H, -OCH2), 0.95 (s, 9H, t-Bu ), 0.11 (s, 6H, (CH3)2-Si) ppm; 13C NMR (100 MHz, CDCl3): δ 141.7, 132.2, 130.6,

130, 127.8, 125.1, 63.6, 25.8, 18.3, -5.3 ppm; ESI-MS(m/z): 291.022 (M+H)+.

Tert-butyldimethyl(2-(naphthalen-1-yl)ethoxy)silane (3h)

S4

OSi

Colourless liquid; Yield: (88%), 1H NMR (400 MHz, CDCl3): δ 8.09-8.07 (m, 1H, Ar-H), 7.87-7.84 (m, 1H, Ar-H), 7.74 (d, J = 8.0 Hz,

1H, Ar-H), 7.54-7.45 (m, 2H, Ar-H), 7.43-7.35 (m, 2H, Ar-H), 3.97-3.93 (m, 2H, -OCH2), 3.33 (t, J = 8.0 Hz, 2H, CH2), 0.88 (s, 9H, t-

Bu), -0.03 (s, 6H, (CH3)2-Si) ppm; 13C NMR (100 MHz, CDCl3): δ 135.0, 133.7, 132.2, 128.6, 127.1, 126.9, 125.7, 125.4, 125.3, 123.8,

63.9, 36.6, 25.9, 18.3, -5.4 ppm; ESI-MS(m/z): 287.0406 (M+H)+, 310.294 (M+Na)+.

Tert-butyl (2-(2, 3-dihydrobenzofuran-5-yl)ethoxy)dimethylsilane (3i)

O

OSi

Colourless liquid, Yield: (92%), 1H NMR (400 MHz, CDCl3): δ 7.04 (s, 1H, Ar-H), 6.94-6.92 (m, 1H, Ar-H), 6.70 (d, J = 8.0 Hz, 1H, Ar-

H), 4.54 (t, J = 8.99, 8.66 Hz, 2H, -OCH2), 3.75 (t, J = 8.0 Hz, 2H, -OCH2), 3.17 (t, J = 8.6 Hz, 2H, CH2), 2.75 (t, J = 12.0, 8.0 Hz, 7.04

Hz, 2H, CH2), 0.89 (s, 9H, t-Bu), 0.01 (s, 6H, (CH3)2-Si) ppm; 13C NMR (100 MHz, CDCl3): δ 158.4, 130.9, 128.4, 126.7, 125.6, 108.8,

71.1, 64.9, 39.01, 29.7, 25.9, 18.3, -5.3 ppm; ESI-MS (m/z): 279.0549 (M+H)+, 301.0227 (M+Na)+.

Tert-butyl ((2, 3-dihydrobenzofuran-5-yl) methoxy)dimethylsilane (3j)

O

OSi

Colourless liquid, Yield: (75%), 1H NMR (400 MHz, CDCl3): δ 7.17 (s, 1H, Ar-H), 7.06-7.03 (m, 1H, Ar-H), 6.74 (d, J = 8.0 Hz, 1H,

Ar-H), 4.65 (s, 2H, -OCH2), 4.56 (t, J = 8.0 Hz, 2H, -OCH2), 3.20 (t, J = 8.0 Hz, 2H, CH2), 0.94 (s, 9H, t-Bu), 0.10 (s, 6H, (CH3)2-Si) ppm;

13C NMR (100 MHz, CDCl3): δ 159.1, 133.4, 126.9, 126.2, 123.2, 108.78 71.2, 65.0, 29.7, 26.0, 18.4, -5.1 ppm; ESI-MS (m/z):

287.0778 (M+Na)+.

2-(1-((Tert-butyldimethylsilyl) oxy) but-3-en-1-yl)phenol (3k)

S5

OH

OSi

Colourless liquid, Yield: (82%), 1H NMR (400 MHz, CDCl3): δ 8.18 (s, 1H, Ar-OH), 7.17-7.13 (m, 1H, Ar-H), 6.89-6.85 (m, 2H, Ar-H),

6.81-6.77 (m, 1H, Ar-H), 5.78-5.67 (m, 1H, -OCH), 5.08 (d, J = 1.17 Hz, 1H, Vinyl-CH), 5.05-5.03 (m, 1H, Vinyl-CH), 4.76 (dd, J = 8.0

Hz, 1H, Vinyl-CH), 2.65-2.45 (m, 2H, Allyl-CH), 0.90 (s, 9H, t-Bu), 0.14 (s, 3H, CH3-Si), 0.02 (s, 3H, CH3-Si) ppm; 13C NMR (100 MHz,

CDCl3): δ 155.7, 134.1, 128.6, 127.0, 126.8, 119.2, 117.9, 117.1, 77.7, 43.2, 25.6, 18.1, -5.0, -5.1 ppm; ESI-MS(m/z): 279.0549

(M+H)+, 301.0227 (M+Na)+.

Tert-Butyl((8-(4-chlorophenyl)-1,4-dioxaspiro[4.5]dec-7-en-7-yl)methoxy)dimethylsilane (3l)

O O

Cl

OSi

Colourless liquid, Yield: 95%, 1H-NMR (CDCl3, 400MHz): δ 7.28 (t, J = 4.0 Hz, 1H, Ar-H), 7.26 (t, J = 4.0 Hz, 1H, Ar-H), 7.12 (t, J = 4.0

Hz, 1H, Ar-H), 7.10 (t, J = 4.0 Hz, 1H, Ar-H), 4.04 – 4.01 (m, 4H, -(OCH2)2), 3.94 (s, 2H, -OCH2), 2.48 (dd, J = 8.0, 4.0 Hz, 4H, 2x CH2),

1.86 (t, J = 4.0 Hz, 2H, -CH2), 0.85 (s, 9H, t-Bu), -0.05 (s, 6H, (CH3)2-Si) ppm; 13C-NMR (CDCl3, 100 MHz): δ 140.3, 132.6, 132.4,

131.2, 129.6, 128.1, 108.1, 64.4, 63.9, 37.0, 31.4, 31.1, 25.8, 18.2, -5.3 ppm; ESI-MS (m/z): 394.9949 (M+H)+, 416.9845 (M+Na)+.

(8-(4-Chlorophenyl)-1,4-dioxaspiro[4.5]dec-7-en-7-yl)methanol (4l)

O O

OH

Cl

S6

Colourless liquid, Yield: 91%, 1H-NMR (CDCl3, 400MHz): δ 7.29 (d, J = 8.0 Hz, 2H, Ar-H), 7.11 (d, J = 8.0 Hz, 2H, Ar-H), 4.05-4.01

(m, 4H, -(OCH2)2), 3.93 (s, 2H, -OCH2), 2.50 (t, J = 12.0, 8Hz, 4H, Allyl-CH2), 1.87 (t, J = 4.0 Hz, 1H, -CH2) ppm; 13C-NMR (CDCl3, 100

MHz): δ 140.0, 134.6, 132.6, 130.7, 129.5, 128.3, 107.9, 64.4, 63.4, 37.0, 31.4, 31.3 ppm; ESI-MS (m/z): 281.9937 (M+2H)+,

302.9126 (M+Na)+.

Tert-butyl ((4-((tert-butyldimethylsilyl) oxy)-3, 5-dimethoxybenzyl) oxy)dimethylsilane (5d)

OO

OSi

OSi

Colourless liquid, Yield: (82%), 1H NMR (400 MHz, CDCl3): δ 6.52 (s, 2H, Ar-CH), 4.66 (s, 2H, -OCH2), 3.78 (s, 6H, -(OCH3)2), 1.00 (s,

9H, t-Bu), 0.94 (s, 9H, t-Bu), 0.11 (s, 6H, CH3)2-Si), 0.09 (s, 6H, (CH3)2-Si) ppm; 13C NMR (100 MHz, CDCl3): δ 151.4, 133.9, 133.0,

103.1, 65.1, 55.6, 25.9, 25.8, 18.7, 18.4, -4.6, -5.1 ppm; ESI-MS (m/z):413.0653 (M+H)+, 435.0308 (M+Na)+.

Tert-butyl (2-(1-((tert-butyldimethylsilyl) oxy) but-3-en-1-yl) phenoxy) dimethylsilane (5e)

OSi

OSi

Colourless liquid, Yield: (90%), 1H NMR (400 MHz, CDCl3): δ 7.48 (dd, J = 8.0, 4.0 Hz, 1H, Ar-H), 7.10 (td, J = 8.0 Hz, 1H, Ar-H), 6.95

(t, J = 8.0 Hz, 1H, Ar-H), 6.77 (d, J = 8.0Hz, 1H, Ar-H), 5.94-5.84 (m, 1H, Vinyl-CH), 5.16 (dd, J = 4.0 Hz, 1H, Vinyl-CH), 5.05 (dd, J =

4.0 Hz, 1H, Vinyl-CH), 5.02 (s, -OCH), 2.47-2.32 (m, 2H, Allyl-CH2), 1.06 (s, 9H, t-Bu), 0.92 (s, 9H, t-Bu), 0.31 (s, 3H, CH3-Si), 0.27 (s,

3H, CH3-Si), 0.05 (s, 3H, CH3-Si), -0.08 (s, 3H, CH3-Si) ppm; 13C NMR (100 MHz, CDCl3): δ 151.2, 135.8, 135.7, 127.3, 127.2, 120.8,

117.4, 116.5, 68.7, 43.8, 25.9, 25.8, 18.3, 18.2, -3.8, -4.2, -4.7, -4.9 ppm; ESI-MS (m/z): 415.0718 (M+Na)+.

S7

Tert-butyl ((1-(4-((tert-butyldimethylsilyl) oxy)-3, 5-dimethoxyphenyl) but-3-en-1-yl) oxy) dimethylsilane (5f)

OOO

Si

OSi

Colourless liquid, Yield: (88%), 1H NMR (400 MHz, CDCl3): δ 6.50 (s, 2H, Ar-H), 5.83-5.74 (m, 1H, -OCH), 5.05-5.00 (m, 2H, Vinyl-CH

), 4.57 (dd, J = 4.0 Hz, 1H, -OCH), 3.78 (s, 6H, -(OCH3)2), 2.48-2.33 (m, 2H, Allyl-CH2), 1.02 (s, 9H, t-Bu), 0.88 (s, 9H, t-Bu), 0.13 (s,

6H, Si-(CH3)2), 0.02 (s, 3H, Si-CH3), -0.12 (s, 3H, Si-CH3) ppm; 13C NMR (100 MHz, CDCl3): δ 151.1, 137.9, 135.5, 132.9, 116.5, 102.9,

75.2, 55.6, 44.5, 25.8, 18.7, 18.2, -4.6, -4.69, -4.7, -4.9 ppm; ESI-MS (m/z): 475.0574 (M+Na)+.

1-(4-((tert-Butyldimethylsilyl)oxy)-3,5-dimethoxyphenyl)but-3-en-1-ol (6f)

OO

HO

OSi

Colourless liquid, Yield: 88%, 1H-NMR (CDCl3, 400MHz): δ 6.55 (s, 2H, Ar-H), 5.86-5.76 (m, 1H, -Vinyl-CH), 5.15 (t, , J = 12 Hz, 2H,

Vinyl-CH), 4.67-4.63 (m, 1H, -OCH), 3.80 (s, 6H, -(OCH3)2), 2.48 (dd, J = 8.0, 4.0 Hz, 2H, Allyl-CH2), 1.98 (d, J = 4.0 Hz, 1H, -OH), 1.01

(s, 9H, t-Bu), 0.12 (s, 6H, , (CH3)2-Si) ppm; 13C-NMR (CDCl3, 100MHz): δ 151.4, 136.4, 134.6, 133.3, 118.0, 102.7, 73.5, 55.6, 43.8,

25.7, 18.6, -4.6 ppm; ESI-MS (m/z): 339. 0476 (M+H)+, 361.8842 (M+Na)+.

S8

IR spectrum of HS-cellulose sulphate

IR spectrum of HS-cellulose sulphate sodium

O

HO3SO

OSO3H

OOSO3H

OSO3HOOHO

HO

O

HO3SO

OSO3H

OOSO3H

OSO3HOOHO

HO

S9

Solid state NMR spectrum of HS-cellulose sulpate sodium

Cellulose sulphuric acid, CSA

Cellulose sulphate sodium

S10

1H NMR spectrum of HS-cellulose sulphate sodium in D2O

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)

DSS-cellulose-sulfate-fiberone_NMR_W012_calib

1.0

4

3.3

3

0.9

9

1.0

0

3.3

6

3.6

6

3.8

3

4.3

34

.42

4.5

44

.58

O

NaO3SOHO

n

OSO3Na

O

HO

OSO3Na

OSO3NaOO

S11

13C NMR spectrum of compound cellulose sulphate sodium in D2O

05101520253035404550556065707580859095100105110115120f1 (ppm)

DSS-cellulosesulfateCMRone_NMR_W012_calib

62

.28

75

.41

76

.37

77

.24

80

.67

10

4.7

6

O

NaO3SOn

OSO3Na

OOSO3Na

OSO3NaOOHO

HO

S12

1H NMR spectrum of compound 3c in CDCl3

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

DSS-2-3C-1HMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz)

5.8

8

9.0

0

2.9

7

2.1

0

2.1

1

2.0

6

2.0

0

1.9

1

-0.0

1

0.8

8

1.3

81

.40

1.4

2

2.7

42

.76

2.7

8

3.7

53

.76

3.7

83

.98

4.0

04

.02

4.0

4

6.8

16

.82

6.8

37

.10

7.1

2

O

OSi

S13

13C NMR spectrum of compound 3c in CDCl3

-100102030405060708090100110120130140150160f1 (ppm)

DSS-2-3C-13CMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz) -5

.39

14

.87

18

.35

25

.94

38

.72

63

.39

64

.80

11

4.2

6

13

0.0

11

31

.07

15

7.3

5

O

OSi

S14

1H NMR spectrum of compound 3d in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

DSS-2-3d-1HMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz)

6.0

0

8.5

5

2.8

0

2.0

2

2.0

32

.90

1.0

0

1.8

1

0.0

1

0.8

9

2.2

0

2.7

22

.74

2.7

5

3.7

43

.75

3.7

73

.80

6.7

36

.73

6.7

56

.98

6.9

96

.99

7.0

07

.00

O

OSi

S15

13C NMR spectrum of compound 3d in CDCl3

-100102030405060708090100110120130140150160f1 (ppm)

DSS-2-3D-13CMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz) -5

.36

16

.14

18

.35

25

.94

38

.74

55

.35

64

.91

10

9.7

9

12

6.2

41

27

.09

13

0.6

81

31

.52

15

6.1

9

O

OSi

S16

1H NMR spectrum of compound 3f in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

DSS-2-3f-1HMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz)

6.2

8

9.2

0

2.2

3

5.1

15

.90

2.1

4

-0.0

1

0.8

7

2.7

32

.75

2.7

7

3.7

83

.80

3.8

13

.81

3.8

23

.84

6.4

3

OO

O OSi

S17

13C NMR spectrum of compound 3f in CDCl3

-100102030405060708090100110120130140150160170f1 (ppm)

DSS-2-3f-13CMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz) -5

.42

18

.25

25

.86

39

.88

55

.98

60

.78

64

.40

10

6.0

4

13

5.1

01

36

.33

15

2.9

1

OO

O OSi

S18

1H NMR spectrum of compound 3g in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

DSS-2-3g-1HMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz)

5.7

2

9.0

0

2.0

8

0.9

2

0.8

80

.83

0.1

1

0.9

5

4.6

8

7.1

37

.13

7.1

37

.14

7.1

47

.14

7.1

57

.15

7.1

57

.15

7.1

67

.16

7.3

87

.40

7.4

17

.41

7.4

17

.42

7.4

2

ClCl

OSi

S19

13C NMR spectrum of compound 3g in CDCl3

-100102030405060708090100110120130140150f1 (ppm)

DSS-2-3g-13CMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz) -5

.32

18

.36

25

.88

63

.68

12

5.1

81

27

.89

13

0.1

41

30

.58

13

2.2

6

14

1.7

5

ClCl

OSi

S20

1H NMR spectrum of compound 3h in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

DSS-2-3H-1HMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz)

6.0

0

9.3

9

2.2

4

2.2

5

2.1

02

.14

1.0

61

.07

1.1

6

-0.0

3

0.8

8

3.3

13

.33

3.3

53

.93

3.9

43

.95

3.9

53

.96

3.9

63

.97

3.9

7

7.3

57

.36

7.3

67

.37

7.3

77

.39

7.4

17

.41

7.4

37

.47

7.4

77

.49

7.5

07

.50

7.5

07

.52

7.5

27

.73

7.7

57

.84

7.8

57

.85

7.8

67

.87

7.8

78

.07

8.0

78

.07

8.0

98

.09

8.0

9

OSi

S21

13C NMR spectrum of compound 3h in CDCl3

-100102030405060708090100110120130140f1 (ppm)

DSS-2-3H-13CMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz) -5

.41

18

.33

25

.93

36

.61

63

.94

12

3.8

51

25

.39

12

5.4

41

25

.78

12

6.9

01

27

.15

12

8.6

91

32

.20

13

3.7

91

35

.09

OSi

S22

1H NMR spectrum of compound 3i in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

DSS-2-3i-1HMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz)

5.7

7

9.0

0

2.0

8

2.1

3

2.1

1

2.2

5

0.9

4

1.1

30

.93

0.0

1

0.8

9

2.7

32

.75

2.7

7

3.1

53

.17

3.2

0

3.7

33

.75

3.7

7

4.5

24

.54

4.5

6

6.6

96

.71

6.9

26

.92

6.9

26

.94

6.9

46

.94

6.9

47

.04

O

OSi

S23

13C NMR spectrum of compound 3i in CDCl3

-100102030405060708090100110120130140150160170180f1 (ppm)

DSS-2-3i-13CMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz) -5

.37

18

.35

25

.93

29

.75

39

.01

64

.99

71

.11

10

8.8

5

12

5.6

51

26

.77

12

8.4

41

30

.97

15

8.4

5

O

OSi

S24

1H NMR spectrum of compound 3j in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

DSS-2-3J-1HMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz)

6.0

0

9.4

6

2.1

9

2.1

62

.09

1.0

4

1.0

50

.96

0.1

0

0.9

4

3.1

83

.20

3.2

2

4.5

44

.56

4.5

84

.65

6.7

36

.75

7.0

37

.04

7.0

47

.05

7.0

67

.06

7.1

77

.17

O

OSi

S25

13C NMR spectrum of compound 3j in CDCl3

-100102030405060708090100110120130140150160f1 (ppm)

DSS-2-3J-13CMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz) -5

.17

18

.45

26

.00

29

.75

65

.05

71

.22

10

8.7

8

12

3.2

51

26

.23

12

6.9

0

13

3.4

9

15

9.1

5

O

OSi

S26

1H NMR spectrum of compound 3k in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

DSS-2-3k-1HMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz)

3.0

32

.77

9.0

0

2.0

8

1.0

9

1.1

01

.05

1.2

3

1.1

31

.94

1.0

7

0.9

2

0.0

20

.14

0.9

02

.45

2.4

52

.45

2.4

72

.47

2.4

72

.48

2.4

92

.50

2.5

02

.50

2.5

22

.52

2.5

22

.56

2.5

82

.58

2.5

82

.60

2.6

02

.60

2.6

22

.63

2.6

32

.64

2.6

54

.74

4.7

64

.76

4.7

85

.03

5.0

35

.04

5.0

45

.04

5.0

45

.05

5.0

55

.05

5.0

85

.08

5.6

75

.68

5.6

85

.69

5.7

05

.71

5.7

25

.73

5.7

35

.74

5.7

45

.74

5.7

55

.76

5.7

65

.78

6.7

76

.77

6.7

96

.79

6.8

16

.81

6.8

56

.85

6.8

66

.87

6.8

76

.87

6.8

86

.89

7.1

37

.14

7.1

57

.15

7.1

77

.18

8.1

8

OH

OSi

S27

13C NMR spectrum of compound 3k in CDCl3

-100102030405060708090100110120130140150160170f1 (ppm)

DSS-2-3k-13CMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz) -5

.18

-5.0

0

18

.11

25

.60

43

.28

11

7.1

01

17

.90

11

9.2

9

12

6.8

81

27

.03

12

8.6

5

13

4.1

5

15

5.7

7

OH

OSi

S28

1H NMR spectrum of compound 3l in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000DSS-2-25BPtest2

5.5

6

8.6

0

2.2

7

4.0

6

1.9

64

.08

0.8

31

.04

1.1

80

.80

-0.0

5

0.8

5

1.8

51

.86

1.8

8

2.4

72

.48

2.4

92

.50

3.9

44

.01

4.0

14

.01

4.0

24

.03

4.0

34

.03

4.0

4

7.0

97

.10

7.1

07

.11

7.1

27

.13

7.2

67

.26

7.2

77

.28

7.2

87

.29

O O

Cl

OSi

S29

13C NMR spectrum of compound 3l in CDCl3

-100102030405060708090100110120130140150160f1 (ppm)

DSS-2-25BCtest2

-5.3

4

18

.27

25

.88

31

.12

31

.43

37

.06

63

.93

64

.41

10

8.1

8

12

8.1

21

29

.65

13

1.2

11

32

.45

13

2.6

6

14

0.3

0

O O

Cl

OSi

S30

1H NMR spectrum of compound 4l in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

pp-165-38p

2.2

0

3.9

7

2.2

03

.81

1.9

1

1.8

0

1.8

61

.87

1.8

9

2.4

82

.50

2.5

3

3.9

34

.01

4.0

14

.02

4.0

34

.03

4.0

5

7.1

07

.12

7.2

87

.30

O O

OH

Cl

S31

13C NMR spectrum of compound 4l in CDCl3

0102030405060708090100110120130140150f1 (ppm)

pp-165-38c

31

.32

31

.36

37

.06

63

.47

64

.47

10

7.9

7

12

8.3

31

29

.50

13

0.7

01

32

.68

13

4.6

4

14

0.0

6

O O

OH

Cl

S32

1H NMR spectrum of compound 5d in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

DSS-2-5d-1Hnew experiment

5.7

45

.83

9.0

08

.84

6.2

1

2.0

8

1.9

4

0.0

90

.11

0.9

41

.00

3.7

8

4.6

6

6.5

2

OO

OSi

OSi

S33

13C NMR spectrum of compound 5d in CDCl3

-100102030405060708090100110120130140150160f1 (ppm)

DSS-2-5d-13Cnew experiment

-5.1

7-4

.68

18.4

218

.72

25.8

225

.95

55.6

7

65.1

5

103.

10

133.

0413

3.92

151.

45

OO

OSi

OSi

S34

1H NMR spectrum of compound 5e in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

DSS-2-5f-1H-bistbs-allylMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz)

3.2

5

3.2

4

2.9

02

.91

9.0

0

9.3

2

2.1

9

1.0

41

.18

1.1

8

1.3

5

1.1

71

.24

1.2

3

1.2

3

-0.0

8

0.0

5

0.2

70

.31

0.9

2

1.0

6

2.3

22

.34

2.3

52

.37

2.3

92

.41

2.4

22

.42

2.4

22

.43

2.4

32

.44

2.4

42

.45

2.4

62

.46

2.4

7

5.0

25

.05

5.0

55

.06

5.0

65

.15

5.1

65

.17

5.1

85

.84

5.8

65

.88

5.8

85

.89

5.9

05

.91

5.9

36

.76

6.7

86

.95

6.9

76

.99

7.1

07

.10

7.1

27

.12

7.4

87

.49

7.5

07

.51

OSi

OSi

S35

13C NMR spectrum of compound 5e in CDCl3

-100102030405060708090100110120130140150160f1 (ppm)

DSS-2-5f-1C-bistbs-allylMC10-1-spot1Selective band center: 4.21 (ppm); width: 13.2 (Hz) -4

.95

-4.7

1-4

.22

-3.8

2

18

.20

18

.30

25

.80

25

.87

43

.82

68

.73

11

6.5

31

17

.47

12

0.8

5

12

7.2

71

27

.30

13

5.7

61

35

.81

15

1.2

6

OSi

OSi

S36

1H NMR spectrum of compound 5f in CDCl3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

DSS-2-5f-1H-dimethylnew experiment

3.0

53

.15

6.0

3

9.0

0

9.0

3

2.2

2

5.7

1

1.1

2

2.1

0

1.2

4

2.2

1

-0.1

20

.02

0.1

3

0.8

8

1.0

2

2.3

32

.34

2.3

42

.36

2.3

72

.38

2.3

92

.41

2.4

32

.44

2.4

62

.48

3.7

8

4.5

64

.57

4.5

84

.59

5.0

05

.00

5.0

05

.02

5.0

25

.05

5.7

45

.76

5.7

75

.78

5.7

95

.80

5.8

15

.82

5.8

35

.85

6.5

0

OOO

Si

OSi

S37

13C NMR spectrum of compound 5f in CDCl3

-100102030405060708090100110120130140150160f1 (ppm)

DSS-2-5f-13C-dimethylnew experiment

-4.9

5-4

.71

-4.6

9-4

.67

18

.26

18

.70

25

.80

25

.82

45

.58

55

.69

75

.25

10

2.9

0

11

6.5

9

13

2.9

61

35

.56

13

7.9

2

15

1.1

9

OOO

Si

OSi

S38

1H NMR spectrum of compound 6f in CDCl3

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

DSS-sulAr-6p-Arnew experiment

5.5

0

8.7

1

1.0

2

2.4

1

5.8

7

1.3

2

1.9

8

1.3

7

2.0

3

0.1

2

1.0

1

1.9

71

.98

2.4

72

.48

2.4

92

.51

3.8

0

4.6

34

.64

4.6

54

.66

4.6

7

5.1

25

.15

5.1

85

.76

5.7

75

.78

5.7

95

.80

5.8

25

.82

5.8

35

.84

5.8

6

6.5

5

OO

HO

OSi

S39

13C NMR spectrum of compound 6f in CDCl3

-100102030405060708090100110120130140150160170180f1 (ppm)

DSS-sulAr-6C-Arnew experiment

-4.6

8

18

.66

25

.76

43

.84

55

.69

73

.58

10

2.7

5

11

8.0

5

13

3.5

01

34

.65

13

6.4

5

15

1.4

4

OO

HO

OSi

S40

1H NMR spectrum of recovered (after 3rd cycle) HS-cellulose sulphate sodium in D2O

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)

cellulosesulfate.recycle

1.00

3.32

0.98

1.00

3.35

3.65

3.74

3.83

3.96

3.99

4.33

4.40

4.52

4.53

O

NaO3SOn

OSO3Na

OOSO3Na

OSO3NaOOHO

HO

S41

13C NMR spectrum of recovered (after 3rd cycle) HS-cellulose sulphate sodium in D2O

05101520253035404550556065707580859095100105110115f1 (ppm)

cellulose.sulfate.1st.recycle.fid.CMR

62

.26

75

.27

76

.32

77

.16

80

.60

10

4.7

0

O

NaO3SOn

OSO3Na

OOSO3Na

OSO3NaOOHO

HO

S42

References

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L. Bogado and M. P. de Araujo, Polyhedron, 2013, 62, 75-82.10. C. L. Zhang, X. L. Zhu, Y. G. Ma and L. W. Zou, Chinese Chem.Lett., 2006, 17, 163-164.11. Y. Zhongzhen, Z. Yong, C. Xin, L. Weijian, L. Guo-Bo and W. Yong, Euro. J. Org. Chem., 2018, 2018,

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Melnyk, P. Berthelot, X. Thuru and N. Lebegue, J. Med. Chem., 2016, 59, 8422-8440.13. F. Shirini, A. F. Shojaei and S. Z. D. Heirati, Phosphorus, Sulfur, and Silicon and the Related

Elements, 2016, 191, 944-951.14. V. H. Jadhav, J. G. Kim, H. J. Jeong and D. W. Kim, J. Org. Chem., 2015, 80, 7275-7280.15. G. Liao, H. Gao, Y. Li, D. Che, chinese patent: CN101857581A, 2012, 8.16. H. Zhang, X. Yang, Y. Li, X. Xu, Y. Li, J. Yan, H. Zhou, chinese patent: CN103408537A, 2013, pp. 30pp.17. C. Vilanova, M. Sánchez-Péris, S. Roldán, B. Dhotare, M. Carda and A. Chattopadhyay, Tetrahedron

Lett., 2013, 54, 6562-6567.18. A. H. Jadhav and H. Kim, Tetrahedron Lett., 2012, 53, 5338-5342.19. K. C. Nicolaou, T. Lister, R. M. Denton and C. F. Gelin, Tetrahedron, 2008, 64, 4736-4757.20. G. R. Pettit, N. Melody, A. Thornhill, J. C. Knight, T. L. Groy and C. L. Herald, J. Nat. Prod., 2009, 72,

1637-1642.21. J. M. Blackwell, W. E. Piers and R. McDonald, J. Am. Chem. Soc., 2002, 124, 1295-1306.