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.