building blocks: Applications in carbohydrate synthesis with the … · 2019. 10. 14. · building blocks: Applications in carbohydrate synthesis with the assistance of continuous

1

Supporting information

Synthesis of photolabile protecting group (PPG) protected uronic acid

building blocks: Applications in carbohydrate synthesis with the

assistance of continuous flow photoreactor

Varsha Tiwari,a# Adesh Kumar Singh,a# Priyanka Chaudhary,a Peter H. Seeberger,b

Jeyakumar Kandasamya*

aDepartment of Chemistry, Indian Institute of Technology (BHU), Varanasi, Uttar Pradesh-

221005, India. E-mail: [email protected] bMax-Planck-Institute of Colloids and Interfaces, Department of Biomolecular Systems,

Am Mühlenberg 1, 14476 Potsdam, Germany

# These authors contributed equally to this work

Table of Contents

S.No. Content Page No.

1 General information 2

2 (a)-General procedure for synthesis of uronic acid esters with 2-

nitrobenzyl bromide (1a-1o)

(b)- General procedure for synthesis of uronic acid esters (1m-

1n):

2-5

3 Analytical data of 2-nitrobenzyl protected uronic acid esters(1a-

1o and 4a-4d)

5 - 12

4 Experimental procedure for deprotection of photolabile 2-

nitrobenzyl protecting group by using a continuous flow

photoreactor

13

5 Analytical data for various deprotected uronic acids (2a-2o) 13- 18

6 Procedure for synthesis of D-Glucopyranuronic acid, 2,3,4-tris-O-

(phenylmethyl)-,2-nitrophenylmethylester,1-(2,2,2-

trichloroethanimidate) (1aa).

18

7 General procedure for glycosylation 19

8 Analytical data for various deprotected uronic acids (5a-5d) 19-21

10 Copy of 1H and 3C-NMR spectra of intermediates and final

compounds

22

Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2019

2

1. General Information

Starting materials were prepared using literature procedures or modified procedures. Solvents

and chemicals were purchased from commercial sources and used without further

purification. Thin layer chromatography was performed using pre-coated plates contained

from E. Merck (TLC silica gel 60 F254). TLC plates were visualized by exposure to

ultraviolet light (UV), and then further analyzed by charring in stain solution (5% H2SO4 in

MeOH). The column chromatography was performed on silica gel (100-200 mesh) using a

mixture of ethyl acetate/hexane and methanol/ethyl acetate as an eluent. The Continuous

Flow Photoreactor was constructed with the help of M/s Lelesil innovative systems, Mumbai,

India. The NMR spectra were recorded on BrukerAvance 500 MHz NMR spectrometer and

Mass spectra were measured on Water’s Quattro Micro V 4.1. All given 13C spectra are

proton decoupled. The 1H NMR and 13C NMRs of the monosaccharide primary alcohol and

corresponding uronic acids were compared with literature reports.

2 (a)- General procedure for synthesis of uronic acid esters with 2-nitrobenzyl bromide:

(1a-1o)

To a stirred solution of appropriate uronicacid (0.5 equiv.) in dry DMF, KHCO3(4.0 equiv.),

Bu4NI (0.2 equiv.) and 2-nitrobenzyl bromide (3 equiv.) were added under argon atmosphere.

The resulting mixture was stirred for 16 h at room temperature. After completion, the reaction

mixture was filtered on celite. The filtrate was washed with water (2×50 mL) and dried over

anhydrous sodium sulfate. The solvent was concentrated under reduced pressure to provide

crude product which was purified by column chromatography on silica gel of 100-200 mesh

size. Ethyl acetate/hexane was used as an eluent.

3

(b)- Preparation of uronic acid esters 1m and 1n:

1m preparation: The compound AA (3.0 g, 8.0 mmol) was stirred in dry pyridine (20 mL) in

the presence of tert-butyldimethylsilyl chloride (1.81 g, 12.0 mmol) for overnight at room

temperature. After completion, the reaction mixture was evaporated till dryness and dissolved

in ethyl acetate. The resulting solution was washed with 0.1N HCl solution and brine

solution. The crude was subjected for the column chromatography on silica (30% EtOAc:

Hexane) to afford the primary TBDMS protected compound as a colorless syrup (3.13 g, 80%

yield).

The TBDMS protected compound (1.0 g, 2.0 mmol) was dissolved in DMF (20 ml) at 0oC to

which NaH (98 mg, 2 equiv.) followed by 4-bromobenzylbromide (562 mg, 1.1 eq.) was

added. The reaction was stirred until TLC starting material got consumed. The reaction was

quenched using water (5 mL) and diluted with ethyl acetate (20 mL). The ethyl acetate layer

was washed with cold water and evaporated in vacuo. The crude product was further dried

under high vacuum and dissolved in THF (20 ml) to which TBAF (3.0 equiv.) was added and

stirred until starting material disappeared. The solvent was evaporated and the residue was

dissolved in ethyl acetate and washed with brine. The organic layer was evaporated in vacuo

and purified using column chromatography (20% EtOAc: Hexane) to afford the pure

compound AB (723 mg, 70%) as yellowish oil.

To a vigorously stirred solution of AB (700 mg, 1.3 mmol) in DCM and H2O was added

TEMPO (0.3 eq) and 1-chloro-1, 2-benziodoxol-3(1H)-one (CBI) (909 mg, 2.5 eq). Stirring

was allowed until TLC indicated complete conversion of the starting material to a lower

running spot (~ 45 min). The reaction mixture was quenched by the addition of 10 ml

Na2S2O3 solution (10% in H2O). The mixture was then extracted twice with EtOAc (10 ml)

4

and the combined organic layers were dried (Na2SO4), filtered and concentrated. The crude

compound was purified by column chromatography using EtOAc/petroleum ether which

afforded the pure glucuronic acid (560 mg, 78%). Further the glucuronic acid (279 mg, 0.5

mmol) was converted into corresponding 2-nitrobenzyl ester 1m by using the general

procedure (2a) mentioned above. The reaction provided 1m as pale yellow viscous liquid

(325 mg, 94%).

1n preparation: The same procedure was adopted as above described for the preparation of

1m. In the place of 4-bromobenzylbromide, 2-napthylmethylbromide (497mg, 1.1 eq.) was

used. The compound AC was obtained as yellowish oil (736 mg, 75%). Corresponding

glucuronic acid was obtained as pale yellow viscous compound (532 mg, 74%). The ester 1n

was obtained as pale yellow viscous liquid (309 mg, 93%).

((2R,3R,4S,5R,6R)-4,5-bis(benzyloxy)-3-((4-bromobenzyl)oxy)-6-methoxytetrahydro-2H-

pyran-2-yl)methanol (AB):

Yellowish oil (667 mg, 60%); Rf value =0.4 in 20% EtOAc/

Hexane.IR: νmax(neat) 3320, 1099, 652 cm-1.[α]D

24= +45.0 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 7.40 (dd, J = 8.6, 1.9 Hz,

2H), 7.35–7.26 (m, 10H), 7.11 (d, J = 8.4 Hz, 2H), 4.98 (d, J = 11.0

Hz, 1H), 4.83–4.73 (m, 3H), 4.64 (d, J = 12.1 Hz, 1H), 4.57 (dd, J =

7.4, 3.9 Hz, 2H), 3.98 (t, J = 9.3 Hz, 1H), 3.76 (dd, J = 11.7, 2.4 Hz,

1H), 3.69–3.62 (m, 2H), 3.52–3.47 (m, 2H), 3.35 (s, 3H), 1.95 (s,

1H). 13C NMR (125 MHz, CDCl3) δ 138.8, 138.1, 137.3, 131.6,

129.5, 128.6, 128.5, 128.2, 128.0, 127.9, 127.7, 121.7, 98.2, 81.9,

80.1, 77.6, 75.8, 74.2, 73.4, 70.8, 61.8, 55.3. HRMS: Calc. for

C28H36BrO6[M+H]+: 543.1382, Obser. 543.1383

((2R,3R,4S,5R,6R)-4,5-bis(benzyloxy)-6-methoxy-3-(naphthalen-2-ylmethoxy)tetrahydro-

2H-pyran-2-yl)methanol (AC):

Yellowish oil (685 mg, 65 %); Rfvalue =0.4 in 20% EtOAc/

Hexane.IR: νmax(neat) 3233, 1052, 631 cm-1.[α]D

24= +25.0 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 7.79–7.74 (m, 3H), 7.69 (s,

1H), 7.45–7.41 (m, 2H), 7.39 (dd, J = 8.4, 1.6 Hz, 1H), 7.36–7.24 (m,

5

10H), 5.01 (dd, J = 11.1, 6.6 Hz, 2H), 4.85 (d, J = 11.0 Hz, 1H), 4.79

(dd, J = 11.7, 7.1 Hz, 2H), 4.65 (d, J = 12.1 Hz, 1H), 4.57 (d, J = 3.6

Hz, 1H), 4.04 (t, J = 9.3 Hz, 1H), 3.78 (dd, J = 11.5, 2.3 Hz, 1H),

3.72–3.66 (m, 2H), 3.58 (t, J = 9.3 Hz, 1H), 3.51 (dd, J = 9.6, 3.6 Hz,

1H), 3.35 (s, 3H), 1.89 (s, 1H). 13C NMR (125 MHz, CDCl3) δ 138.9,

138.2, 135.7, 133.4, 133.1, 128.6, 128.5, 128.3, 128.2, 128.1, 127.8,

127.7, 126.8, 126.26, 126.0, 126.0, 98.3, 82.1, 80.1, 77.6, 75.8, 75.2,

73.5, 70.9, 62.0, 55.3. HRMS: Calc. for C32H34O6 [M+H]+: 515.2434,

Obser. 515.2436

3. Analytical data of 2-nitrobenzyl protected uronic acid esters:

α-D-Glucopyranosiduronic acid, methyl-2,3,4-tris-O-(phenylmethyl)-2-nitrophenylmethyl

ester(1a)

Pale yellow viscous liquid (289 mg, 94%), Rfvalue =0.7 in 30% EtOAc/

Hexane. IR: νmax(neat) 1742, 1425, 1120, 1090 cm-1. [α]D

24= -21.7 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 8.12 (dd, J = 5.9, 3.6 Hz, 1H), 7.53 (dd,

J = 5.7, 3.5 Hz, 1H), 7.47–7.43 (m, 2H), 7.41–7.32 (m, 11H), 7.27 (dd, J = 4.8,

1.7 Hz, 2H), 7.21–7.19 (m, 2H), 5.60–5.53 (m, 2H), 5.02 (d, J = 10.9 Hz, 1H),

4.90–4.84 (m, 3H), 4.69 (t, J = 7.7 Hz, 2H), 4.60 (d, J = 11.0 Hz, 1H), 4.34 (d,

J = 10.0 Hz, 1H), 4.07 (t, J = 9.3 Hz, 1H), 3.84 (t, J = 9.5 Hz, 1H), 3.64 (dd, J

= 9.6, 3.5 Hz, 1H), 3.47 (s, 3H).13C NMR (125 MHz, CDCl3) δ 169.1, 147.1,

138.4, 137.9, 133.9, 131.5, 128.7, 128.6, 128.5, 128.4, 128.4, 128.3, 128.2,

128.1, 128.0, 127.7, 127.7, 125.0, 98.8, 81.5, 79.4, 79.3, 75.9, 75.0, 73.6, 70.3,

63.7, 55.7. HRMS: Calc. for C35H36NO9[M+H]+:614.2390, Obser.614.2397.

α-D-Glucopyranosiduronic acid, methyl-2,3,4-tri-O-benzoyl-2-nitrophenylmethyl ester(1b)

Pale yellow viscous liquid (304 mg, 91%); Rfvalue =0.4 in 30% EtOAc/

Hexane.IR: νmax(neat) 1750, 1719, 1420, 1099 cm-1.[α]D

24= +93.0 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 8.16–8.10 (m, 2H), 8.00 (dd, J = 17.6,

9.4 Hz, 3H), 7.77 (d, J = 7.7 Hz, 1H), 7.70 (dd, J= 11.9, 5.7 Hz, 2H), 7.62–7.33

(m, 11H), 5.86 (t, J = 9.6 Hz, 1H), 5.73 (d, J = 6.8 Hz, 1H), 5.51–5.41 (m, 1H),

5.26 (tdd, J = 42.0, 9.9, 3.6 Hz, 2H), 5.00 (s, 1H), 4.60 (d, J = 10.1 Hz, 1H),

4.49 (d, J = 9.8 Hz, 1H), 4.22 (td, J = 9.5, 2.7 Hz, 1H), 3.52 (s, 3H).13C NMR

(125 MHz, CDCl3) δ 169.0, 167.5, 166.8, 165.9, 147.4, 136.8, 134.1, 134.0,

133.6, 133.5, 133.4, 133.4, 131.3, 129.9, 129.9, 129.8, 129.4, 129.2, 129.0,

6

129.0, 128.9, 128.9, 128.4, 128.4, 128.4, 127.9, 125.2, 125.0, 97.5, 72.6, 71.0,

70.6, 64.1, 62.5, 56.0. HRMS: Calc. for C35H30NO12[M+H]+: 656.1768, Obser.

656.1772.

α-D-Glucopyranosiduronic acid, methyl 2, 3-di-O-acetyl-4-O-benzyl-2-nitrophenylmethyl ester

(1c)

Pale yellow viscous liquid (240 mg, 93%); Rfvalue = 0.36 in 30% EtOAc/

Hexane. IR: νmax(neat) 1745, 1735, 1410, 1215, 1090 cm-1.[α]D

23= +44.5 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 8.15–8.13 (m, 1H), 7.54–7.48 (m, 3H),

7.29–7.27 (m, 4H), 7.20–7.18 (m, 2H), 5.65–5.56 (m, 3H), 5.00 (d, J = 3.5 Hz,

1H), 4.90 (dd, J = 10.2, 3.6 Hz, 1H), 4.59 (s, 2H), 4.40 (d, J = 9.9 Hz, 1H), 3.96

(t, J = 9.6 Hz, 1H), 3.48 (s, 3H), 2.09 (s, 3H), 1.98 (s, 3H). 13C NMR (125 MHz,

CDCl3) δ 170.3, 169.7, 168.4, 147.2, 137.3, 133.9, 131.4, 128.8, 128.5, 128.4,

127.9, 127.8, 125.1, 97.4, 77.6, 74.7, 71.3, 70.9, 69.9, 63.9, 55.7, 20.8, 20.7.

HRMS: Calc. for C25H28NO11 [M+H]+: 518.1662, Obser. 518.1668

α-D-Glucopyranosiduronic acid, methyl 2, 3-di-O-benzoyl-4-O-benzyl-2-nitrophenylmethyl

ester (1d)

Yellow viscous liquid (312 mg, 95%); Rf value = 0.42 in 30% EtOAc/ Hexane.

IR: νmax(neat) 1736, 1716, 1290, 1088, 1375 cm-1[α]D

24= +62.9 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 8.16 (dd, J = 8.0, 1.2 Hz, 1H), 8.01–7.98

(m, 4H), 7.60–7.48 (m, 5H), 7.40 (ddd, J = 12.9, 7.5, 5.3 Hz, 4H), 7.16–7.08 (m,

5H), 6.11 (t, J = 9.7 Hz, 1H), 5.65 (q, J = 15.2 Hz, 2H), 5.26–5.21 (m, 2H),

4.63–4.58 (m, 2H), 4.55 (d, J = 9.9 Hz, 1H), 4.21 (t, J = 9.5 Hz, 1H), 3.50 (s,

3H). 13C NMR (125 MHz, CDCl3) δ 168.4, 165.8, 165.4, 147.0, 136.9, 133.9,

133.3, 133.2, 131.4, 129.8, 129.6, 129.3, 128.8, 128.7, 128.4, 128.3, 128.2,

127.9, 127.8, 125.0, 97.5, 77.4, 74.7, 71.8, 71.7, 70.0, 63.8, 55.8. HRMS: Calc.

for C35H32NO11 [M+H]+: 642.1975, Obser. 642.1970

α-D-Mannopyranosiduronic acid, methyl-2, 3, 4-tris-O-(phenylmethyl)-2-nitrophenylmethyl

ester (1e)

Pale yellow viscous liquid (261 mg, 85%); Rf value = 0.5 in 20% EtOAc/ Hexane.

IR: νmax(neat) 1752, 1445, 1135, 1075 cm-1. [α]D

24= +4.7 [c 0.1, CHCl3];1H NMR

(500 MHz, CDCl3) δ 8.11–8.13 (m, 1H), 7.55-7.53 (m, 1H), 7.45–7.22 (m, 18H),

5.54 (q, J = 15.3 Hz, 2H), 4.94 (d, J = 2.9 Hz, 1H), 4.85-4.73 (m, 3H), 4.66-4.60

(m, 3H), 4.36–4.27 (m, 2H), 3.93 (dd, J = 8.1, 3.0 Hz, 1H), 3.80 (t, J = 3.1 Hz,

1H), 3.46 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 168.8, 147.1, 138.2, 138.0,

138.0, 133.8, 131.9, 128.5, 128.5, 128.3, 128.3, 127.8, 127.7, 127.6, 127.6, 125.0,

7

99.7, 78.7, 75.6, 74.5, 74.3, 72.9, 72.3, 72.0, 63.5, 55.6. HRMS: Calc. for

C35H36NO9 [M+H]+: 614.2390, Obser. 614.2386

α-D-Mannopyranosiduronic acid, methyl 2, 3, 4-tri-O-benzoyl-2-nitrophenylmethyl ester (1f)

Pale yellow solid (291 mg, 89%); M.P:133-135 ℃; Rf value = 0.6 in 30%

EtOAc/ Hexane. IR: νmax(neat) 1755, 1729, 1414, 1040 cm-1. [α]D

25= -60.2 [c

0.1, CHCl3];1H NMR (500 MHz, CDCl3) δ 8.14–8.08 (m, 4H), 7.99–7.97 (m,

2H), 7.87 (d, J = 8.1 Hz, 2H), 7.63–7.58 (m, 2H), 7.54–7.51 (m, 1H), 7.46–7.37

(m, 7H), 7.30–7.27 (m, 2H), 6.14 (t, J = 10.1 Hz, 1H), 5.95 (dd, J = 10.1, 3.3

Hz, 1H), 5.74 (dd, J = 3.1, 1.7 Hz, 1H), 5.03 (s, 1H), 4.75 (dd, J = 12.1, 2.4 Hz,

1H), 4.54 (dd, J = 12.1, 4.4 Hz, 1H), 4.47–4.39 (m, 1H), 3.57 (s, 3H). 13C NMR

(125 MHz, CDCl3) δ 166.2, 165.5, 165.4, 133.4, 133.4, 133.1, 133.0, 129.8,

129.8, 129.8, 129.7, 129.7, 129.3, 129.1, 129.0, 128.6, 128.47, 128.3, 98.7, 70.4,

70.0, 68.7, 66.9, 62.9, 55.6. HRMS: Calc. for C35H30NO12 [M+H]+: 656.1768,

Obser. 656.1770

β-D-Glucopyranosiduronic acid, phenyl 2, 3, 4-tri-O-benzoyl-1-thio-2-nitrophenylmethyl ester

(1g)

Yellow viscous liquid (338 mg, 92%); Rf value = 0.48 in 30% EtOAc/

Hexane.IR: νmax(neat) 1748, 1718, 1422, 1140 cm-1 .[α]D

24= +18.7 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 8.07 (dd, J = 8.0, 1.5 Hz, 1H), 8.00–

7.98(m, 2H), 7.86–7.82 (m, 4H), 7.58–7.28 (m, 17H), 5.94 (t, J = 9.4 Hz, 1H),

5.73 (t, J = 9.7 Hz, 1H), 5.65–5.51 (m, 3H), 5.11 (d, J = 9.9 Hz, 1H), 4.51 (d, J

= 9.8 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 165.9, 165.6, 165.0, 164.9, 147.2,

133.8, 133.7, 133.4, 133.4, 133.3, 131.0, 130.9, 129.9, 129.8, 129.8, 129.0,

128.8, 128.7, 128.6, 128.5, 128.4, 128.4, 128.3, 125.0, 86.4, 77.2, 76.6, 73.5,

70.0, 69.9, 64.3. HRMS: Calc. for C40H32NO11S [M+H]+: 734.1696, Obser.

734.1699

β-D-Glucopyranosiduronic acid, phenyl-2, 3, 4-tris-O-(phenylmethyl)-1-thio-2-

nitrophenylmethyl ester (1h)

Pale yellow viscous liquid (311 mg, 90%); Rf value = 0.6 in 30% EtOAc/

Hexane. IR: νmax(neat) 1743, 1520, 1145, 1130 cm-1. [α]D

24= -2.9 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 8.18–8.10 (m, 1H), 7.56–7.20 (m,

22H), 5.53 (d, J = 5.3 Hz, 2H), 5.28 (d, J = 3.1 Hz, 1H), 4.94 (d, J = 10.8

Hz, 1H), 4.87–4.80 (m, 3H), 4.71 (d, J = 11.8 Hz, 1H), 4.61 (t, J = 10.4 Hz,

2H), 4.04 (t, J = 9.0 Hz, 1H), 3.84 (t, J = 9.2 Hz, 1H), 3.65 (dd, J = 9.1, 3.3

8

Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 169.1, 147.0, 138.2, 137.7, 137.5,

133.9, 131.6, 128.6, 128.6, 128.5, 128.4, 128.3, 128.2, 128.1, 128.1, 127.9,

127.9, 127.8, 127.7, 125.0, 97.8, 91.7, 80.7, 79.2, 78.9, 75.7, 74.9, 73.5,

70.6, 63.6. HRMS: Calc. for C40H38NO8S [M+H]+: 692.2318, Obser.

692.2315

α-D-galactopyranosiduronic acid- 1, 2, 3, 4-Di-O-isopropylidene-2-nitrophenylmethyl ester (1i)


Hexane. IR: νmax(neat) 1747, 1465, 1235 cm-1. [α]D

24= -62.4 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 8.13 (d, J = 8.2 Hz, 1H), 7.75 (d, J =

7.8 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H), 7.49 (t, J = 7.8 Hz, 1H), 5.75–5.67 (m,

11H), 5.31 (s, 1H), 4.68 (ddd, J = 28.6, 7.7, 2.3 Hz, 2H), 4.56 (d, J = 2.0 Hz,

1H), 4.41 (dd, J = 4.9, 2.6 Hz, 1H), 1.55 (s, 3H), 1.46 (s, 3H), 1.36 (s,

3H).13C NMR (125 MHz, CDCl3) δ 167.8, 147.2, 133.6, 132.0, 129.0, 128.6,

124.9, 110.0, 109.1, 96.5, 72.1, 70.7, 70.2, 68.6, 63.5, 25.9, 25.8, 24.7, 24.6.


β-D-Glucopyranosiduronic acid, 4-Methylphenyl-2, 3, 4-tri-O-benzoyl-1-thio-2-nitrophenyl-

methyl ester (1j)


Hexane.IR:νmax(neat) 1738, 1720, 1255, 1445 cm-1[α]D

24= +10.7 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 8.05 (dd, J = 8.0, 1.4 Hz, 1H),

7.99–7.97 (m, 2H), 7.84–7.80 (m, 4H), 7.52 (dd, J = 10.5, 4.2 Hz, 2H),

7.46–7.38 (m, 8H), 7.32–7.25 (m, 5H), 7.13 (d, J = 7.9 Hz, 2H), 5.93 (t, J

= 9.4 Hz, 1H), 5.69 (t, J = 9.7 Hz, 1H), 5.58 (dd, J = 38.5, 14.8 Hz, 2H),

5.48 (t, J = 9.6 Hz, 1H), 5.04 (d, J = 9.9 Hz, 1H), 4.48 (d, J = 9.8 Hz, 1H),

2.35 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 165.9, 165.6, 165.0, 164.9,

147.2, 139.1, 134.4, 133.7, 133.4, 133.4, 133.3, 131.0, 129.8, 129.8, 129.8,

129.8, 129.1, 129.0, 128.8, 128.6, 128.5, 128.4, 128.4, 128.3, 126.8, 125.0,

86.5, 76.6, 73.5, 70.0, 69.9, 64.2, 21.2. HRMS: Calc. for C41H34NO11S

[M+H]+: 748.1853, Obser. 748.1855

9

α-D-Glucopyranosiduronic acid, methyl-2-nitrophenylmethyl ester-2, 3-dibenzoate (1k)


Hexane. IR: νmax(neat) 3250, 1756, 1718, 1360, 1180, 1080 cm-1[α]D

23=

+134.5 [c 0.1, CHCl3];1H NMR (500 MHz, CDCl3) δ 8.13 (d, J = 8.2 Hz,

1H), 8.00–7.95 (m, 4H), 7.73–7.68 (m, 1H), 7.50 (dd, J = 4.5, 2.9 Hz, 3H),

7.36 (t, J = 7.5 Hz, 5H), 5.89–5.85 (m, 1H), 5.71 (q, J = 15.0 Hz, 2H), 5.25

(s, 2H), 4.49 (d, J = 9.9 Hz, 1H), 4.22 (t, J = 9.6 Hz, 1H), 3.49 (s, 3H), 3.47

(d, J = 0.9 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 168.9, 165.7, 162.5,

147.1, 133.9, 133.3, 133.2, 131.3, 129.7, 129.7, 129.5, 129.1, 128.8, 128.8,

128.7, 128.3, 128.2, 125.0, 97.4, 72.4, 71.0, 70.6, 70.5, 63.9, 55.8. HRMS:

Calc. for C28H26NO11 [M+H]+: 552.1506, Obser. 552.1501

(2S)-2-nitrobenzyl-2-((3aR, 6R, 6aR)-1-benzyl-6-(benzyloxy)-2-oxohexahydrofuro[3, 2-d]oxazol-5-yl)-2-hydroxyacetate (1l)

Pale yellow viscous liquid (214 mg, 80%); Rf value = 0.6 in 50%

EtOAc/ Hexane. IR: νmax(neat) 3355, 1762, 1751, 1290, 1120, 1075 cm-

1. [α]D24= -48.6 [c 0.1, CHCl3];

1H NMR (500 MHz, CDCl3) δ 8.10–

8.09(m, 1H), 7.52–7.45 (m, 3H), 7.41–7.38 (m, 3H), 7.29–7.27 (m,

4H), 7.24–7.22 (m, 2H), 7.12–7.10 (m, 2H), 6.22 (d, J = 5.5 Hz, 1H),

5.61 (dd, J = 80.6, 14.8 Hz, 2H), 4.85 (d, J = 3.6 Hz, 1H), 4.69 (d, J =

15.1 Hz, 1H), 4.32 (s, 2H), 4.20–4.17 (m, 2H), 4.10 (d, J = 5.6 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 166.0, 156.3, 147.3, 136.2, 134.9,

133.8, 131.1, 129.2, 129.1, 129.0, 128.6, 128.6, 128.3, 128.2, 127.6,

125.0, 101.0, 80.0, 79.9, 77.2, 72.4, 63.8, 63.7, 47.6. HRMS: Calc. for

C28H27N2O9 [M+H]+: 535.1717, Obser. 535.1723

(2S,3S,4S,5R,6R)-2-nitrobenzyl-4,5-bis(benzyloxy)-3-(4-bromobenzyloxy)-6-methoxytetra-

hydro-2H-pyran-2-carboxylate (1m)


EtOAc/ Hexane. IR: νmax(neat)1730, 1520, 1250, 1070, 565 cm-1

[α]D24= -7.8 [c 0.1, CHCl3];

1H NMR (500 MHz, CDCl3) δ 8.17–8.06

(m, 1H), 7.50–7.46 (m, 3H), 7.38–7.28 (m, 12H), 7.02 (d, J = 8.1 Hz,

2H), 5.57 (q, J = 15.0 Hz, 2H), 4.99 (d, J = 10.9 Hz, 1H), 4.83–4.76

(m, 3H), 4.69–4.66 (m, 2H), 4.50 (d, J = 11.3 Hz, 1H), 4.29 (d, J = 10.0

Hz, 1H), 4.02 (t, J = 9.3 Hz, 1H), 3.77 (t, J = 9.5 Hz, 1H), 3.61 (dd, J =

9.6, 3.5 Hz, 1H), 3.46 (s, 3H).13C NMR (125 MHz, CDCl3) δ 169.0,

10

147.3, 138.4, 137.8, 136.9, 133.7, 131.3, 131.3, 129.2, 128.8, 128.7,

128.5, 128.4, 128.1, 128.1, 127.9, 127.7, 125.1, 121.5, 98.8, 81.3, 79.4,

79.3, 75.8, 74.1, 73.6, 70.1, 63.7, 55.7. HRMS: Calc. for

C35H34BrNO9[M+H]+: 691.1417, Obser.691.1415

(2S,3S,4S,5R,6R)-2-nitrobenzyl-4,5-bis(benzyloxy)-6-methoxy-3-(naphthalen-2-ylmethoxy)-

tetrahydro-2H-pyran-2-carboxylate (1n)


EtOAc/ Hexane. IR: νmax(neat) 1735, 1515, 1268, 1077 cm-1. [α]D

25=

-8.9 [c 0.1, CHCl3];1H NMR (500 MHz, CDCl3) δ 8.03 (d, J = 7.9

Hz, 1H), 7.79–7.78 (m, 1H), 7.73–7.68 (m, 2H), 7.61 (s, 1H), 7.47–

7.25 (m, 17H), 5.50 (dd, J = 45.3, 15.2 Hz, 2H), 5.03 (dd, J = 11.0,

5.5 Hz, 2H), 4.87 (dd, J = 14.7, 11.6 Hz, 2H), 4.71 (dd, J = 21.0, 8.6

Hz, 3H), 4.36 (d, J = 9.9 Hz, 1H), 4.10 (t, J = 9.2 Hz, 1H), 3.88 (t, J

= 9.5 Hz, 1H), 3.66 (dd, J = 9.6, 3.4 Hz, 1H), 3.47 (s, 3H).13C NMR

(125 MHz, CDCl3) δ 169.0, 147.0, 138.4, 137.9, 135.3, 133.7,

133.1, 132.9, 131.4, 128.5, 128.4, 128.1, 128.1, 128.0, 128.0, 127.8,

127.7, 127.6, 126.4, 126.0, 125.9, 125.7, 124.9, 98.8, 81.5, 79.4,

79.3, 75.9, 75.1, 73.6, 70.3, 63.7, 55.7. HRMS: Calc. for C39H37NO9

[M+H]+: 663.2468, Obser. 663.2471

β-D-Glucopyranosiduronic acid, phenyl-4-O-[6-methyl-2, 3, 4-tris-O-(phenylmethyl)-β-D-

mannopyranuronosyl]-2, 3-bis-O-(phenylmethyl)-1-thio-2-nitrophenylmethyl ester (1o)


EtOAc/ Hexane. IR: νmax(neat) 1755, 1745, 1395, 1285, 1076 cm-1.

[α]D24= +8.8 [c 0.1, CHCl3];

1H NMR (500 MHz, CDCl3) δ 8.12-7.20

(m, 38H), 5.88 (s, 1H), 5.57 (dd, J = 42.3, 15.3 Hz, 2H), 4.96–4.47

(m, 15H), 4.06 (t, J = 9.3 Hz, 1H), 3.91-3.83 (m, 3H), 3.64–3.61 (m,

2H). 13C NMR (125 MHz, CDCl3) δ 169.7, 168.9, 147.1, 138.5,

138.0, 138.0, 137.1, 137.0, 134.1, 131.7, 128.8, 128.7, 128.7, 128.7,

128.6, 128.5, 128.2, 128.2, 128.0, 128.0, 128.0, 127.9, 127.9, 127.8,

127.8, 125.2, 102.5, 98.9, 81.2, 79.3, 77.4, 75.9, 75.3, 75.3, 74.1,

73.5, 73.0, 73.0, 72.3, 72.2, 71.1, 63.9. HRMS: Calc. for

C67H63N2O16S [M+H]+: 1183.3898, Obser. 1183.3900

11

β-D-Glucopyranosiduronicacid,hexyl, 2, 3, 4-tri-O-benzyl-2-nitrophenylmethyl ester (4a)

Pale yellow solid (304 mg, 89%); M.P: 96-97 ℃; Rf value = 0.7 in

30% EtOAc/ Hexane. β:α isomer (>20:1); IR: νmax(neat) 1751, 1517,

1305, 1125 cm-1. [α]D24= -9.6 [c 0.1, CHCl3];

1H NMR (500 MHz,

CDCl3) δ 8.15–8.13 (m, 1H), 7.58–7.56 (m, 1H), 7.49–7.45 (m, 2H),

7.39–7.30 (m, 10H), 7.29–7.25 (m, 3H), 7.19 (dd, J = 6.8, 2.8 Hz,

2H), 5.63 (d, J = 15.3 Hz, 1H), 5.53 (d, J = 15.2 Hz, 1H), 4.97 (dd, J

= 10.8, 9.6 Hz, 2H), 4.85 (dd, J = 16.8, 11.0 Hz, 2H), 4.76 (d, J =

10.9 Hz, 1H), 4.61 (d, J = 11.0 Hz, 1H), 4.53 (d, J = 7.7 Hz, 1H),

4.04–3.96 (m, 2H), 3.92 (t, J = 9.4 Hz, 1H), 3.73 (t, J = 9.1 Hz, 1H),

3.61-3.53 (m, 2H), 1.71–1.66 (m, 3H), 1.45–1.29 (m, 7H), 0.92 (dd,

J = 9.5, 4.6 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 167.9, 147.1,

138.3, 138.2, 137.8, 133.8, 131.7, 128.6, 128.5, 128.4, 128.3, 128.1,

127.9, 127.8, 127.8, 127.7, 127.7, 125.0, 104.0, 83.9, 81.7, 78.9,

75.7, 74.9, 74.8, 74.5, 70.5, 63.6, 31.6, 29.6, 25.8, 22.5, 14.0.


β-D-Glucopyranosiduronic acid-1, 2, 3, 4-tetra-O-benzyl-2-nitrophenylmethyl ester (4b)

OBnOBnO

OBn

O

ONO2

OBn

4b

Pale yellow powder. (293 mg, 85%); M.P: 124-126 ℃; Rf value = 0.72 in 30%

EtOAc/ Hexane. β:α isomer (>20:1); IR: νmax(neat) 1775, 1480, 1310, 1095

cm-1. [α]D24= -22.9 [c 0.1, CHCl3];

1H NMR (500 MHz, CDCl3) δ 8.15–8.13(m,

1H), 7.59–7.57 (m, 1H), 7.48–7.45 (m, 2H), 7.41–7.26 (m, 19H), 7.21–7.18

(m, 2H), 5.59 (dd, J = 49.7, 15.2 Hz, 2H), 5.02–4.93 (m, 3H), 4.84 (dd, J =

21.8, 11.0 Hz, 2H), 4.73 (dd, J = 22.2, 11.3 Hz, 2H), 4.64 (dd, J = 13.2, 9.3

Hz, 2H), 4.05 (d, J = 9.7 Hz, 1H), 3.96–3.93 (m, 1H), 3.74 (t, J = 9.0 Hz, 1H),

3.63 (dd, J = 9.0, 7.6 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 167.9, 147.2,

138.2, 138.1, 137.8, 137.0, 133.8, 131.6, 128.7, 128.6, 128.5, 128.4, 128.4,

128.4, 128.3, 128.1, 128.0, 127.9, 127.9, 127.8, 127.8, 127.7, 127.7, 125.0,

102.8, 83.9, 81.8, 78.9, 75.7, 74.9, 74.6, 71.4, 63.7. HRMS: Calc. for

C41H40NO9 [M+H]+: 690.2703, Obser. 690.2702

12

α-D-Glucopyranoside,methyl-6-O-[6-methyl-2,3,4-tris-O-(phenylmethyl)-D-glucopyranurono-

syl]-2, 3, 4-tris-O-(phenylmethyl)-2-nitrophenylmethyl ester (4c)

Yellow solid (408 mg, 78%); M.P: 103-105 ℃; Rf value = 0.5 in 30%

EtOAc/ Hexane. β:α isomer (3:2); IR: νmax(neat) 1762, 1487, 1254,

1082 cm-1. [α]D24= +12.1 [c 0.1, CHCl3];

1H NMR (500 MHz, CDCl3)

δ 8.12–8.09 (m, 1H), 7.45–7.39 (m, 2H), 7.38–7.24 (m, 29H), 7.18

(ddd, J = 7.7, 6.7, 1.7 Hz, 3H), 5.62–5.43(m, 2H), 5.03–4.92 (m, 3H),

4.88–4.52 (m, 10H), 4.44 (t, J = 8.8 Hz, 1H), 4.17 (dd, J = 10.8, 1.7

Hz, 1H), 4.04–3.97 (m, 2H), 3.91–3.78 (m, 3H), 3.71–3.46 (m, 4H),

3.37 (d, J = 29.8 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 169.2,

167.7, 147.1, 138.8, 138.4, 138.3, 138.3, 138.2, 138.1, 138.1, 138.0,

137.8, 133.8, 133.7, 131.6, 131.6, 128.6, 128.5, 128.5, 128.4, 128.4,

128.4, 128.3, 128.2, 128.1, 128.0, 128.0, 127.9, 127.9, 127.9, 127.8,

127.7, 127.7, 127.7, 127.6, 127.6, 127.6, 127.5, 127.5, 125.0, 124.9,

104.1, 98.0, 98.0, 97.8, 84.0, 82.1, 81.9, 81.5, 81.0, 80.1, 79.8, 79.5,

79.3, 78.8, 77.9, 77.7, 77.2, 75.7, 75.7, 75.6, 75.0, 74.9, 74.9, 74.8,

74.6, 73.3, 72.7, 70.4, 70.3, 69.8, 68.9, 66.7, 63.6, 63.5, 55.2. HRMS:

Calc. for C62H64NO14 [M+H]+: 1046.4327, Obser. 1046.4329

D-Glucopyranosiduronic acid-1, 2, 3, 4-tetra-O-benzyl-2-nitrophenylmethyl ester (4d)

White solid. (165 mg, 52%); M.P: 123-125 ℃;Rf value = 0.5 in 20% EtOAc/

Hexane. β:α isomer (3:1); IR: νmax(neat) 1775, 1480, 1310, 1095 cm-1.

[α]D24= -9.9 [c 0.1, CHCl3];

1H NMR (500 MHz, CDCl3) δ 8.15–8.14 (m,

1H), 7.60–7.20 (m, 24H), 5.66–5.53 (m, 2H), 5.03–4.95 (m, 3H), 4.89–4.71

(m, 4H), 4.65 (dd, J = 12.6, 9.4 Hz, 2H), 4.07 (d, J = 9.7 Hz, 1H), 3.97 (t, J =

9.3 Hz, 1H), 3.75 (t, J = 9.0 Hz, 1H), 3.65–3.62 (m, 1H).13C NMR (125

MHz, CDCl3) δ 169.1, 168.0, 147.2, 138.5, 138.3, 138.1, 137.9, 137.8, 137.0,

136.7, 133.8, 131.6, 128.7, 128.7, 128.6, 128.6, 128.5, 128.4, 128.4, 128.4,

128.3, 128.3, 128.2, 128.1, 128.0, 128.0, 127.9, 127.8, 127.8, 127.8, 127.7,

125.1, 102.8, 96.1, 83.9, 81.8, 81.5, 79.4, 79.4, 78.9, 75.9, 75.7, 75.1, 74.9,

74.6, 73.2, 71.4, 70.6, 69.6, 63.7. Calc. for C41H40NO9 [M+H]+: 690.2703,

Obser. 690.2705

13

4. Experimental procedure for deprotection of photolabile 2-nitrobenzyl protecting

group by using a continuous flow photoreactor:

Approximately 0.005M solution of photolabile protected uronic acid building blocks were

prepared in methanol and added to the reactor B. The solution was circulated with the help of

peristaltic pump to the flexi coil with a flow rate 50 RPM which required approx. 3 minutes

for completing one cycle. Total six cycles were repeated after which the solvent was

evaporated and purified through column chromatography.

5. Analytical data for various deprotected uronic acids:

Methyl-2, 3, 4-tri-O-benzyl-α-D-glucopyranosiduronic acid (2a)1

Colourless oily syrup (110mg, 92%); Rfvalue =0.6 in 50% EtOAc/ Hexane.

IR:νmax(neat) 3482, 1712, 1120 cm-1. [α]D

24= +4.4 [c 0.1, CHCl3]; 1H NMR

(500 MHz, DMSO-D6) δ 7.40–7.22 (m, 16H), 4.91 (d, J = 3.4 Hz, 1H), 4.84

(d, J = 11.3 Hz, 1H), 4.75–4.66 (m, 4H), 4.58 (d, J = 11.0 Hz, 1H), 3.93 (d,

J = 9.9 Hz, 1H), 3.79 (t, J = 9.3 Hz, 1H), 3.66–3.62 (m, 1H), 3.56 (dd, J =

9.6, 3.4 Hz, 1H), 3.34 (s, 3H).13C NMR (125 MHz, DMSO-D6) δ 170.9,

139.0, 138.8, 138.6, 128.7, 128.6, 128.6, 128.1, 128.1, 128.0, 127.9, 127.9,

127.8, 127.8, 98.0, 80.8, 79.6, 75.0, 74.5, 72.0, 70.4, 55.3.HRMS: Calc. for

C28H31O7[M+H]+: 479.2070, Obser.479.2075.

Methyl-2, 3, 4-tri-O-benzoyl-α-D-glucopyranosiduronic acid (2b)

Colourless Oily syrup (116 mg, 89%);Rfvalue =0.5 in 60% EtOAc/ Hexane.

IR: νmax(neat) 3545, 1718, 1710 cm-1. [α]D

24= +62.2 [c 0.1, CHCl3];1H NMR

(500 MHz, CDCl3) δ 8.00–7.89 (m, 6H), 7.53 (q, J = 7.6 Hz, 2H), 7.46 (t, J

= 7.4 Hz, 1H), 7.41-7.36 (m, 4H), 7.32 (t, J = 7.8 Hz, 2H), 6.20 (t, J = 9.8

Hz, 1H), 5.75 (t, J = 9.8 Hz, 1H), 5.37 (d, J = 3.6 Hz, 1H), 5.33 (dd, J =

10.1, 3.6 Hz, 1H), 4.66 (d, J = 10.1 Hz, 1H), 3.54 (s, 3H).13C NMR (125

MHz, CDCl3) δ 171.1, 165.7, 165.6, 165.4, 133.4, 133.4, 133.2, 129.9,

129.9, 129.7, 129.0, 128.8, 128.4, 128.4, 128.3, 97.4, 77.2, 71.4, 69.8, 68.0,

56.3.HRMS: Calc. for C28H25O10[M+H]+: 521.1448, Obser. 521.1446

Methyl-2, 3-di-O-acetyl-4-benzyl-α-D-glucopyranosiduronic acid (2c)

Colourless oily syrup (87mg, 91 %); Rfvalue =0.5 in 50% EtOAc/Hexane. IR:

νmax(neat) 3353, 1735, 1719, 1082 cm-1. [α]D

24= +53.6 [c 0.1, CHCl3];1H

NMR (500 MHz, CDCl3) δ 7.34–7.29 (m, 7H), 7.26–7.25 (m, 2H), 5.59–5.55

(m, 1H), 4.99 (d, J = 3.5 Hz, 1H), 4.88 (dd, J = 10.2, 3.6 Hz, 1H), 4.65 (dd, J

14

= 54.8, 11.1 Hz, 3H), 4.33 (d, J = 9.9 Hz, 1H), 3.89 (t, J = 9.5 Hz, 1H), 3.46

(s, 3H), 2.09 (s, 3H), 1.97 (s, 3H).13C NMR (125 MHz, CDCl3) δ 172.2,

170.3, 169.7, 137.2, 128.4, 128.0, 128.0, 97.3, 77.5, 74.7, 71.3, 70.8, 69.4,

55.8, 20.7, 20.7. HRMS: Calc. for C18H23O9[M+H]+: 383.1342, Obser.

383.1343

Methyl-2, 3-di-O-benzoyl-4-benzyl-α-D-glucopyranosiduronic acid (2d)

Colourless oily liquid (119 mg, 94%);Rfvalue =0.6 in 50% EtOAc/ Hexane.

IR: νmax(neat) 3260, 1715, 1708, 1124 cm-1. [α]D

24= +108.1 [c 0.1, CHCl3];1H

NMR (500 MHz, CDCl3) δ 8.10–8.08 (m, 4H), 7.62 (dd, J = 15.5, 7.5 Hz,

2H), 7.49 (dt, J = 15.8, 7.9 Hz, 4H), 7.26 (s, 5H), 6.20 (t, J = 9.6 Hz, 1H),

5.35 (dt, J = 10.0, 3.6 Hz, 2H), 4.77 (dd, J = 38.0, 10.9 Hz, 2H), 4.61 (d, J =

9.9 Hz, 1H), 4.28 (t, J= 9.5 Hz, 1H), 3.58 (s, 3H).13C NMR (125 MHz,

CDCl3) δ 173.6, 166.0, 165.6, 136.9, 133.5, 133.3, 129.9, 129.7, 129.4, 128.8,

128.4, 128.3, 128.2, 128.0, 97.5, 77.4, 77.3, 77.1, 76.9, 74.8, 71.9, 71.7, 69.8,

55.9.HRMS:Calc. for C28H27O9[M+H]+: 507.1650, Obser.507.1648

Methyl-2, 3, 4-tri-O-benzyl-α-D-mannopyranosiduronic acid (2e)1

Colourless oily syrup (105 mg, 88 %); Rfvalue =0.5 in50% EtOAc/PE;

IR:νmax (neat) 3386, 1725, 1135 cm-1.[α]D

23=+15.0 (c, 1.2 in CHCl3); 1H

NMR (500 MHz, CDCl3) δ 7.39–7.28 (m, 15H), 4.96 (s, 1H), 4.76 (dt, J =

24.4, 11.2 Hz, 4H), 4.64 (d, J = 3.9 Hz, 2H), 4.31–4.21 (m, 2H), 3.93–3.91

(m, 1H), 3.80–3.79 (m, 1H), 3.46 (d, J = 1.3 Hz, 3H).13C NMR (125 MHz,

CDCl3) δ 174.1, 138.1, 138.0, 137.7, 128.4, 128.1, 127.9, 127.8, 127.7, 127.7,

127.6, 99.6, 78.5, 75.6, 74.5, 72.9, 72.4, 71.3, 55.7.HRMS: Calc. for

C28H30O7Na [M+Na]+: 501.1890, Obser.501.1893.

Methyl-2, 3, 4-tri-O-benzoyl-α-D-mannopyranosiduronic acid (2f)

Colorless oily syrup (121 mg, 93 %); Rf value =0.4 in 50% EtOAc/PE; IR:

νmax(neat) 3558, 1712, 1708 cm-1. [α]D

24= -61.4 [c 0.1, CHCl3];1H NMR (500

MHz, CDCl3) δ 8.10 (dd, J = 8.2, 1.2 Hz, 2H), 7.98–7.97 (m, 2H), 7.87 (dd, J =

8.3, 1.2 Hz, 2H), 7.62 (t, J= 7.4 Hz, 1H), 7.54–7.45 (m, 4H), 7.39 (t, J = 7.7

Hz, 2H), 7.31 (t, J = 7.8 Hz, 2H), 6.05 (t, J = 9.5 Hz, 1H), 5.92 (dd, J = 9.6, 3.4

Hz, 1H), 5.69 (dd, J = 3.2, 2.5 Hz, 1H), 5.16 (d, J = 2.2 Hz, 1H), 4.69 (d, J =

9.4 Hz, 1H), 3.59 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 171.4, 165.5, 165.4,

165.3, 133.6, 133.4, 133.3, 129.9, 129.8, 129.7, 129.1, 129.0, 128.9, 128.6,

15

128.4, 128.3, 98.8, 69.8, 69.4, 69.3, 67.4, 56.2. HRMS: Calc. for C28H25O10

[M+H]+β: 521.1448, Obser. 521.1455

Phenyl-2, 3, 4-tri-O-benzoyl-1-thio-β-D-glucopyranosyduronic acid (2g)

Colorless oily syrup (133 mg, 89%); Rf value = 0.53 in 50% EtOAc/PE; IR:

νmax(neat) 3440, 1712, 1705 cm-1. [α]D

24= +23.3 [c 0.1, CHCl3];1H NMR

(500 MHz, CDCl3) δ 7.99–7.97 (m, 2H), 7.92–7.91 (m, 2H), 7.84–7.83 (m,

2H), 7.56–7.28 (m, 14H), 5.92 (t, J = 9.3 Hz, 1H), 5.73 (t, J = 9.6 Hz, 1H),

5.54 (t, J = 9.6 Hz, 1H), 5.11 (d, J = 9.9 Hz, 1H), 4.39 (d, J = 9.8 Hz, 1H).

13C NMR (125 MHz, CDCl3) δ170.4, 165.6, 165.1, 164.9, 133.3, 133.3,

133.2, 131.7, 129.9, 129.8, 129.8, 129.2, 129.0, 129.0, 128.8, 128.4, 128.4,

128.3, 128.2, 86.5, 73.8, 70.3, 69.9, 66.2. HRMS: Calc. for C33H27O9S

[M+H]+: 599.1376, Obser. 599.1377

Phenyl-2, 3, 4-tri-O-benzyl-1-thio-β-D-glucopyranosyduronic acid (2h)

Colorless oily syrup (132 mg, 95%); Rf value = 0.56 in 50% EtOAc/PE;

IR:νmax (neat) 3280, 1730, 1095 cm-1. [α]D

24= -7.5 [c 0.1, CHCl3];1H NMR

(500 MHz, CDCl3) δ7.60–7.58 (m, 2H), 7.42–7.26 (m, 19H), 4.93 (d, J = 10.3

Hz, 1H), 4.88 (t, J= 7.8 Hz, 2H), 4.81–4.75 (m, 3H), 4.70 (d, J = 10.8 Hz,

1H), 4.01 (d, J = 9.3 Hz, 1H), 3.87 (t, J = 9.0 Hz, 1H), 3.77 (t, J = 8.6 Hz,

1H), 3.58 (dd, J = 9.6, 8.4 Hz, 1H).. 13C NMR (125 MHz, CDCl3) δ 172.3,

138.0, 137.7, 137.3, 133.0, 132.3, 129.1, 128.5, 128.4, 128.4, 128.2, 128.1,

128.0, 127.9, 127.8, 88.1, 85.3, 80.2, 78.7, 77.5, 75.7, 75.4, 75.0. HRMS:

Calc. for C33H33O6S [M+H]+: 557.1998, Obser.557.2001

1, 2, 3, 4-Di-O-isopropylidene-α-D-galactopyranosiduronic acid (2i)

Colorless viscous liquid (62 mg, 90%); Rf value = 0.6 in 50% EtOAc/

Hexane.IR:νmax (neat) 3315, 1715 cm-1.1H NMR (500 MHz, DMSO-d6) δ 5.53

(d, J = 5.0 Hz, 1H), 4.65 (dd, J = 7.7, 2.5 Hz, 1H), 4.51 (dd, J = 7.7, 2.3 Hz, 1H),

4.40 (dd, J = 5.0, 2.5 Hz, 1H), 4.18 (d, J = 2.2 Hz, 1H), 1.43 (s, 3H), 1.32 (s,

3H), 1.28 (d, J = 3.3 Hz, 6H). 13C NMR (125 MHz, DMSO-d6) δ 169.3, 109.1,

108.5, 96.2, 71.9, 70.5, 69.9, 67.7, 26.2, 26.1, 25.1, 24.8. HRMS: Calc.

forC12H19O7 [M+H]+: 275.1131, Obser. 275.1129

16

Tolyl-2, 3, 4-tri-O-benzoyl-1-thio-β-D-glucopyranosyduronic acid (2j)

White solid (147 mg, 96%); M.P: 195-197 ℃;Rf value = 0.5 in 50%

EtOAc/ Hexane. IR:νmax (neat) 3356, 1727, 1702 cm-1[α]D

24= +12.6 [c

0.1, CHCl3];1H NMR (500 MHz, CDCl3) δ 8.00–7.98 (m, 2H), 7.92 (dd,

J = 8.4, 1.2 Hz, 2H), 7.85–7.83 (m, 2H), 7.57–7.53 (m, 1H), 7.52–7.48

(m, 1H), 7.47–7.45 (m, 3H), 7.43–7.40 (m, 2H), 7.35 (dd, J = 10.8, 4.9

Hz, 2H), 7.31–7.28 (m, 2H), 7.16 (d, J = 7.9 Hz, 2H), 5.93 (t, J = 9.3 Hz,

1H), 5.70 (t, J = 9.6 Hz, 1H), 5.51–5.47 (m, 1H), 5.05 (d, J = 9.9 Hz,

1H), 4.42 (d, J = 9.7 Hz, 1H), 2.37 (s, 3H). 13C NMR (125 MHz, CDCl3)

δ 170.1, 165.7, 165.2, 164.9, 139.1, 134.3, 133.4, 133.4, 133.3, 129.9,

129.9, 129.8, 129.8, 129.1, 128.7, 128.6, 128.4, 128.4, 128.3, 127.0, 86.5,

75.9, 73.5, 70.0, 69.7, 21.2. HRMS: Calc. forC34H29O9S [M+H]+:

613.1532, Obser. 613.1536

Methyl-2, 3-di-O-benzoyl-α-D-glucopyranosiduronic acid (2k)

Colorless oil (94 mg, 90%);Rf value = 0.55 in 50% EtOAc/PE; [α]D24= +4.4 [c

0.1, CHCl3]; IR:νmax (neat) 3520, 3286, 1725, 1718, 1135 cm-1[α]D

24= +151.7

[c 0.1, CHCl3];1H NMR (500 MHz, MeOD-d4) δ 8.00–7.98 (m, 2H), 7.91 (dd,

J = 6.0, 4.7 Hz, 2H), 7.54 (t, J = 7.4 Hz, 2H), 7.42-7.37 (m, 4H), 5.83–5.78

(m, 1H), 5.20 (dd, J = 8.8, 2.7 Hz, 2H), 4.28 (d, J = 10.0 Hz, 1H), 4.09 (t, J =

9.7 Hz, 1H), 3.49 (s, 3H).13C NMR (125 MHz, MeOD-d4) δ 170.9, 166.1,

165.6, 133.2, 132.9, 129.6, 129.3, 129.2, 128.9, 128.1, 128.1, 97.5, 72.5, 71.7,

71.1, 69.8, 54.7. HRMS: Calc. for C21H21O9 [M+H]+: 417.1186,

Obser.416.1190

2-(1-benzyl-6-(benzyloxy)-2-oxohexahydrofuro[3, 2-d]oxazol-5-yl)-2-hydroxyacetic acid (2l)

Colorless oily syrup (54 mg, 79%); Rf value = 0.43 in 60% EtOAc/PE;

IR:νmax (neat) 3306, 3120, 1711, 1302, 1135, 1070 cm-1. [α]D

24= -49.4 [c

0.1, CHCl3];1H NMR (500 MHz, CDCl3) δ 7.37–7.27 (m, 8H), 7.17 (t, J

= 7.4 Hz, 3H), 6.14 (d, J = 5.0 Hz, 1H), 4.73 (s, 1H), 4.65 (d, J = 15.1

Hz, 1H), 4.40–4.31 (m, 2H), 4.17 (d, J = 3.3 Hz, 1H), 4.10 (s, 1H), 4.06–

4.04 (m, 2H). 13C NMR (125 MHz, CDCl3) δ169.3, 156.8, 136.3, 134.7,

129.2, 128.6, 128.6, 128.3, 128.2, 127.8, 101.2, 79.5, 77.4, 77.1, 76.9,

72.6, 64.2, 47.5.HRMS: Calc. for C21H22NO7 [M+H]+: 400.1396, Obser.

400.1395

17

(2S,3S,4S,5R,6R)-4,5-bis(benzyloxy)-3-(4-bromobenzyloxy)-6-methoxytetrahydro-2H-pyran-

2-carboxylic acid (2m)

Colorless viscous liquid (124 mg, 89%); Rf value = 0.20 in 50%

EtOAc/PE. IR:νmax (neat) 3263, 1727, 1077, 585 cm-1;[α]D

24= -1.9 [c

0.1, CHCl3];1H NMR (500 MHz, CDCl3) δ 7.40–7.28 (m, 12H), 7.09

(d, J = 8.3 Hz, 2H), 4.99 (d, J = 11.0 Hz, 1H), 4.83–4.74 (m, 3H), 4.66

(t, J = 7.3 Hz, 2H), 4.58 (d, J = 11.1 Hz, 1H), 4.24 (d, J = 10.0 Hz,

1H), 4.02 (t, J = 9.3 Hz, 1H), 3.70 (t, J = 9.5 Hz, 1H), 3.60–3.58 (m,

1H), 3.44 (s, 3H).13C NMR (125 MHz, CDCl3) δ 173.9, 138.3, 137.7,

136.6, 131.4, 129.5, 128.5, 128.4, 128.2, 128.1, 127.9, 127.8, 121.7,

98.6, 81.3, 79.2, 79.1, 75.9, 74.3, 73.6, 69.6, 55.8. HRMS: Calc. for

C28H29BrO7 [M+H]+: 556.1097 , Obser. 556.1094

(2S,3S,4S,5R,6R)-4,5-bis(benzyloxy)-6-methoxy-3-(naphthalen-2-ylmethoxy)tetrahydro-2H-

pyran-2-carboxylic acid (2n)

Colorless viscous liquid (115 mg, 87%); Rfvalue = 0.20 in 50%

EtOAc/PE; IR:νmax (neat) 3215, 1712, 1120 cm-1. [α]D

25= -6.2 [c 0.1,

CHCl3];1H NMR (500 MHz, CDCl3) δ 7.79–7.74 (m, 3H), 7.66 (s,

1H), 7.47–7.44 (m, 2H), 7.39–7.32 (m, 11H), 4.99 (dd, J = 26.3, 10.9

Hz, 2H), 4.86–4.78 (m, 3H), 4.67 (t, J = 7.9 Hz, 2H), 4.29 (d, J = 10.1

Hz, 1H), 4.07 (t, J = 9.3 Hz, 1H), 3.78 (t, J = 9.5 Hz, 1H), 3.62 (dd, J

= 9.6, 3.4 Hz, 1H), 3.44 (s, 3H).13C NMR (125 MHz, CDCl3) δ 173.3,

138.4, 137.8, 134.9, 133.2, 133.0, 128.5, 128.4, 128.2, 128.1, 128.1,

127.9, 127.9, 127.7, 127.6, 126.8, 126.0, 125.9, 125.8, 98.6, 81.4,

79.2, 79.2, 75.9, 75.3, 73.6, 69.6, 55.8. HRMS: Calc. for C32H32O7

[M+H]+: 528.2148, Obser. 528.2150

β-D-Glucopyranosiduronic acid, phenyl-2, 3-di-O-(benzyl)-1-thio-4-O-[2, 3, 4-tri-O-(benzyl)-β-

D-glucopyranosiduronic acid] (2o)

Colorless viscous liquid (207 mg, 91%); Rf value = 0.40 in 60%

EtOAc/PE; IR:νmax (neat) 3540, 3325, 1722, 1710, 1130 cm-1.

[α]D24= +21.0 [c 0.1, CHCl3];

1H NMR (500 MHz, CDCl3) δ

7.38–7.26 (m, 31H), 5.88 (s, 1H), 4.97–4.72 (m, 8H), 4.64–4.57

(m, 4H), 4.49 (t, J = 11.6 Hz, 2H), 4.06 (t, J = 9.3 Hz, 1H), 3.90

(d, J = 16.9 Hz, 2H), 3.80 (t, J = 9.5 Hz, 1H), 3.62 (dd, J = 10.0,

3.8 Hz, 2H). 13C NMR (125 MHz, CDCl3) δ 172.8, 169.6,

18

6. Procedure for synthesis of D-Glucopyranuronic acid, 2,3,4-tris-O-(phenylmethyl)-,2-

nitrophenylmethyl ester, 1-(2,2,2-trichloroethanimidate) (1aa):

To a stirred solution of thioglycosides,1h (4g, 5.78 mmol) in 40 ml acetone-water (9:1; v/v)

was added N-bromosuccinamide (3.09 g, 17.35 mmol) and stirred for 1hour at room

temperature. After thatthe reaction was quenched with NaHCO3 and evaporated to dryness.

The residue was dissolved in ethyl acetate (150mL) and successively washed with

sat.aq.NaHCO3, water and brine. Organic layer was separated, dried using anhydrous sodium

sulphate, evaporated in vacuo. The resulting residue was purified using silica gel column

chromatography (2:1 hexane/ EtOAc) to give the corresponding hemiacetal2.43 g (70%) as

viscous oil. The hemiacetalwas dissolved in dry CH2Cl2 (20mL) and cooled to 0oC under

argon atmosphere. DBU (0.2 ml,1.33mmol) andtrichloroacetonitrile (3.34 ml, 33.35

mmol)were added slowly and allowed to stir for 2h. After complete consumption of starting

material, the reaction mixture was concentrated in vacuo and purified by silica gel column

chromatography (30% EtOAc/ Hexane) with 1% added Et3N to afford 2.23g (90%) as

colourless foam; α:β isomer (15.31:1); Rf value =0.6 in 20% EtOAc/ Hexane. 1H NMR (500

MHz, CDCl3) δ 8.74 (s, 1H), 8.13 (dd, J = 7.7, 1.7 Hz, 1H), 7.54-7.46 (m, 3H), 7.37–7.33 (m,

10H), 7.30-7.28 (m, 3H), 7.23 (dd, J = 6.6, 3.0 Hz, 2H), 6.61 (d, J = 3.5 Hz, 1H), 5.56 (q, J =

15.3 Hz, 2H), 5.03 (d, J = 10.9 Hz, 1H), 4.91 (t, J = 11.2 Hz, 2H), 4.78 (dd, J = 25.2, 11.7

Hz, 2H), 4.61 (dd, J = 29.5, 10.5 Hz, 2H), 4.16 (t, J = 9.3 Hz, 1H), 3.97–3.87 (m, 2H). 13C

NMR (125 MHz, CDCl3) δ 168.1, 161.0, 147.1, 138.2, 137.6, 137.6, 133.9, 131.4, 128.7,

128.5, 128.5, 128.4, 128.4, 128.1, 128.0, 127.9, 127.9, 127.8, 127.8, 127.7, 125.0, 94.0, 91.0,

80.8, 78.8, 78.5, 75.8, 75.3, 73.1, 72.7, 63.8.

138.4, 137.9, 137.6, 137.0, 136.9, 128.6, 128.6, 128.4, 128.4,

128.2, 128.1, 128.1, 128.0, 127.9, 127.9, 127.7, 127.7, 102.3,

98.4, 81.0, 79.1, 79.0, 77.3, 75.7, 75.2, 75.0, 73.8, 73.4, 72.7,

72.7, 72.2, 72.0, 70.5. HRMS: Calc. for C53H53O12S [M+H]+:

913.3258, Obser. 913.3262

19

7. General procedure for Glycosylation:

7.a. Glycosylation through Glycosyl Imidate donor: Donor 1aa(0.5 mmol, 1equiv.) and

acceptor (non- sugar 3 equiv. and sugar 1.2equiv.) were dissolved in freshly dried CH2Cl2

(8ml)and added to a flame dried round bottomed flask containing activated 4Å molecular

sieves (300mg) under argon atmosphere. The reaction mixture was then cooled to 0oC to

which the activator B(C6F5)3 (10mol%) was added. The reaction was stirred further for 1.5 h

allowing temperature to reach room temperature slowly.Quenching was done by the addition

of Et3N and filtered through Celite. The mixture was concentrated in vacuo and the resulting

residue was purified by silica gel column chromatography to afford the desired glycosylated

product (78-89%).

7.b.Glycosylation through thioglycoside donor: Typical NIS/TfOH-promoted

glycosylation procedure: A mixture of glycosyl donor (1h)(0.5 mmol, 1equiv.), glycosyl

acceptor (3 equiv.), and freshly activated molecular sieves (4℃, 300 mg) in CH2Cl2(8.0 mL)

was stirred under argon for 1 h. The solution was cooled to – 78 °C and NIS (1.1equiv.) and

TfOH (10mol %) were added. The reaction was slowly allowed to reach 0 °C. Upon

completion, the reaction was quenched by adding Et3N. The solid was filtered off and the

filtrate was washed with 1 M HCl, sat. NaHCO3 solution, 10% Na2S2O3and brine. The

organic layer was separated, dried with anhydrous Na2SO4, and concentrated in vacuo. The

residue was purified by flash column chromatography on silica gel to afford the

corresponding glycoside with 52% yield.

8. Analytical data for various deprotected uronic acids:

n-Hexyl-2, 3, 4-tri-O-benzyl-D-glucopyranosiduronic acid (5a)

White foam (123 mg, 90%);Rfvalue =0.5 in 50% EtOAc/

Hexane. IR:νmax (neat) 3105, 1716, 1132 cm-1; β:α isomer

(>20:1);[α]D24= -6.4 [c 0.1, CHCl3];

1H NMR (500 MHz, CDCl3)

δ 7.38–7.25 (m, 16H), 4.94 (dd, J = 17.6, 11.0 Hz, 2H), 4.81 (d,

J = 10.2 Hz, 2H), 4.75 (d, J = 11.0 Hz, 1H), 4.67 (d, J = 10.7

Hz, 1H), 4.54 (d, J = 7.6 Hz, 1H), 4.01–3.96 (m, 2H), 3.85 (t, J

= 9.1 Hz, 1H), 3.72 (t, J = 8.8 Hz, 1H), 3.59–3.52 (m, 2H),

1.70–1.64(m, 2H), 1.43–1.30 (m, 8H), 0.92–0.89 (m, 3H).13C

NMR (125 MHz, CDCl3) δ 172.9, 138.2, 138.1, 137.4, 128.4,

128.4, 128.1, 128.1, 127.9, 127.8, 127.7, 127.7, 103.7, 83.5,

20

81.5, 78.8, 75.6, 75.0, 74.7, 74.0, 70.5, 31.6, 29.6, 25.7, 22.5,

14.0.HRMS: Calc. for C33H41O7[M+H]+:549.2852, Obser.

549.2849

(Phenylmethyl)-2,3,4-tri-O-benzyl-D-glucopyranosiduronic acid (5b)

Viscous liquid. (130 mg, 94%); Rf value =0.6 in 50% EtOAc/ Hexane.

IR:νmax (neat) 3215, 1705, 1145 cm-1. β:α isomer (>20:1);[α]D

24= -19.6 [c

0.1, CHCl3];1H NMR (500 MHz, CDCl3) δ 7.37-7.24 (m, 21H), 4.98 (d, J

= 12.1 Hz, 1H), 4.90 (dd, J = 15.9, 10.9 Hz, 2H), 4.79 (t, J = 10.4 Hz,

2H), 4.68 (ddd, J = 18.2, 16.6, 9.2 Hz, 4H), 4.00 (d, J = 9.3 Hz, 1H),

3.88–3.84 (m, 1H), 3.70 (t, J = 8.7 Hz, 1H), 3.59 (t, J = 7.7 Hz, 1H). 13C

NMR (125 MHz, CDCl3) δ 172.7, 138.2, 138.0, 137.4, 136.9, 128.5,

128.4, 128.4, 128.3, 128.1, 128.0, 128.0, 127.9, 127.8, 127.7, 127.7,

102.5, 83.5, 81.6, 78.7, 75.6, 75.0, 74.8, 74.0, 71.5. HRMS: Calc. for

C34H35O7[M+H]+:555.2383, Obser. 555.2387

(2S,4S,5S,6R)-3,4,5-tris(benzyloxy)-6-(((2R,4S,5S,6S)-3,4,5-tris(benzyloxy)-6-methoxytetra-

hydro-2H-pyran-2-yl)methoxy)tetrahydro-2H-pyran-2-carboxylic acid (5c)

White solid (198 mg, 87%); M.P: 93-95 oC; Rfvalue =0.5 in 60%

EtOAc/ Hexane. IR:νmax (neat) 3345, 1701, 1065 cm-1. β:α isomer

(3:2); [α]D24= +34.5 [c 0.1, CHCl3];

1H NMR (500 MHz, CDCl3) δ

7.38–7.19 (m, 31H), 5.01–4.50 (m, 14H), 4.10–3.44 (m, 10H),

3.36 (d, J = 20.3 Hz, 3H).13C NMR (125 MHz, CDCl3) δ172.0,

170.4, 138.8, 138.7, 138.3, 138.2, 138.2, 138.1, 138.1, 138.0,

138.0, 137.5, 137.5, 128.4, 128.4, 128.3, 128.3, 128.3, 128.1,

128.1, 128.0, 128.0, 127.9, 127.9, 127.8, 127.8, 127.8, 127.7,

127.7, 127.6, 127.5, 103.5, 98.1, 98.0, 97.5, 96.1, 83.1, 82.0, 81.9,

81.2, 80.9, 80.1, 79.9, 79.3, 79.0, 78.7, 77.8, 77.7, 75.7, 75.7,

75.6, 75.3, 75.1, 75.0, 74.9, 74.8, 74.6, 73.9, 73.3, 72.6, 70.3,

69.9, 69.4, 69.0, 66.7, 55.3, 55.2.HRMS: Calc. for

C55H59O12[M+H]+:911.4007, Obser. 911.4012

21

References:

1. D. J. Chambers, G. R. Evans and A. J. Fairbanks, Tetrahedron 2005, 61, 7184–7192.

(Phenylmethyl)-2, 3, 4-tri-O-benzyl-D-glucopyranosiduronic acid (5d)

Viscous liquid. (116 mg, 84%); Rf value = 0.6 in 50% EtOAc/ Hexane.

IR:νmax (neat) 3217, 1708, 1085 cm-1.β:α isomer (~3:1);[α]D

24= +8.8 [c

0.1, CHCl3];1H NMR (500 MHz, CDCl3) δ 7.43–7.26 (m, 20H), 5.00 (dd,

J = 17.1, 11.4 Hz, 1H), 4.93–4.85 (m, 2H), 4.83–4.66 (m, 5H), 4.03 (d, J

= 9.1 Hz, 1H), 3.87 (t, J = 8.9 Hz, 1H), 3.71 (t, J = 8.6 Hz, 1H), 3.61–

3.58 (m, 1H).13C NMR (125 MHz, CDCl3) δ 174.0, 173.0, 138.5, 138.2,

138.0, 137.8, 137.5, 136.96, 136.5, 128.5, 128.5, 128.5, 128.4, 128.4,

128.4, 128.2, 128.1, 128.1, 128.0, 128.0, 128.0, 127.9, 127.9, 127.8,

127.7, 127.7, 102.6, 95.9, 83.6, 81.6, 81.4, 79.3, 79.1, 78.7, 75.9, 75.6,

75.3, 75.0, 74.8, 74.0, 73.2, 71.5, 69.9, 69.7. HRMS: Calc. for C34H35O7

[M+H]+:555.2383, Obser. 555.2381

22

1H-NMR (500 MHz, CDCl3) spectrum of compound AB

13

C-NMR (125 MHz, CDCl3) spectrum of compound AB

1.1

7

3.0

8

2.0

7

2.0

6

1.0

2

1.0

1

2.0

4

1.0

3

3.0

8

1.0

0

2.0

4

10.0

0

2.0

1

1.9

53

3.3

51

3.4

74

3.4

81

3.4

93

3.5

00

3.5

06

3.5

25

3.6

59

3.6

83

3.6

91

3.7

48

3.7

53

3.9

61

3.9

80

4.5

60

4.5

68

4.5

75

4.5

83

4.6

57

4.7

55

4.7

58

4.7

77

4.7

80

4.9

66

4.9

88

7.0

99

7.1

16

7.2

22

7.2

59

7.2

62

7.2

66

7.2

73

7.2

83

7.2

86

7.2

90

7.2

97

7.3

03

7.3

11

7.3

20

7.3

25

7.3

28

7.3

41

7.3

55

7.3

58

7.3

93

7.3

97

7.4

11

7.4

14

55.3

51

61.8

48

70.7

99

73.4

85

74.2

48

75.8

03

77.0

06

77.2

60

77.5

15

77.6

61

81.9

36

98.2

68

121.7

31

127.7

63

127.9

81

128.0

89

128.2

19

128.5

34

128.6

09

129.5

57

131.6

22

137.3

89

138.1

93

138.8

16

23

1H-NMR (500 MHz, CDCl3) spectrum of compound AC

13

C-NMR (125 MHz, CDCl3) spectrum of compound AC

1.1

2

3.0

4

1.0

6

1.0

5

2.0

3

1.0

1

1.0

0

1.0

2

1.0

4

2.0

3

1.0

3

2.0

2

10.0

8

1.0

6

2.0

6

1.0

0

3.0

3

1.8

91

3.3

49

3.4

98

3.5

05

3.5

17

3.5

24

3.5

78

3.5

97

3.6

73

3.6

78

3.6

96

3.7

18

3.7

26

3.7

69

3.7

74

3.7

92

4.0

21

4.0

39

4.0

58

4.5

69

4.5

76

4.6

40

4.6

64

4.7

68

4.7

83

4.7

93

4.8

06

4.8

41

4.8

63

4.9

93

5.0

06

5.0

15

5.0

29

7.1

92

7.2

63

7.2

70

7.2

77

7.2

81

7.2

86

7.2

96

7.3

01

7.3

07

7.3

10

7.3

18

7.3

24

7.3

27

7.3

45

7.3

57

7.3

61

7.3

76

7.3

79

7.3

93

7.3

96

7.4

23

7.4

25

7.4

34

7.4

41

7.4

44

7.6

93

7.7

49

7.7

63

7.7

74

7.7

80

7.7

92

55.3

40

61.9

99

70.9

06

73.5

38

75.8

76

77.0

05

77.2

60

77.5

14

77.6

83

80.1

86

82.1

02

98.3

24

126.0

31

126.0

85

126.2

59

126.8

21

127.7

57

127.8

36

128.0

95

128.2

52

128.3

64

128.5

53

128.6

22

133.1

35

133.4

14

135.7

85

138.2

81

138.9

30

24

1H-NMR (500 MHz, CDCl3) spectrum of compound 1a

13C-NMR (125 MHz, CDCl3) spectrum of compound 1a

3.0

0

1.0

4

1.0

2

1.0

0

1.0

0

1.0

6

2.0

8

3.0

3

1.0

2

1.9

1

1.9

4

2.1

4

11.0

2

2.0

8

1.0

7

1.0

4

3.4

73

3.6

32

3.6

39

3.6

51

3.6

58

3.8

18

3.8

37

3.8

56

4.0

56

4.0

75

4.0

93

4.3

27

4.3

47

4.5

87

4.6

09

4.6

81

4.6

87

4.7

12

4.8

41

4.8

54

4.8

65

4.8

77

4.8

99

5.0

07

5.0

28

5.5

25

5.5

55

5.5

70

5.6

00

7.1

95

7.2

03

7.2

10

7.2

62

7.2

67

7.2

73

7.2

75

7.2

83

7.3

22

7.3

29

7.3

35

7.3

38

7.3

44

7.3

49

7.3

53

7.3

59

7.3

72

7.3

86

7.3

88

7.3

94

7.4

09

7.4

30

7.4

38

7.4

45

7.4

50

7.4

57

7.4

65

7.5

17

7.5

24

7.5

29

7.5

36

8.1

10

8.1

17

8.1

22

8.1

29

55.7

64

63.7

25

70.3

23

73.6

73

75.0

64

75.9

53

76.8

76

77.1

31

77.3

85

79.3

11

79.4

15

81.5

02

98.8

47

125.0

72

127.7

45

127.7

71

128.0

30

128.1

16

128.2

13

128.3

67

128.4

76

128.5

82

128.6

21

128.7

28

131.5

90

133.9

05

137.9

25

138.4

65

147.1

91

169.1

09

OBnOBnO

BnOOCH3

O

O

NO2

1a

OBnOBnO

BnOOCH3

O

O

NO2

1a

25

1H-NMR (500 MHz, CDCl3) spectrum of compound 1b

13C-NMR (125 MHz, CDCl3) spectrum of compound 1b

26

1H-NMR (500 MHz, CDCl3) spectrum of compound 1c

13C-NMR (125 MHz, CDCl3) spectrum of compound 1c

3.0

2

3.0

0

3.0

1

1.0

1

1.0

0

2.0

1

1.0

0

1.0

1

3.0

0

1.7

0

4.4

4

3.0

3

0.9

7

1.9

88

2.0

96

3.4

80

3.9

45

3.9

64

3.9

84

4.3

91

4.4

10

4.5

91

4.9

11

4.9

97

5.0

05

5.5

65

5.5

80

5.5

96

5.6

23

5.6

53

7.1

85

7.1

96

7.2

00

7.2

72

7.2

76

7.2

84

7.2

90

7.5

00

7.5

16

7.5

18

7.5

47

8.1

35

8.1

38

8.1

53

27

1H-NMR (500 MHz, CDCl3) spectrum of compound 1d

13C-NMR (125 MHz, CDCl3) spectrum of compound 1d

3.0

0

1.0

2

1.0

0

2.0

3

2.0

2

2.0

2

1.0

0

5.0

0

4.0

4

5.0

1

4.0

1

1.0

0

3.5

07

4.1

98

4.2

17

4.2

36

4.5

39

4.5

59

4.6

07

4.6

10

5.2

14

5.2

22

5.2

35

5.2

42

5.2

58

5.2

65

5.5

98

5.6

29

5.6

62

5.6

93

6.0

88

6.1

07

6.1

27

7.0

84

7.0

92

7.0

99

7.1

03

7.1

46

7.1

50

7.1

56

7.1

60

7.2

81

7.2

81

7.3

77

7.3

88

7.3

93

7.4

03

7.4

04

7.4

08

7.4

18

7.4

95

7.5

11

7.5

14

7.5

16

7.5

19

7.5

29

7.5

31

7.5

33

7.5

39

7.5

41

7.5

48

7.5

88

7.6

03

7.9

84

7.9

86

7.9

91

7.9

94

7.9

98

8.0

01

8.0

02

8.0

08

8.0

10

8.1

52

8.1

54

8.1

68

8.1

70

55.8

38

63.8

77

70.0

89

71.7

03

71.8

63

74.7

13

77.4

46

97.5

05

125.0

77

127.8

27

127.9

52

128.2

28

128.3

87

128.4

23

128.7

51

128.8

72

129.6

44

129.8

89

131.4

60

133.2

24

133.3

65

133.9

73

136.9

98

147.0

93

165.4

71

165.8

92

168.4

68

28

1H-NMR (500 MHz, CDCl3) spectrum of compound 1e

13C-NMR (125 MHz, CDCl3) spectrum of compound 1e

55.6

64

63.5

31

72.0

23

72.3

96

72.9

55

74.3

02

74.5

39

75.6

63

78.7

18

99.7

51

125.0

20

127.6

84

127.6

99

127.7

23

127.8

46

128.3

51

128.3

98

128.5

51

128.5

85

131.9

22

133.8

82

138.0

42

138.0

73

138.2

67

147.1

37

168.8

97

29

1H-NMR (500 MHz, CDCl3) spectrum of compound 1f

13C-NMR (125 MHz, CDCl3) spectrum of compound 1f

3.0

0

1.0

0

0.9

8

0.9

9

1.0

0

0.9

8

0.9

8

0.9

6

2.4

1

7.0

3

1.0

3

2.0

6

1.9

5

1.9

2

3.9

3

3.5

75

4.4

67

4.5

21

4.5

30

4.5

45

4.5

54

4.7

33

4.7

37

4.7

57

4.7

62

5.0

39

5.7

33

5.7

36

5.7

39

5.7

43

5.9

55

5.9

62

6.1

28

6.1

48

7.2

82

7.2

83

7.2

87

7.3

03

7.3

86

7.4

01

7.4

25

7.4

40

7.4

47

7.4

55

7.6

01

7.8

63

7.8

79

7.9

79

7.9

94

7.9

95

8.0

83

8.1

00

8.1

25

8.1

39

8.1

41

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

55.6

03

62.9

49

66.9

74

68.7

81

70.0

69

70.4

46

98.7

22

128.3

06

128.4

68

128.6

05

129.0

18

129.1

22

129.3

58

129.7

50

129.7

57

129.8

19

129.8

69

129.8

94

133.0

85

133.1

78

133.4

51

133.4

83

165.4

46

165.5

02

166.2

04

OBzOBzO

OBz

OCH3

O

O

NO2

1f

30

1H-NMR (500 MHz, CDCl3) spectrum of compound 1g

13C-NMR (125 MHz, CDCl3) spectrum of compound 1g

OBzOBzO

OBz

O

ONO2

SPh

1g

OBzOBzO

OBz

O

ONO2

SPh

1g

1H-NMR (500 MHz, CDCl

13C-NMR (125 MHz, CDCl

500 MHz, CDCl3) spectrum of compound 1h

125 MHz, CDCl3) spectrum of compound 1h

31

32

1H-NMR (500 MHz, CDCl3) spectrum of compound 1i

13C-NMR (125 MHz, CDCl3) spectrum of compound 1i

33

1H-NMR (500 MHz, CDCl3) spectrum of compound 1j

13C-NMR (125 MHz, CDCl3) spectrum of compound 1j

34

1H-NMR (500 MHz, CDCl3) spectrum of compound 1k

13C-NMR (125 MHz, CDCl3) spectrum of compound 1k

OHOBzO

BzOOCH3

O

ONO2

1k

OHOBzO

BzOOCH3

O

ONO2

1k

35

1H-NMR (500 MHz, CDCl3) spectrum of compound 1l

13C-NMR (125 MHz, CDCl3) spectrum of compound 1l

36

1H-NMR (500 MHz, CDCl3) spectrum of compound 1m

13C-NMR (125 MHz, CDCl3) spectrum of compound 1m

3.0

0

1.0

0

1.0

0

1.0

0

1.0

0

1.0

0

2.0

1

3.0

0

1.0

0

2.0

1

2.0

0

12.0

3

3.0

4

1.0

0

3.4

56

3.5

97

3.6

04

3.6

16

3.6

23

3.7

54

3.7

74

3.7

92

4.0

04

4.0

23

4.0

41

4.2

78

4.2

98

4.4

92

4.5

14

4.6

58

4.6

64

4.6

86

4.7

64

4.7

72

4.7

87

4.7

94

4.8

12

4.8

37

4.9

84

5.0

06

5.5

36

5.5

66

5.5

82

5.6

12

7.0

12

7.0

28

7.2

81

7.3

26

7.3

35

7.3

38

7.3

44

7.3

60

7.3

72

7.4

70

7.4

80

7.4

84

8.1

07

8.1

18

8.1

25

55.7

66

63.7

84

70.1

89

73.6

23

74.1

54

75.8

67

79.3

31

79.4

45

81.3

39

98.8

05

125.1

22

127.7

60

127.8

98

128.1

07

128.1

74

128.4

54

128.5

63

128.7

49

128.8

84

129.2

19

131.3

36

131.3

80

133.7

70

136.9

73

137.8

56

138.4

07

147.3

20

169.0

59

OOBnO

BnOOCH3

O

O

NO2

1m

Br

OOBnO

BnOOCH3

O

O

NO2

1m

Br

37

1H-NMR (500 MHz, CDCl3) spectrum of compound 1n

13C-NMR (125 MHz, CDCl3) spectrum of compound 1n

3.0

0

1.0

1

1.0

1

1.0

0

1.0

1

3.0

1

2.0

2

2.0

0

2.0

2

17.3

9

1.0

1

2.0

0

1.0

2

0.9

5

3.4

72

3.6

44

3.6

51

3.6

64

3.6

70

3.8

59

3.8

78

3.8

97

4.0

80

4.0

99

4.1

17

4.3

45

4.3

65

4.6

90

4.7

15

4.8

42

5.0

23

5.4

40

5.4

70

5.5

31

5.5

61

7.2

69

7.2

82

7.2

95

7.3

08

7.3

25

7.3

35

7.3

41

7.3

47

7.3

56

7.3

70

7.3

84

7.3

86

7.3

94

7.4

06

7.4

20

7.4

46

7.4

53

7.4

61

7.6

14

7.6

86

7.7

04

7.7

14

7.7

31

7.7

80

8.0

22

8.0

37

55.7

71

63.7

39

70.3

77

73.6

66

75.1

23

75.9

38

79.3

91

79.4

65

81.5

14

98.8

60

124.9

59

125.7

22

125.9

09

126.0

69

126.4

59

127.6

29

127.7

47

127.8

33

128.0

11

128.0

58

128.0

99

128.1

94

128.4

62

128.5

68

133.7

19

147.0

27

169.0

92

38

1H-NMR (500 MHz, CDCl3) spectrum of compound 1o

13C-NMR (125 MHz, CDCl3) spectrum of compound 1o

OO

O

O

BnOBnO

BnO

O

BnOBnO

SPh

NO2O

O

NO2

1o

OO

O

O

BnOBnO

BnO

O

BnOBnO

SPh

NO2O

O

NO2

1o

39

1H-NMR (500 MHz, CDCl3) spectrum of compound 4a

13C-NMR (125 MHz, CDCl3) spectrum of compound 4a

3.0

1

7.0

6

2.9

7

2.0

0

1.0

1

1.0

0

2.0

3

0.9

9

1.0

0

0.9

8

2.0

7

2.0

8

1.0

2

1.0

1

2.0

2

2.9

5

10.1

5

2.0

5

1.0

2

1.0

0

0.8

99

0.9

13

0.9

23

0.9

27

1.3

20

1.3

27

1.3

35

1.3

42

1.6

87

1.6

99

3.5

52

3.5

54

3.5

70

3.7

16

3.7

34

3.9

20

3.9

38

4.0

27

4.0

46

4.5

20

4.5

35

4.6

04

4.6

26

4.7

51

4.7

73

4.8

19

4.8

41

4.8

53

4.8

75

4.9

54

4.9

73

4.9

75

4.9

94

5.5

14

5.5

44

5.6

19

5.6

49

7.1

85

7.1

89

7.1

97

7.2

04

7.2

66

7.2

70

7.2

77

7.2

82

7.3

16

7.3

20

7.3

27

7.3

29

7.3

33

7.3

37

7.3

43

7.3

49

7.3

52

7.3

65

7.3

70

7.3

74

7.4

62

7.4

64

7.4

70

7.4

78

7.4

83

8.1

32

8.1

51

14.0

52

22.5

97

25.8

26

29.6

97

31.6

24

63.6

06

70.5

30

74.5

97

74.8

90

74.9

65

75.7

73

78.9

78

81.7

86

83.9

64

104.0

49

125.0

59

127.7

23

127.7

79

127.8

02

127.8

59

127.9

07

128.1

56

128.3

59

128.4

11

128.5

43

128.6

61

131.7

58

133.8

54

138.3

20

147.1

60

167.9

92

40



1.0

2

1.0

1

1.0

2

1.0

0

2.1

4

2.1

5

2.2

1

3.1

2

2.1

8

2.0

9

19.3

5

2.2

3

1.0

0

1.0

4

3.6

28

3.6

43

3.7

20

3.7

38

3.9

51

3.9

69

4.0

44

4.0

64

4.6

13

4.6

35

4.6

43

4.6

58

4.6

97

4.7

21

4.7

43

4.7

64

4.8

11

4.8

32

4.8

54

4.8

76

4.9

38

4.9

58

4.9

79

4.9

97

5.0

21

5.5

27

5.5

58

5.6

27

7.1

87

7.1

92

7.2

00

7.2

07

7.2

68

7.2

72

7.2

78

7.2

82

7.3

04

7.3

10

7.3

12

7.3

19

7.3

22

7.3

28

7.3

31

7.3

37

7.3

39

7.3

48

7.3

52

7.3

56

7.3

60

7.3

68

7.3

71

7.3

84

7.3

99

7.4

01

7.4

03

7.4

14

7.4

61

7.4

66

7.4

69

7.4

72

7.4

75

7.4

80

8.1

35

8.1

54

63.7

07

71.4

50

74.6

26

74.9

53

75.7

72

78.9

36

81.8

13

83.9

44

102.8

45

127.7

52

127.7

91

127.8

19

127.8

52

127.9

13

127.9

87

128.0

35

128.1

92

128.3

73

128.4

05

128.4

30

128.5

11

128.7

45

133.8

81

147.2

32

167.9

93

41



O

O

O

O

O

BnOBnO

BnO BnO

BnOBnO

O

NO2

4c

O

O

O

O

O

BnOBnO

BnO BnO

BnOBnO

O

NO2

4c

42


13

C-NMR (125 MHz, CDCl3) spectrum of compound 4d

1.0

0

0.7

6

0.7

8

0.7

5

2.0

9

4.0

1

2.9

5

2.0

0

24.0

2

0.9

4

3.6

25

3.6

43

3.6

58

3.7

34

3.7

52

3.7

70

3.9

48

3.9

67

3.9

85

4.0

59

4.0

79

4.6

51

4.6

57

4.7

11

4.7

34

4.9

72

5.5

38

5.5

69

5.5

85

5.6

38

5.6

69

7.2

15

7.2

82

7.2

90

7.3

33

7.3

60

7.3

63

7.3

68

7.3

83

7.4

13

7.4

68

7.4

77

8.1

41

8.1

46

8.1

49

8.1

55

8.1

59

63.7

17

69.6

33

71.4

57

74.6

45

74.9

63

75.7

81

75.8

99

78.9

53

79.4

01

81.8

30

83.9

62

96.1

13

102.8

60

127.7

64

127.8

00

127.8

28

127.8

62

127.9

25

127.9

97

128.0

48

128.2

02

128.3

86

128.4

17

128.4

43

128.5

25

128.7

58

133.8

87

147.2

47

168.0

02

169.1

15

43

1H-NMR (500 MHz, CDCl3) spectrum of compound 1aa

13C-NMR (125 MHz, CDCl3) spectrum of compound 1aa

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.0

2

1.0

0

2.0

0

2.0

1

2.0

6

1.0

0

2.0

5

1.0

0

2.0

6

3.0

2

10.0

7

3.0

7

1.0

0

0.9

3

3.8

72

3.8

79

3.8

91

3.8

98

3.9

35

3.9

53

3.9

73

4.1

46

4.1

64

4.1

83

4.5

72

4.5

93

4.6

31

4.6

52

4.7

48

4.7

71

4.7

98

4.8

22

4.8

89

4.9

11

4.9

34

5.0

14

5.0

36

5.5

17

5.5

47

5.5

76

5.6

07

6.6

08

6.6

15

7.2

21

7.2

26

7.2

33

7.2

40

7.2

82

7.2

90

7.2

95

7.2

99

7.3

03

7.3

33

7.3

36

7.3

45

7.3

51

7.3

53

7.3

60

7.3

61

7.3

68

7.3

70

7.3

75

7.4

61

7.4

65

7.4

76

7.4

80

7.4

91

7.4

94

7.5

05

7.5

29

7.5

31

7.5

43

7.5

47

8.1

24

8.1

28

8.1

40

8.1

43

8.7

49

0102030405060708090100110120130140150160170180f1 (ppm)

44

1H-NMR (500 MHz, DMSO-d6) spectrum of compound 2a

13C-NMR (125 MHz, DMSO-d6) spectrum of compound 2a

3.0

0

1.0

0

1.0

0

1.0

0

1.0

0

1.0

0

4.0

0

0.8

9

0.9

5

16.0

0

2.4

97

2.5

00

2.5

04

2.5

08

2.5

11

3.3

02

3.3

45

3.5

70

3.6

43

3.7

94

3.9

24

3.9

44

4.5

89

4.6

69

4.6

75

4.7

17

4.7

37

4.7

40

4.8

33

4.8

56

4.9

11

4.9

18

7.2

29

7.2

42

7.2

45

7.2

58

7.2

65

7.2

72

7.2

77

7.2

81

7.2

83

7.2

86

7.2

89

7.2

97

7.3

01

7.3

04

7.3

06

7.3

12

7.3

16

7.3

22

7.3

24

7.3

29

7.3

33

7.3

41

7.3

45

7.3

58

7.3

69

7.3

74

7.3

77

7.4

00

55.3

72

70.4

92

72.0

63

74.5

30

75.0

01

79.6

50

80.8

51

98.0

20

127.8

69

127.8

93

127.9

45

127.9

70

128.0

14

128.1

17

128.1

45

128.6

20

128.6

30

128.7

06

138.6

07

138.8

32

139.0

71

170.9

59

45



3.0

0

1.0

0

1.0

0

1.0

0

1.0

0

1.0

0

2.0

0

4.0

0

1.0

1

2.0

0

6.0

0

3.5

43

4.6

52

4.6

73

5.3

25

5.3

45

5.3

70

5.3

77

5.7

55

5.7

74

6.1

81

6.2

01

6.2

21

7.3

23

7.3

79

7.3

95

7.4

02

7.4

17

7.5

24

7.5

39

7.8

95

7.8

97

7.9

12

7.9

13

7.9

47

7.9

50

7.9

64

7.9

65

7.9

87

7.9

89

8.0

04

8.0

05

56.3

43

68.0

80

69.8

17

71.4

79

77.2

34

97.4

32

128.3

45

128.4

06

128.4

66

128.8

73

129.0

32

129.7

42

129.9

05

129.9

64

133.2

47

133.4

01

133.4

90

165.4

10

165.6

85

165.7

63

171.1

12

OBzOBzO

BzOOCH3

OH

O

2b

OBzOBzO

BzOOCH3

OH

O

2b

46



3.0

0

3.0

3

3.0

3

1.0

8

1.0

6

3.0

2

1.0

9

1.0

3

1.0

6

2.0

5

3.4

2

1.9

71

2.0

85

3.4

61

3.8

74

3.8

94

3.9

13

4.3

25

4.3

45

4.6

02

4.6

89

4.7

12

4.9

89

4.9

96

5.5

55

5.5

74

5.5

94

7.2

51

7.2

64

7.2

67

7.2

82

7.2

94

7.2

97

7.3

00

7.3

12

7.3

23

7.3

26

7.3

40

7.3

43

7.3

46

20.7

14

20.7

81

55.8

10

69.4

39

70.8

58

71.3

00

74.7

57

77.5

39

97.3

06

128.0

10

128.0

46

128.4

80

137.2

15

169.7

64

170.3

85

172.2

30

47


13C-NMR (125 MHz, CDCl3) spectrum of compound 2d

3.0

0

1.0

1

1.0

0

2.0

0

2.0

1

1.0

0

5.1

5

4.0

2

2.0

1

4.0

3

3.5

83

4.2

80

4.2

99

4.6

04

4.6

23

4.7

18

4.7

40

4.7

94

4.8

16

5.3

29

5.3

36

5.3

56

5.3

67

5.3

75

6.1

87

6.2

06

6.2

26

7.2

60

7.4

61

7.4

76

7.4

93

7.4

96

7.5

12

7.6

09

7.6

25

8.0

86

8.0

88

8.0

91

8.0

94

8.1

03

8.1

05

8.1

08

55.9

82

69.8

00

71.7

77

71.9

35

74.8

30

76.9

01

77.1

55

77.3

58

77.4

09

97.5

08

128.0

37

128.2

38

128.3

73

128.4

99

128.8

99

129.4

24

129.7

64

129.9

97

133.3

61

133.5

23

136.9

02

165.6

54

166.0

85

173.6

84

48

1H-NMR (500 MHz, CDCl3) spectrum of compound 2e

13C-NMR (125 MHz, CDCl3) spectrum of compound 2e

3.0

0

1.0

0

1.0

0

2.0

0

2.0

0

4.0

2

1.0

0

15.1

1

3.4

62

3.4

64

3.7

95

3.7

97

3.8

01

4.2

33

4.3

06

4.6

32

4.6

39

4.7

02

4.7

25

4.7

51

4.7

77

4.8

02

4.8

24

4.9

65

7.2

81

7.3

02

7.3

16

7.3

27

7.3

43

7.3

48

7.3

50

7.3

64

7.3

67

7.3

81

7.3

84

7.3

91

55.7

67

71.3

70

72.4

30

72.9

91

74.5

23

75.6

56

78.5

35

99.6

26

127.6

92

127.7

09

127.7

42

127.8

72

127.9

21

128.1

09

128.4

23

137.7

63

138.0

76

138.1

93

174.1

30

49

1H-NMR (500 MHz, CDCl3) spectrum of compound 2f

13C-NMR (125 MHz, CDCl3) spectrum of compound 2f

3.0

0

1.0

0

1.0

1

1.0

1

1.0

3

1.0

8

2.0

7

2.0

1

4.0

3

1.0

4

2.0

0

2.0

1

2.0

1

3.5

95

4.6

83

4.7

02

5.1

54

5.1

58

5.6

85

5.6

90

5.6

91

5.6

96

5.9

27

5.9

34

6.0

28

6.0

47

7.2

82

7.2

93

7.3

08

7.3

24

7.3

86

7.4

02

7.4

67

7.4

78

7.4

93

7.5

09

7.8

60

7.8

62

7.8

77

7.8

79

7.9

70

7.9

72

7.9

86

8.0

93

8.0

95

8.1

10

8.1

12

56.2

43

67.4

42

69.3

59

69.4

16

69.8

91

98.8

93

128.3

64

128.4

21

128.6

24

128.9

41

129.0

17

129.1

10

129.7

85

129.8

56

129.9

82

133.3

12

133.4

07

133.6

14

165.3

03

165.4

99

165.5

42

171.4

62

50

1H-NMR (500 MHz, CDCl3) spectrum of compound 2g

13

C-NMR (125 MHz, CDCl3) spectrum of compound 2g

1.0

0

1.0

0

1.0

2

1.0

1

1.0

2

14.1

2

2.0

0

2.0

1

2.0

0

4.3

85

4.4

04

5.0

96

5.1

15

5.5

20

5.5

39

5.5

59

5.7

15

5.7

34

5.7

53

5.8

99

5.9

17

7.2

82

7.2

98

7.3

14

7.3

23

7.3

27

7.3

34

7.3

37

7.3

51

7.4

10

7.5

43

7.5

50

7.5

58

7.8

32

7.8

34

7.8

49

7.9

12

7.9

15

7.9

29

7.9

76

7.9

78

7.9

92

66.2

31

69.9

94

70.3

35

73.8

46

86.5

66

128.2

93

128.3

50

128.4

14

128.4

97

128.8

08

129.0

62

129.0

83

129.2

02

129.8

26

129.8

77

129.8

98

131.7

37

133.2

47

133.3

12

133.3

38

164.9

87

165.1

17

165.6

74

170.4

20

51

1H-NMR (500 MHz, CDCl3) spectrum of compound 2h

13C-NMR (125 MHz, CDCl3) spectrum of compound 2h

1.0

0

1.0

2

1.0

1

1.0

0

1.0

0

3.0

4

2.0

7

1.0

0

19.4

4

2.0

5

3.5

61

3.5

78

3.5

81

3.5

97

3.7

54

3.7

71

3.7

88

3.8

56

3.8

74

3.8

92

4.0

05

4.0

23

4.7

09

4.7

59

4.7

74

4.7

80

4.7

94

4.8

13

4.8

66

4.8

76

4.9

21

4.9

42

7.2

74

7.2

80

7.2

82

7.2

86

7.2

96

7.3

12

7.3

14

7.3

17

7.3

28

7.3

35

7.3

42

7.3

45

7.3

46

7.3

50

7.3

54

7.3

58

7.3

61

7.3

73

7.3

77

7.4

08

7.4

10

7.5

85

7.5

88

7.6

00

7.6

04

75.0

64

75.4

45

75.7

56

77.5

21

78.7

49

80.2

89

85.3

70

88.1

33

127.8

56

127.9

99

128.0

52

128.1

78

128.2

42

128.4

62

128.4

84

128.5

14

129.1

36

132.3

66

133.0

68

137.3

77

137.7

95

138.0

28

172.3

92

OBnOBnO

OBn

OH

O

SPh

2h

OBnOBnO

OBn

OH

O

SPh

2h

52

1H-NMR (500 MHz, DMSO-d6) spectrum of compound 2i

13C-NMR (125 MHz, DMSO-d6) spectrum of compound 2i

6.0

1

3.0

0

3.0

0

1.0

1

1.0

1

1.0

3

1.0

4

1.0

0

1.2

74

1.2

81

1.3

20

1.4

31

2.4

93

2.4

96

2.5

00

2.5

04

3.3

66

4.1

79

4.1

84

4.3

91

4.3

96

4.4

01

4.4

06

4.4

96

4.5

12

4.5

16

4.6

37

4.6

42

5.5

27

5.5

37

24.8

73

25.1

19

26.1

34

26.2

80

67.7

03

69.9

93

70.5

16

71.9

25

96.2

30

108.5

41

109.1

76

169.3

44

53

1H-NMR (500 MHz, CDCl3) spectrum of compound 2j

13C-NMR (125 MHz, CDCl3) spectrum of compound 2j

54

1H-NMR (500 MHz, Methanol-d4) spectrum of compound 2k

13C-NMR (125 MHz, Methanol-d4) spectrum of compound 2k

3.0

0

1.0

3

1.0

0

2.0

0

1.0

0

4.0

0

2.0

1

2.0

2

2.0

0

3.4

97

4.0

73

4.0

93

4.1

12

4.2

67

4.2

87

5.1

83

5.1

91

5.2

03

5.2

06

5.7

88

5.7

92

5.8

07

5.8

11

5.8

14

5.8

30

7.3

87

7.3

90

7.4

03

7.4

06

7.4

22

7.5

37

7.9

03

7.9

07

7.9

10

7.9

24

7.9

83

7.9

86

8.0

00

54.7

78

69.8

65

71.1

76

71.7

25

72.5

28

97.5

54

128.1

06

128.1

46

128.9

33

129.2

29

129.3

03

129.6

16

132.9

68

133.2

26

165.6

75

166.1

72

170.9

20

55

1H-NMR (500 MHz, CDCl3) spectrum of compound 2l

13C-NMR (125 MHz, CDCl3) spectrum of compound 2l

2.0

2

0.9

6

1.0

1

2.0

5

1.0

0

1.0

0

1.0

0

3.1

7

8.0

4

4.0

46

4.0

57

4.0

69

4.0

99

4.1

70

4.1

77

4.3

18

4.3

43

4.3

79

4.4

03

4.6

34

4.6

64

4.7

38

6.1

38

6.1

48

7.1

59

7.1

74

7.1

89

7.2

79

7.2

93

7.3

07

7.3

27

7.3

63

7.3

72

47.5

15

64.2

07

72.6

59

76.9

28

77.1

82

77.4

37

79.5

35

101.2

51

127.8

63

128.2

67

128.3

54

128.6

40

128.6

66

129.2

18

134.7

26

136.3

23

156.8

54

169.3

48

56

1H-NMR (500 MHz, CDCl3) spectrum of compound 2m

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building blocks: Applications in carbohydrate synthesis with the … · 2019. 10. 14. · building blocks: Applications in carbohydrate synthesis with the assistance of continuous