IBr-catalyzed O-glycosylation of D-glucals: Facile synthesis of 2,3-unsaturated-o-glycosides

Article abstract of DOI:10.3987/COM-15-13174

Iodine monobromide (IBr) is explored as an alternative catalyst for the selective synthesis of 2,3-unsaturated glycosides from tri-O-acetyl-D-glucal 1 with several alcohols through Ferrier rearrangement. This reaction was shown to be a simple, efficient and cost-effective method, affords twenty examples of corresponding glycoside products in high yields with good α-selectivity.

Full text of DOI:10.3987/COM-15-13174

HETEROCYCLES, Vol. 91, No. 4, 2015
849
HETEROCYCLES, Vol. 91, No. 4, 2015, pp. 849 - 861. © 2015 The Japan Institute of Heterocyclic Chemistry
Received, 18th January, 2015, Accepted, 20th February, 2015, Published online, 4th March, 2015
DOI: 10.3987/COM-15-13174
IBr-CATALYZED O-GLYCOSYLATION OF D-GLUCALS: FACILE
SYNTHESIS OF 2,3-UNSATURATED-O-GLYCOSIDES
Rungnapha Saeeng, Onanong Siripru, and Uthaiwan Sirion*
Department of Chemistry and Center for Innovation in Chemistry, Faculty of
Science, Burapha University, Sangsook, Chonburi 20131, Thailand; E-mail:
uthaiwan@buu.ac.th
Abstract – Iodine monobromide (IBr) is explored as an alternative catalyst for the
selective synthesis of 2,3-unsaturated glycosides from tri-O-acetyl-D-glucal 1 with
several alcohols through Ferrier rearrangement. This reaction was shown to be a
simple, efficient and cost-effective method, affords twenty examples of
corresponding glycoside products in high yields with good D-selectivity.
2,3-Unsaturated-O-glycosides are useful chiral intermediates for the synthesis of building block of
bioactive molecules. They could use to link with interesting scaffold for enhancing the pharmacological
potential.1,2 2,3-Unsaturated-O-glycosides can be easily synthesized from Ferrier’s rearrangement of
with various nucleophiles in the presence of a Lewis acid catalyst. Originally, BF3∙Et2O was used.3 In
past ten years, a large number of effective reagents to promote the Ferrier glycosylation reaction have
developed, including InCl3,4 Sc(OTf)3,5 Montmorillionite K-10,6 NbCl5,7 Bi(OTf)3,8 Er(OTf)3,9
Yb(OTf)3,10 ZnCl2-Al2O3,11 NaHSO4-SiO2,12 TMSOTf,13 Pd(OAc)2,14 FeCl3,15 CeCl3∙7H2O,16 Fe2(SO4)3,
17
Fe(OTf)3,18 TiCl3(OTf),19 and CF3SO3H-SiO2.20 In addition, oxidants also have been employed such as
DDQ,21 I2,22 and CAN.23 Although these methods are available, new facile methods are still highly
desirable due to the important of this transformation in glycoside synthesis.ꢀIodine monobromide (IBr) is
a highly polar interhalogen compound and can be used as a source of iodonium ion (Iꢀ). IBr was early
used as a catalyst for the electrophilic cyclization of homoallylic carbonates.24 Recently, IBr was used to
promote the iodocyclization for synthesis of 3-bromo-4-iodo-substituted furans, pyrroles and thiophenes in
good to high yields.25 In the field of glycoside chemistry, IBr can promote glycosylation of sugar alcohols
by disarmed glycosyl bromide and thioglycosides.26 Combination of IBr with AgClO4∙H2O or AgOTf were
used effectively as promoter in glycosylation of sialic acid27 and Kdo-thioglycoside28 respectively to obtain
glycoside products in high yield.ꢀWe have previously reported that iodine can be efficiently promoted the
O-glycosylation of D-glucal.29 In continuation of our efforts to develop new glycosylation methods, we

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HETEROCYCLES, Vol. 91, No. 4, 2015
report herein the synthesis of 2,3-unsaturated-O-glycosides from D-glucal via Ferrier reaction by using
IBr as a new catalyst for this reaction (Scheme 1).
AcO
AcO
AcO
O
O
ROH
AcO
AcO
OR
IBr
0-20 oC
2
1
Scheme 1
We optimized the reaction conditions for preparing 2,3-unsaturated glycosides from tri-O-acetyl-D-glucal
1 by using benzyl alcohol as nucleophile for the model reaction. First, the glycosylation was optimized
using IBr 50 mol% as the I+ source in various solvent (Table 1, entries 1-5). Employing MeCN or Et2O as
solvent, glycoside 2a was obtained as a major product in fair yields (entries 1 and 4). Using THF as
solvent resulted in low yield of product (entry 2). In the presence of CH2Cl2, the reaction turned out to be
a complex mixture. Interestingly, when the non-polar solvent as toluene was used, glycoside 2a was
obtained as a major product in good yield, however the reaction was completed as long as 24 h (entry 5).
Further evaluation of the IBr loading revealed that performing the reaction using IBr 20 mol%, the yield
of product was improved and completed in short reaction time (entry 6). This result indicated that the use
of 50 mol% IBr (entry 5) may lead to the formation of glycosyl-bromide which can be coupling with
alcohol nucleophile at anomeric position to produce the desired product in longer reaction time than the
direct glycosylation.26 When the molecular sieve was used as desiccant, complex mixture was obtained
without desired product (entry 7). Further experimental using a mixture of toluene and CH2Cl2 1:1 as
solvents, the reaction proceeded smoothly and gave 2a in 89% yield (entry 8). CH2Cl2 was used as
co-solvent for enhancing the solubility of IBr in the reaction mixture.
Table 1. Optimization for the synthesis of 2,3-unsaturated glycosides
AcO
AcO
AcO
AcO
O
O
BnOH
OBn
x mol% IBr
solvent, 0-20 oC
AcO
2a
1
Entrya
Solvent
IBr (mol%)
Time (h)
Yield (%)b
47
1
2
3
4
5
MeCN
THF
50
50
50
50
50
1.0
4.0
20
_c
CH2Cl2
Et2O
1.0
4.0
49
72
toluene
24.0
6
7
8
toluene
20
20
1.0
24.0
1.0
83
_d
toluene/add 4 ÅMS
toluene+CH2Cl2 (1:1)
20
89
a 0.184 mmol of tri-O-acetyl-D-glucal (1); bIsolated yields; cComplex mixtures
dThe use of 4 AoMS resulted complex mixture and no desired product was obtained

HETEROCYCLES, Vol. 91, No. 4, 2015
851
To explore the efficacy of IBr catalyzed Ferrier reaction of glycal, we have studied the reactions of
different alcohols with glycal. Under optimized condition in Table 1, entry 8, a series of glycosylation of
tri-O-acetyl-D-glucal 1 with various alcohol nucleophiles were carried out using 20 mol% IBr in the
o
mixture of toluene and CH2Cl2 (1:1) at 0-20 C. As shown in Table 2, the versatile of IBr promoted
glycosylation of tri-O-acetyl-D-glucal 1 via Ferrier reaction proved to be suitable for several types of
alcohol nucleophiles leading to the corresponding glycosides 2b-2t in good to excellent yields with
D-anomeric selectivity.
The glycosylation reactions of tri-O-acetyl-D-glucal 1 were carried out with substituted benzyl alcohols to
afford the desired 2,3-unsaturated-O-glycoside products 2a-2f (Table 2, entries 1-6). Reaction of
electron-rich 2-methoxybenzyl alcohol led to glycoside 2b in high yield in 1 h (entry 2). Di- and
trimethoxy benzyl alcohols are found to undergo glycosylation smoothly with glucal 1 using IBr (entries
5-6).
Reactions of phenyl-, di-phenyl ethanol and 1-phenyl-1-propanol resulted in the formation of the
glycosides 2g-2i in excellent yields (entries 7-9). Reaction of hindered diphenylmethanol required more
time to complete the reaction to obtain glycoside 2j with high D-stereoselective (entry 10). The high
D-stereoselectivity was observed with the more hindered alcohol nucleophiles. The predominant
formation of D-anomer may arise from a thermodynamic anomeric effect.
Moreover, the IBr-catalyzed Ferrier reaction of glycal was also tested employing diverse commercial
available alcohols as octanol, 2-methyl-1-butanol, 2-propyn-1-ol, 2-bromoethanol, 2-butanol and
cyclohexanol (entries 11-16) providing the corresponding glycosides in good yields. Glycosylation with
2-bromoethanol was completed within 30 min to obtain 2n in 79% yield. Mild reaction conditions using
IBr, allow alkyne- and halide-functional groups in compounds 2j and 2n to be tolerated in this reaction.
Interestingly, D-anomers were obtained exclusively in good yields when using natural product alcohols as
(-)-menthol and fencyl alcohol (entries 17-18). Proving the generality of this methodology by addition of
tri-benzyl and tri-acetyl-D-glucopyranoside as nucleophiles, disaccharides 2s and 2t were afforded in high
yields (entries 17-18).
In summary, a new method of IBr-catalyzed O-glycosylation of D-glucal with various alcohols was
developed. IBr an inexpensive, easily handle and readily available compound is found to be an efficient
catalyst for O-glycosylation via Ferrier reaction. Using this catalyst, twenty examples of 2,3-unsaturated
glycosides can be obtained in high yields with D-anomeric selectivity.

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HETEROCYCLES, Vol. 91, No. 4, 2015
Table 2. Synthesis of 2,3-unsaturated glycoside derivatives
AcO
AcO
AcO
O
ROH
O
AcO
AcO
OR
20 mol% IBr
toluene/CH2Cl2, 0-20 oC
2a-2t
1
a
a
b
 b

)
Entry
1
Major Productc
O
Time (h)
1.0
Yield (%) (
)
Entry
Major Productc
AcO
AcO
Time (h)
1.0
Yield (%) (
AcO
AcO
O
89 (4:1)
11
91 (6:1)
82 (4:1)
83 (7:1)
O
O
6
2a
2k
AcO
AcO
AcO
AcO
O
O
1.0
12
13
2
3
1.0
1.0
90 (5:1)
71 (5:1)
O
O
OMe
2b
2l
AcO
AcO
AcO
AcO
O
O
1.0
0.5
3.0
O
O
NO2
NO2
2m
2c
AcO
AcO
AcO
AcO
O
O
14
15
4
5
1.0
1.0
79 (5:1)
72 (4:1)
83 (4:1)
86 (8:1)
O
O
Br
2n
2o
2d
AcO
AcO
OMe
AcO
AcO
O
O
O
O
2e
AcO
AcO
OMe
OMe
O
AcO
AcO
O
OMe
OMe
5.0
1.5
72 (10:1)
O
16
17
6
7
1.0
1.0
82 (6:1)
99 (4:1)
2p
2q
O
2f
AcO
AcO
O
Me Me
AcO
AcO
O

78 ( -only)
O
O
2g
AcO
AcO
Me
Me
O
AcO
AcO
O

84 ( -only)
O
1.5
1.0
18
19
8
9
1.0
1.0
95 (7:1)
94 (4:1)
2r
O
2h
Me
O
Me
AcO
AcO
AcO
AcO
O
80 (4:1)
86 (5:1)
O
O
BnO
BnO
2s
2i
O
AcO
AcO
O
AcO
BnO
AcO
O
OMe
AcO
O
83 (15:1)
1.0
9.0
20
10
O
AcO
AcO
2j
2t
O
OMe
a Isolated yields were calculated from diastereomeric mixtures.
b The ratio of - and -isomers of 2 was determined by 1H NMR spectroscopy of the crude products.


c Major product can be separated by simple column chromatography.
EXPERIMENTAL
Proton NMR spectra were recorded on a BRUKER AVANC (400 MHz). All spectra were measured in
CDCl3 solvent and chemical shifts are reported as  values in parts per million (ppm) relative to CDCl3 (

HETEROCYCLES, Vol. 91, No. 4, 2015
853
7.26) as internal standard. Carbon NMR spectra were recorded on a BRUKER AVANC (100 MHz). All
spectra were measured in CDCl3 solvent and chemical shifts are reported as  values in parts per million
(ppm) relative to CDCl3 ( 77.0) as internal standard. High-resolution mass spectra (HRMS) were
obtained with a Finnigan MAT 95. Infrared spectra were determined on a PERKIN ELMER FT/IR-2000S
spectrophotometer and are reported in wave number (cm-1). Optical rotation was determined with a
JASCO P-1020 digital polarimeter. Analytical thin-layer chromatography (tlc) was conducted on
precoated tlc plates; silica gel 60F-254 [E. Merck, Darmstadt, Germany]. Silica gel columns for
open-column chromatography utilized silica gel 60 (0.040-0.063 mm) [E. Merck, Darmstadt, Germany].
Melting points were measured using a Melting point apparatus (Griffin) and are uncorrected.
General procedure for the synthesis of 2,3-unsaturated-O-glycosides.
A
mixture of
3,4,6-tri-O-acetyl-D-glucal 1 (50.0 mg, 0.184 mmol) and alcohol (0.193 mmol) was dissolved in
dry-CH2Cl2 : dry-toluene (125 : 200 L) under gas-nitrogen. The solution was cooled to 0 oC, then 0.5 M
o
IBr in CH2Cl2 (20 mol%, 75 L) was added slowly. The stirring was continued at 0-20 C for 1-10 h.
After TLC showed the completed conversion, the reaction mixture was quenched carefully with cooled aq.
Na2S2O3 (20 mL) and washed with satd aq. NaHCO3 (20 mL), and extracted with EtOAc (3×20 mL). The
combined organic layer was washed with brine (20 mL), dried over anhydrous Na2SO4, and then
concentrated under reduced pressure. The residues were purified by silica gel column chromatography
(EtOAc/n-hexane) to give the 2,3-unsaturated-O-glycoside products 2a-2t in good to high yields
(71-99%). In most cases, a mixture of  and -anomers of glycoside 2 was obtained. The ratio of the
1
isomers was determined by comparison of the integration values of the peaks in H NMR analysis. The
-configuration was characterized from the position of anomeric proton which appears in an up field
position compared to -anomer in most cases. The -isomers was not separated but characterized
compared with the literature data of the mixture.30 Spectral data of pure -isomers are as followed.
Benzyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2a): a white solid; -anomer Rf
o
= 0.61 (30% EtOAc/n-hexane); mp 38-40 C; []D26 +82.22 (c 0.50, CHCl3); IR (CHCl3) 3025, 2929,
1745, 1497, 1455, 1370, 1231, 1039, 750, 699 cm-1; 1H NMR (400 MHz, CDCl3)  7.40-7.30 (m, 5H, Ph),
5.92 (brd, 1H, J = 10.0 Hz, H-3), 5.87 (ddd, 1H, J = 10.0, 2.5, 1.5 Hz, H-2), 5.36 (dm, 1H, J = 9.5 Hz,
H-4), 5.16 (brs, 1H, H-1), 4.83 (d, 1H, J = 11.5 Hz, H-1'a), 4.62 (d, 1H, J = 11.5 Hz, H-1'b), 4.27 (dd, 1H,
J = 11.5, 5.0 Hz, H-6a), 4.18 (ddd, 1H, J = 9.5, 5.0, 2.0 Hz, H-5), 4.14 (dd, 1H, J = 11.5, 2.0 Hz, H-6b),
2.13 (s, 3H, Ac), 2.10 (s, 3H, Ac); 13C NMR (100 MHz, CDCl3)  170.81, 170.30, 137.61, 129.32, 128.49
(2×C), 128.05 (2×C), 127.90, 127.77, 93.67, 70.32, 67.11, 65.34, 62.96, 20.97, 20.81; HRMS (ESI)
C17H20O6 (M++Na), Calcd 343.1158, Found 343.1192.
3-Methoxybenzyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2b): a colorless oil;

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HETEROCYCLES, Vol. 91, No. 4, 2015
-anomer Rf = 0.45 (30% EtOAc/n-hexane), []D24 +67.13 (c 1.00, CHCl3); IR (CHCl3) 2927, 1741, 1597,
1583, 1488, 1454, 1434, 1368, 1221, 1034, 750 cm-1; 1H NMR (400 MHz, CDCl3)  7.29 (t, 1H, J = 8.0
Hz, Ph), 6.96 (d, 1H, J = 8.0 Hz, Ph), 6.93 (d, 1H, J = 2.0 Hz, Ph), 6.86 (dd, 1H, J = 8.0, 2.0 Hz, Ph), 5.92
(brd, 1H, J = 10.0 Hz, H-3), 5.88 (ddd, 1H, J = 10.0, 2.5, 1.5 Hz, H-2), 5.36 (dm, 1H, J = 9.5 Hz, H-4),
5.15 (brs, 1H, H-1), 4.80 (d, 1H, J = 11.5 Hz, H-1'a), 4.60 (d, 1H, J = 11.5 Hz, H-1'b), 4.27 (dd, 1H, J =
11.5, 5.0 Hz, H-6a), 4.18 (ddd, 1H, J = 9.5, 5.0, 2.0 Hz, H-5), 4.16 (dd, 1H, J = 11.5, 2.0 Hz, H-6b), 3.84
(s, 3H, OCH3), 2.13 (s, 3H, Ac), 2.11 (s, 3H, Ac); 13C NMR (100 MHz, CDCl3)  170.84, 170.33, 159.76,
139.16, 129.55, 129.35, 127.74, 120.27, 113.60, 113.26, 93.62, 70.13, 67.11, 65.32, 62.95, 55.25, 21.00,
20.83; HRMS (ESI) C18H22O7 (M++Na) Calcd 373.1263, Found 373.1295.
3-Nitrobenzyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2c): a colorless oil;
-anomer Rf = 0.36 (30% EtOAc/n-hexane); []D24 +52.78 (c 0.50, CHCl3), IR (CHCl3) 2922, 2852, 1741,
1
1530, 1456, 1367, 1350, 1256, 1226, 1036, 750 cm-1; H NMR (400 MHz, CDCl3)  8.26 (brs, 1H, Ph),
8.19 (d, 1H, J = 8.0 Hz, Ph), 7.71 (d, 1H, J = 8.0 Hz, Ph), 7.56 (t, 1H, J = 8.0 Hz, Ph), 5.97 (brd, 1H, J =
10.0 Hz, H-3), 5.91 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.37 (dm, 1H, J = 9.5 Hz, H-4), 5.18 (brs, 1H,
H-1), 4.93 (d, 1H, J = 12.5 Hz, H-1'a), 4.71 (d, 1H, J = 12.5 Hz, H-1'b), 4.27 (dd, 1H, J = 12.0, 5.0 Hz,
H-6a), 4.18 (dd, 1H, J = 12.0, 2.0 Hz, H-6b), 4.16 (ddd, 1H, J = 9.5, 5.0, 2.0 Hz, H-5), 2.12 (s, 3H, Ac),
2.11 (s, 3H, Ac); 13C NMR (100 MHz, CDCl3)  170.73, 170.26, 148.42, 139.87, 133.61, 129.85, 129.46,
127.16, 122.82, 122.57, 94.10, 69.01, 67.33, 65.19, 62.87, 20.97, 20.78; HRMS (ESI) C17H19NO8
(M++Na) Calcd 388.1008, Found 388.1037.
4-Nitrobenzyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2d): a white solid;
-anomer Rf = 0.39 (30% EtOAc/n-hexane)mp 80-82 oC; []D24 +44.38 (c 0.50, CHCl3); IR (CHCl3)
1
2924, 2852, 1740, 1606, 1520, 1365, 1346, 1260, 1220, 1034, 750 cm-1; H NMR (400 MHz, CDCl3) 
8.24 (d, 2H, J = 8.5 Hz, Ph), 7.55 (d, 2H, J = 8.5 Hz, Ph), 5.97 (brd, 1H, J = 10.0 Hz, H-3), 5.91 (ddd, 1H,
J = 10.0, 2.5, 2.0 Hz, H-2), 5.37 (dm, 1H, J = 9.5 Hz, H-4), 5.17 (brs, 1H, H-1), 4.93 (d, 1H, J = 13.0 Hz,
H-1'a), 4.72 (d, 1H, J = 13.0 Hz, H-1'b), 4.26 (dd, 1H, J = 12.0, 5.5 Hz, H-6a), 4.17 (dd, 1H, J = 12.0, 2.5
13
Hz, H-6b), 4.15 (ddd, 1H, J = 9.5, 5.5, 2.5 Hz, H-5), 2.12 (s, 3H, Ac), 2.10 (s, 3H, Ac); C NMR (100
MHz, CDCl3)  170.66, 170.21, 147.53, 145.17, 129.89, 128.00 (2×C), 127.12, 123.71 (2×C), 94.13,
68.95, 67.36, 65.20, 62.84, 20.94, 20.75; HRMS (ESI) C17H19NO8 (M++Na) Calcd 388.1008, Found
388.1061.
2,5-Dimethoxybenzyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2e): a white
solid; -anomer Rf = 0.48 (30% EtOAc/n-hexane); mp 50-52 oC; []D24 +58.43 (c 1.00, CHCl3); IR
(CHCl3) 2934, 2835, 1743, 1501, 1465, 1371, 1221, 1044 cm-1; 1H NMR (400 MHz, CDCl3)  6.99 (brs,
1H, Ph), 6.83-6.81 (m, 2H, Ph), 5.92-5.89 (m, 2H, H-2, H-3), 5.37 (dm, 1H, J = 9.5 Hz, H-4), 5.19 (brs,

HETEROCYCLES, Vol. 91, No. 4, 2015
855
1H, H-1), 4.85 (d, 1H, J = 12.5 Hz, H-1'a), 4.62 (d, 1H, J = 12.5 Hz, H-1'b), 4.30 (dd, 1H, J = 12.0, 5.5
Hz, H-6a), 4.21 (ddd, 1H, J = 9.5, 5.5, 2.5 Hz, H-5), 4.18 (dd, 1H, J = 12.0, 2.5 Hz, H-6b), 3.81 (s, 3H,
OCH3), 3.80 (s, 3H, OCH3), 2.12 (s, 3H, Ac), 2.10 (s, 3H, Ac); 13C NMR (100 MHz, CDCl3)  170.87,
170.33, 153.57, 151.43, 129.20, 127.93, 127.20, 115.50, 113.04, 111.38, 93.99, 67.02, 65.39, 65.27, 62.94,
55.97, 55.78, 20.99, 20.77; HRMS (ESI) C19H24O8 (M++Na) Calcd 403.1369, Found 403.1363.
3,4,5-Trimethoxybenzyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2f): colorless
oil; -anomer Rf = 0.26 (30% EtOAc/n-hexane); []D26 +62.41 (c 1.00, CHCl3); IR (CHCl3) 2941, 2835,
1743, 1592, 1507, 1460, 1371, 1235, 1128, 1033, 750 cm-1; 1H NMR (400 MHz, CDCl3)  6.60 (s, 2H,
Ph), 5.93 (brd, 1H, J = 10.0 Hz, H-3), 5.88 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.37 (dm, 1H, J = 9.5 Hz,
H-4), 5.15 (brs, 1H, H-1), 4.75 (d, 1H, J = 11.5 Hz, H-1'a), 4.54 (d, 1H, J = 11.5 Hz, H-1'b), 4.30 (dd, 1H,
J = 12.0, 5.0 Hz, H-6a), 4.20 (dd, 1H, J = 12.0, 2.5 Hz, H-6b), 4.19 (ddd, 1H, J = 9.5, 5.0, 2.5 Hz, H-5),
3.89 (s, 6H, 2×OCH3), 3.85 (s, 3H, OCH3), 2.13 (s, 3H, Ac), 2.11 (s, 3H, Ac); 13C NMR (100 MHz,
CDCl3)  170.80, 170.32, 153.33, 137.67, 133.11 (2×C), 129.46, 127.67, 105.11 (2×C), 93.45, 70.41,
67.12, 65.31, 62.93, 60.86, 56.14 (2×C), 21.00, 20.85; HRMS (ESI) C20H26O9 (M++Na) Calcd 433.1475,
Found 433.1469.
2-Phenylethyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2g): a colorless oil;
-anomer Rf = 0.36 (20% EtOAc/n-hexane); []D24 +107.78 (c 1.00, CHCl3); IR (CHCl3) 3028, 2927,
1
1744, 1604, 1497, 1454, 1370, 1237, 1040, 751, 701 cm-1; H NMR (400 MHz, CDCl3)  7.35-7.21 (m,
5H, Ph), 5.89 (brd, 1H, J = 10.0 Hz, H-3), 5.83 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.31 (dm, 1H, J =
9.5 Hz, H-4), 5.04 (brs, 1H, H-1), 4.20 (dd, 1H, J = 12.0, 5.0 Hz, H-6a), 4.06 (dd, 1H, J = 12.0, 2.5 Hz,
H-6b), 4.00 (dt, 1H, J = 10.0, 7.0 Hz, H-1’a), 3.98 (ddd, 1H, J = 9.5, 5.0, 2.5 Hz, H-5), 3.78 (dt, 1H, J =
10.0, 7.0 Hz, H-1’b), 2.95 (t, 2H, J = 7.0 Hz, H-2’), 2.10 (s, 3H, Ac), 2.09 (s, 3H, Ac); 13C NMR (100
MHz, CDCl3)  170.84, 170.34, 138.78, 129.13, 128.90 (2×C), 128.39 (2×C), 127.75, 126.33, 94.45,
69.55, 66.90, 65.20, 62.89, 36.35, 21.01, 20.81; HRMS (ESI) C18H22O6 (M+ +Na) Calcd 357.1314, Found
357.1330.
2,2-Diphenylethyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2h): a colorless oil;
-anomer Rf = 0.33 (20% EtOAc/n-hexane); []D24 +64.62 (c 0.50, CHCl3), IR (CHCl3) 3028, 2925, 1744,
1
1495, 1451, 1370, 1231, 1040, 744, 701 cm-1; H NMR (400 MHz, CDCl3)  7.36-7.20 (m, 10H, Ph),
5.84 (brd, 1H, J = 10.0 Hz, H-3), 5.75 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.30 (dm, 1H, J = 9.5 Hz,
H-4), 5.05 (brs, 1H, H-1), 4.39 (dd, 1H, J = 9.0, 8.0 Hz, H-1’a), 4.35 (dd, 1H, J = 8.0, 6.0 Hz, H-2’), 4.19
(dd, 1H, J = 12.5, 5.0 Hz, H-6a), 4.07 (dd, 1H, J = 9.0, 6.0 Hz, H-1’b), 4.05 (dd, 1H, J = 12.5, 2.5 Hz,
H-6b), 3.83 (ddd, 1H, J = 9.5, 5.0, 2.5 Hz, H-5), 2.10 (s, 3H, Ac), 2.08 (s, 3H, Ac); 13C NMR (100 MHz,
CDCl3)  170.77, 170.23, 142.07, 141.99, 129.13, 128.47 (2×C), 128.42 (2×C), 128.30 (2×C), 128.24

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(2×C), 127.59, 126.58, 126.56, 94.63, 71.83, 67.07, 65.14, 62.84, 50.98, 20.94, 20.78; HRMS (ESI)
C24H26O6 (M+ + Na) Calcd 433.1627, Found 433.1657.
1-Phenylpropyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2i): a colorless oil;
-anomer Rf = 0.77 (30% EtOAc/n-hexane); []D24 +201.20 (c 1.00, CHCl3); IR (CHCl3) 3030, 2964,
2934, 1745, 1454, 1370, 1237, 1032, 757, 702 cm-1; 1H NMR (400 MHz, CDCl3)  7.39-7.29 (m, 5H, Ph),
5.90 (brd, 1H, J = 10.0 Hz, H-3), 5.77 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.31 (dm, 1H, J = 8.0 Hz,
H-4), 4.88 (brs, 1H, H-1), 4.64 (dd, 1H, J = 8.0, 5.0 Hz, H-1’), 4.30-4.23 (m, 3H, H-5, H-6), 2.15 (s, 3H,
Ac), 2.12 (s, 3H, Ac), 1.93-1.81 (m, 1H, H-2’a), 1.77-1.67 (m, 1H, H-2’b), 1.00 (t, 3H, J = 7.0 Hz, H-3’);
13C NMR (100 MHz, CDCl3)  170.84, 170.32, 141.87, 128.96, 128.46 (2×C), 128.21, 127.75, 126.86
(2×C), 91.59, 80.74, 67.35, 65.42, 63.23, 31.18, 20.99, 20.93, 10.84; HRMS (ESI) C19H24O6 (M++Na)
Calcd 371.1471, Found 371.1469.
Benzhydryl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2j): a colorless oil;
-anomer Rf = 0.30 (20% EtOAc/n-hexane); []D26 +97.82 (c 1.00, CHCl3); IR (CHCl3) 3025, 2924, 2854,
1742, 1494, 1454, 1367, 1222, 1013, 744, 700 cm-1; 1H NMR (400 MHz, CDCl3)  7.42-7.24 (m, 10H,
Ph), 5.93 (brd, 1H, J = 10.0 Hz, H-3), 5.89 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.88 (s, 1H, H-1’), 5.35
(dm, 1H, J = 9.5 Hz, H-4), 5.16 (brs, 1H, H-1), 4.21 (dd, 1H, J = 11.5, 5.0 Hz, H-6a), 4.18 (ddd, 1H, J =
9.5, 5.0, 2.0 Hz, H-5), 4.03 (dd, 1H, J = 11.5, 2.0 Hz, H-6b), 2.10 (s, 3H, Ac), 2.09 (s, 3H, Ac); 13C NMR
(100 MHz, CDCl3)  170.77, 170.28, 142.29, 140.87, 129.34, 128.60 (2×C), 128.31 (2×C), 127.88 (2×C),
127.87, 127.45 (2×C), 127.08 (2×C), 92.59, 80.59, 67.37, 65.36, 62.86, 20.96, 20.76; HRMS (ESI)
C23H24O6 (M++Na) Calcd 419.1471, Found 419.1465.
2-Octyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2k): a colorless oil; -anomer
Rf = 0.58 (20% EtOAc/n-hexane); []D25 +77.70 (c 0.50, CHCl3); IR (CHCl3) 2927, 2856, 1748, 1457,
1
1370, 1234, 1042, 736, 604 cm-1; H NMR (400 MHz, CDCl3)  5.90 (brd, 1H, J = 10.0 Hz, H-3), 5.86
(ddd, 1H, J = 10.0, 2.0, 1.0 Hz, H-2), 5.33 (dm, 1H, J = 9.5 Hz, H-4), 5.04 (brs, 1H, H-1), 4.27 (dd, 1H, J
= 12.0, 5.5 Hz, H-6a), 4.19 (dd, 1H, J = 12.0, 2.5 Hz, H-6b), 4.13 (ddd, 1H, J = 9.5, 5.5, 2.5 Hz, H-5),
3.79 (dt, 1H, J = 9.5, 7.0 Hz, H-1’a), 3.52 (dt, 1H, J = 9.5, 7.0 Hz, H-1’b), 2.12 (s, 3H, Ac), 2.10 (s, 3H,
13
Ac), 1.67-1.58 (m, 4H, 2×CH2), 1.40-1.25 (m, 8H, 4×CH2), 0.90 (t, 3H, CH3); C NMR (100 MHz,
CDCl3)  170.79, 170.31, 128.87, 128.00, 94.40, 69.02, 66.90, 65.37, 63.07, 31.81, 29.73, 29.37, 29.24,
26.24, 22.63, 20.95, 20.77, 14.06; HRMS (ESI) C18H30O6 (M++Na), Calcd 365.1940, Found 365.1957.
2-Ethylbutyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2l): a colorless oil;
-anomer Rf = 0.52 (20% EtOAc/n-hexane); []D26 +95.30 (c 0.50, CHCl3); IR (CHCl3) 2962, 2932, 2877,
1747, 1462, 1370, 1236, 1042, 742 cm-1; 1H NMR (400 MHz, CDCl3)  5.89 (brd, 1H, J = 10.5 Hz, H-3),
5.85 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.32 (dm, 1H, J = 9.5 Hz, H-4), 5.02 (brs, 1H, H-1), 4.25 (dd,

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1H, J = 12.0, 5.5 Hz, H-6a), 4.20 (dd, 1H, J = 12.0, 2.5 Hz, H-6b), 4.11 (ddd, 1H, J = 9.5, 5.5, 2.5 Hz,
H-5), 3.73 (dd, 1H, J = 9.5, 6.0 Hz, H-1’a), 3.40 (dd, 1H, J = 9.5, 5.5 Hz, H-1’b), 2.12 (s, 3H, Ac), 2.11 (s,
3H, Ac), 1.53-1.44 (m, 1H, H-2’), 1.44-1.32 (m, 4H, H-3’, H-4’), 0.98 (t, 3H, J = 7.0 Hz, H-5’), 0.96 (t,
13
3H, J = 7.0 Hz, H- 6’); C NMR (100 MHz, CDCl3)  170.82, 170.30, 128.83, 128.05, 94.59, 71.16,
66.97, 65.39, 63.15, 41.11, 23.36, 23.30, 20.97, 20.78, 11.05, 10.94; HRMS (ESI) C16H26O6 (M++Na)
Calcd 337.1627, Found 337.1629.
1-Propynyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2m): a white solid;
o
25
-anomer Rf = 0.27 (20% EtOAc/n-hexane); mp 64-66 C; []D +164.07 (c 1.00, CHCl3); IR (CHCl3)
1
3272, 2923, 2853, 2118, 1740, 1440, 1369, 1226, 1037, 749 cm-1; H NMR (400 MHz, CDCl3)  5.95
(brd, 1H, J = 10.0 Hz, H-3), 5.86 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.36 (dm, 1H, J = 9.5 Hz, H-4),
5.26 (brs, 1H, H-1), 4.33 (d, 2H, J = 2.5 Hz, H-1’), 4.28 (dd, 1H, J = 12.0, 5.0 Hz, H-6a), 4.20 (dd, 1H, J
= 12.0, 2.5 Hz, H-6b), 4.11 (ddd, 1H, J = 9.5, 5.0, 2.5 Hz, H-5), 2.48 (t, 1H, J = 2.5 Hz, H-3’), 2.13 (s, 3H,
Ac), 2.11 (s, 3H, Ac); 13C NMR (100 MHz, CDCl3)  170.76, 170.24, 129.78, 127.24, 92.79, 79.09, 74.79,
67.22, 65.18, 62.80, 55.07, 20.93, 20.77; HRMS (ESI) C13H16O6 (M+ + Na) Calcd 291.0845, Found
291.0850.
2-Bromoethyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2n): a yellow oil;
26
-anomer Rf = 0.33 (20% EtOAc/n-hexane); []D +83.93 (c 1.00, CHCl3); IR (CHCl3) 2924, 2852,
1742, 1446, 1370, 1227, 1033, 750 cm-1; 1H NMR (400 MHz, CDCl3)  5.94 (brd, 1H, J = 10.0 Hz, H-3),
5.87 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.33 (dm, 1H, J = 9.5 Hz, H-4), 5.11 (brs, 1H, H-1), 4.26-4.16
(m, 3H, H-5, H-6), 4.07 (dt, 1H, J = 11.5, 6.0 Hz, H-1’a), 3.93 (dt, 1H, J = 11.5, 6.0 Hz, H-1’b), 3.56 (t,
2H, J = 6.0 Hz, H-2’), 2.13 (s, 3H, Ac), 2.11 (s, 3H, Ac); 13C NMR (100 MHz, CDCl3)  170.76, 170.28,
129.62, 127.21, 94.78, 69.66, 67.24, 65.16, 62.95, 30.59, 20.96, 20.81; HRMS (ESI) C12H17BrO6
(M++Na) Calcd 359.0107, Found 359.0105.
1-Methylpropyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2o): a mixture of
isomers, colorless oil Rf = 0.42 (20% EtOAc/n-hexane); []D26 +95.90 (c 1.00, CHCl3); IR (CHCl3) 2963,
2930, 1745, 1457, 1371, 1230, 1036, 746 cm-1; 1H NMR (400 MHz, CDCl3)  5.90 (brd, 2H, J = 10.0 Hz,
H-3 isomer A,B), 5.85 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2 isomer A), 5.82 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz,
H-2 isomer B), 5.31 (dm, 2H, J = 9.5 Hz, H-4 isomer A,B), 5.15 (brs, 1H, H-1 isomer B), 5.14 (brs, 1H,
H-1 isomer A), 4.29-4.14 (m, 6H, H-5, H-6 isomer A,B), 3.83-3.69 (m, 2H, H-1’ isomer A,B), 2.11 (s, 6H,
Ac isomer A), 2.10 (s, 3H, Ac isomer B), 2.09 (s, 3H, Ac isomer B), 1.65-1.43 (m, 4H, H-2’ isomer A,B),
1.26 (d, 3H, J = 6.0 Hz, H-4’ isomer A), 1.16 (d, 3H, J = 6.0 Hz, H-4’ isomer B), 0.97 (t, 3H, J = 7.0 Hz,
13
H-3’ isomer A), 0.92 (t, 3H, J = 7.0 Hz, H-3’ isomer B); C NMR (100 MHz, CDCl3)  170.81, 170.33,
128.83, 128.73, 128.44, 128.28, 94.33, 92.04, 77.15, 75.10, 66.97, 66.78, 65.45, 65.37, 63.19, 30.10,

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29.51, 21.16, 20.97, 20.76, 19.24, 10.31, 9.79; HRMS (ESI) C14H22O6 (M++Na) Calcd 309.1314, Found
309.1300.
Cyclohexyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2p): a colorless oil;
24
-anomer Rf = 0.74 (30% EtOAc/n-hexane); []D +111.72 (c 1.00, CHCl3); IR (CHCl3) 2933, 2857,
1745, 1450, 1370, 1229, 1035, 744 cm-1; 1H NMR (400 MHz, CDCl3)  5.89 (brd, 1H, J = 10.0 Hz, H-3),
5.83 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.31 (ddd, 1H, J = 9.5, 2.5, 1.5 Hz, H-4), 5.19 (brs, 1H, H-1),
4.25 (dd, 1H, J = 12.0, 6.0 Hz, H-6a), 4.19 (dd, 1H, J = 12.0, 2.0 Hz, H-6b), 4.21-4.15 (m, 1H, H-5),
3.70-3.62 (m, 1H, H-1’), 2.11 (s, 3H, Ac), 2.10 (s, 3H, Ac), 2.01-1.88 (m, 2H, CH2), 1.81-1.72 (m, 2H,
CH2), 1.60-1.16 (m, 6H, 3×CH2); 13C NMR (100 MHz, CDCl3)  170.77, 170.32, 128.75, 128.58, 92.81,
76.73, 66.80, 65.49, 63.20, 33.78, 32.15, 25.57, 24.39, 24.17, 20.96, 20.74; HRMS (ESI) C16H24O6
(M++Na) Calcd 335.1471, Found 335.1460.
2-Isopropyl-5-methylcyclohexyl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (2q):
26
a colorless oil; -anomer Rf = 0.58 (20% EtOAc/n-hexane); []D +52.26 (c 1.00, CHCl3); IR (CHCl3)
2956, 2925, 2871, 1747, 1456, 1370, 1236, 1037, 748 cm-1; 1H NMR (400 MHz, CDCl3)  5.90-5.87 (m,
2H, H-2, H-3), 5.30 (dm, 1H, J = 9.0 Hz, H-4), 5.12 (brs, 1H, H-1), 4.25 (dd, 1H, J = 12.0, 6.0 Hz, H-6a),
4.22-4.19 (m, 1H, H-5), 4.20 (dd, 1H, J = 12.0, 2.0 Hz, H-6b), 3.44 (td, 1H, J = 10.0, 4.0 Hz, H-1’), 2.13
(s, 3H, Ac), 2.09 (s, 3H, Ac), 2.12-2.05 (m, 1H, H-2’), 1.70-1.60 (m, 2H, H-6’), 1.51-1.39 (m, 1H, H-7’),
1.31-1.22 (m, 1H, H-5’), 1.13-0.82 (m, 4H, H-3’, H-4’), 0.93 (d, 3H, J = 6.5 Hz, H-8’), 0.92 (d, 3H, J =
13
7.0 Hz, H-9’), 0.79 (d, 3H, J = 7.0 Hz, H-10’); C NMR (100 MHz, CDCl3)  170.85, 170.34, 128.57,
128.03, 96.15, 81.07, 66.70, 65.35, 63.35, 48.85, 43.34, 34.29, 31.73, 25.63, 23.18, 22.38, 21.15, 20.97,
20.84, 16.22; HRMS (ESI) C20H32O6 (M++Na) Calcd 391.2097, Found 391.2105.
1,3,3-Trimethylbicyclo[2.2.1]heptan-2-yl-4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyrano-
26
side (2r): a white solid; -anomer Rf = 0.61 (20% EtOAc/n-hexane); []D +95.36 (c 0.50, CHCl3); mp
64-66 oC; IR (CHCl3) 2954, 2872, 1747, 1459, 1370, 1236, 1033, 745 cm-1; 1H NMR (400 MHz, CDCl3)
 5.89-5.86 (m, 2H, H-2, H-3), 5.31 (dm, 1H, J = 9.5 Hz, H-4), 5.00 (brs, 1H, H-1), 4.26 (dd, 1H, J = 12.5,
5.5 Hz, H-6a), 4.19-4.13 (m, 1H, H-5), 4.17 (dd, 1H, J = 12.5, 2.0 Hz, H-6b), 3.47 (s, 1H, H-1’), 2.11 (s,
3H, Ac), 2.10 (s, 3H, Ac), 1.79-1.63 (m, 2H, H-3’), 1.53-1.37 (m, 2H, H-4’), 1.15-0.96 (m, 3H, H-5’,
H-7’), 1.13 (s, 3H, H-8’), 1.06 (s, 3H, H-9’), 0.89 (s, 3H, H-10’); 13C NMR (100 MHz, CDCl3)  170.94,
170.32, 128.57, 127.99, 94.19, 90.18, 66.80, 65.29, 63.16, 48.86, 48.76, 41.37, 39.42, 31.85, 25.97 (2×C),
21.17, 21.03, 20.85, 19.75; HRMS (ESI) C20H30O6 (M++Na) Calcd 389.1940, Found 389.1957.
Methyl-2,3,4-tri-O-benzyl-6-O-(4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-α-D-
glucopyranoside (2s): a colorless oil; -anomer Rf = 0.45 (40% EtOAc/n-hexane); []D26 +55.36 (c 0.50,
CHCl3); IR (CHCl3) 3025, 2932, 1743, 1453, 1369, 1240, 1096, 1029, 749, 712 cm-1; 1H NMR (400 MHz,

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859
CDCl3)  7.41-7.29 (m, 15H, Ph), 5.89-5.85 (m, 2H, H-2, H-3), 5.32 (d, 1H, J = 9.5 Hz, H-4), 5.13 (brs,
1H, H-1), 5.00 (d, 1H, J = 10.5 Hz, CHHPh), 4.95 (d, 1H, J = 11.5 Hz, CHHPh), 4.82 (d, 1H, J = 10.5 Hz,
CHHPh), 4.81 (d, 1H, J = 13.0 Hz, CHHPh), 4.69 (d, 1H, J = 13.0 Hz, CHHPh), 4.66 (d, 1H, J = 11.5 Hz,
CHHPh), 4.63 (d, 1H, J = 3.5 Hz, H-6’), 4.18 (dd, 1H, J = 12.0, 5.0 Hz, H-6a), 4.07-3.99 (m, 4H, H-5,
H-6b, H-1’a, H-4’), 3.79 (ddd, 1H, J = 10.0, 4.0, 1.5 Hz, H-2’), 3.74 (dd, 1H, J = 11.5, 1.5 Hz, H-1’b),
3.60 (t, 1H, J = 9.5 Hz, H-3’), 3.54 (dd, 1H, J = 9.5, 3.5 Hz, H-5’), 3.40 (s, 3H, OCH3), 2.09 (s, 3H, Ac),
2.02 (s, 3H, Ac); 13C NMR (100 MHz, CDCl3) 170.72, 170.23, 138.73, 138.37, 138.16, 128.99, 128.47
(2×C), 128.43 (2×C), 128.39 (2×C), 128.06 (2×C), 127.96 (2×C), 127.92, 127.74, 127.72, 127.61, 127.45
(2×C), 98.07, 94.80, 82.03, 80.02, 77.84, 75.75, 74.92, 73.34, 70.01, 67.09, 66.99, 65.20, 62.75, 55.19,
20.95, 20.69; HRMS (ESI) C38H44O11 (M+ + Na) Calcd 699.2781, Found 699.2772.
Methyl-2,3,4-tri-O-acetyl-6-O-(4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-α-D-
24
glucopyranoside (2t): a colorless oil; -anomer Rf = 0.18 (40% EtOAc/n-hexane); []D +163.14 (c
0.50, CHCl3); IR (CHCl3) 3031, 2924, 2854, 1745, 1454, 1228, 1029, 746, 697 cm-1; 1H NMR (400 MHz,
CDCl3)  5.92 (brd, 1H, J = 10.0 Hz, H-3), 5.85 (ddd, 1H, J = 10.0, 2.5, 2.0 Hz, H-2), 5.49 (t, 1H, J = 9.5
Hz, H-4’), 5.36 (dm, 1H, J = 9.5 Hz, H-4), 5.19 (t, 1H, J = 9.5 Hz, H-3’), 5.07 (brs, 1H, H-1), 4.96 (d, 1H,
J = 3.5 Hz, H-6’), 4.90 (dd, 1H, J = 9.5, 3.5 Hz, H-5’), 4.29 (dd, 1H, J = 12.0, 4.5 Hz, H-6a), 4.11 (dd, 1H,
J = 12.0, 2.5 Hz, H-6b), 4.09 (ddd, 1H, J = 9.5, 4.5, 2.5 Hz, H-5), 3.95 (ddd, 1H, J = 9.5, 4.0, 2.5 Hz,
H-2’), 3.86 (dd, 1H, J = 11.0, 4.0 Hz, H-1’a), 3.65 (dd, 1H, J = 11.0, 2.5 Hz, H-1’b), 3.42 (s, 3H, OCH3),
13
2.12 (s, 3H, Ac), 2.11 (s, 3H, Ac), 2.10 (s, 3H, Ac), 2.06 (s, 3H, Ac), 2.02 (s, 3H, Ac); C NMR (100
MHz, CDCl3) 170.78, 170.32, 170.15 (2×C), 169.63, 129.53, 127.18, 96.73, 94.53, 70.81, 70.37, 69.02,
67.93, 66.93, 66.28, 65.05, 62.67, 55.43, 20.97, 20.79, 20.71 (2×C), 20.67; HRMS (ESI) C23H32O14 (M+ +
Na), Calcd 555.1690, Found 555.1690.
ACKNOWLEDGEMENTS
This work was supported by the Thailand Research Fund (TRF) (Grant no. TRG5780298) and the
Research Grant of Burapha University through National Research Council of Thailand and the Center of
Excellence for Innovation in Chemistry (PERCH-CIC). Special thanks to Professor Apichart Suksamrarn
(Ramkhamhaeng University) for specific rotation measurement.
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