An efficient method for the selective synthesis of 2-deoxy-2-iodo- glycosides by O-glycosidation of d-glucal using I2-Cu(OAc) 2

Article abstract of DOI:10.1016/j.carres.2010.08.020

An efficient and convenient method for the synthesis of 2-deoxy-2-iodo-O-glycosides from tri-O-acetyl-d-glucal with various alcohols by using I₂-Cu(OAc)₂ is described. The 21 examples of corresponding glycosides were obtained in high

Full text of DOI:10.1016/j.carres.2010.08.020

Carbohydrate Research 345 (2010) 2401–2407
Contents lists available at ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Note
An efficient method for the selective synthesis of 2-deoxy-2-iodo-glycosides
by O-glycosidation of D-glucal using I2–Cu(OAc)2
Uthaiwan Sirion a, Sittidate Purintawarrakun a, Poolsak Sahakitpichan b, Rungnapha Saeeng a,
⇑
a Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Burapha University, Sangsook, Chonburi 20131, Thailand
b Laboratory of Natural Products, Chulabhorn Research Institute, Bangkok 10400, Thailand
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 24 July 2010
Received in revised form 30 August 2010
Accepted 31 August 2010
Available online 6 September 2010
An efficient and convenient method for the synthesis of 2-deoxy-2-iodo-O-glycosides from tri-O-acetyl-
-glucal with various alcohols by using I2–Cu(OAc)2 is described. The 21 examples of corresponding gly-
cosides were obtained in high yields, with good anomeric selectivity.
Ó 2010 Elsevier Ltd. All rights reserved.
D
Keywords:
Glycosylation
Iodine
2-Deoxy-2-iodo-glycosides
Cupric acetate
D-Glucal
2-Deoxy-glycosides are important structural units in many
iodate reagent,9 hypervalent iodine,10 and recently NH4I–H2O2–
Ac2O.11 However, most of these catalysts were not used for wide
variety in organic reactions. In the search for a versatile reagent
to generate an iodonium ion source for the synthesis of 2-deoxy-
2-iodo-glycosides, molecular iodine has received considerable
attention due to its ready availability, low cost, easy handling, high
efficiency, and environmentally benign nature. Recently, our group
has reported a convenient procedure using iodine catalyst in place
biologically significant natural products1 such as aureolic acid,
anthracycline, cardiac glycosides, avermectins, erythromycins,
mitemcinal fumarate, and steroidal glycoside PP57.2. The presence
of 2-deoxy-glycosides is found as important components in glyco-
proteins, glycolipids, and a great variety of secondary metabolites.
In some cases, the presence of these sugars is crucial for recognition,
binding, and activity.2 As the biological importance of 2-deoxy-
glycosides has increased, the investigation of potential methods
for the synthesis of these glycosides becomes a challenging target
for glycoside chemists.3
of Lewis acid in the C-glycosidation of
which provided
D-glucal with silylacetylenes,
a
-glycosyl-acetylene products in high yield and
high selectivity.12 Therefore, to continue our interest in the use
of iodine for glycoside synthesis, we report herein an efficient
method for the synthesis of various 2-deoxy-2-iodo-glycosides as
The most extensive synthetic methods of 2-deoxy-glycosides uti-
lize glycoside donors with C-2 heteroatom substituents4 such as -Br,
-SR, -SeR, -OAc, and -I, which are removed reductively after the
glycosylation step by radical-induced reductive cleavage to give
2-deoxy-glycosides. Among these glycoside donors, 2-deoxy-2-
iodo-glycosides have been widely investigated and employed in
the preparation of 2-deoxy-glycosides as versatile synthetic
intermediates.5 Moreover, 2-deoxy-2-iodo-glycosides have been
alternatively used as novel potential imaging or therapeutic imagine
agents.6
precursors for 2-deoxy-glycoside, via glycosidation of
D-glucal
employing a combination of iodine and cupric acetate (Scheme 1).
The synthesis of 2-deoxy-2-iodo-glycosides was investigated by
O-glycosidation of
D-glucal (1) with 1.5 equiv of iodine and
1.5 equiv of cupric acetate. Cupric acetate has been reported to
be used with iodine for cohalogenation reactions of alkenes in
the presence of water to generate iodohydrins.13 For application
to the glycosylation reaction, we first examined suitable conditions
The synthesis of 2-deoxy-2-iodo-glycosides from
D
-glucal has
as shown in Table 1. The glycosylation of
D-glucal with ethanol was
been reported by the glycosylation reactions using iodonium ion
(I+) equivalent reagents such as N-iodosuccinimide (NIS)7 or iodo-
nium-sym-collidine perchlorate (IDCP),5d,8 polymer-supported
I
AcO
AcO
AcO
AcO
O
O
ROH
AcO
AcO
I2–Cu(OAc)2
OR
2
1
⇑
Corresponding author. Tel.: +66 81 656 7524; fax: +66 3 839 3494.
E-mail addresses: rungnaph@buu.ac.th, rungnaph@yahoo.com (R. Saeeng).
Scheme 1.
0008-6215/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2010.08.020

2402
U. Sirion et al. / Carbohydrate Research 345 (2010) 2401–2407
Table 1
With the optimized conditions in hand (Table 1, entry 7), a
number of alcohols were investigated to react with -glucal to
O-Glycosidation of D-glucal 1 under various conditions
D
I
examine the efficiency, scope, and limitations of this method. The
results are summarized in Table 2. The first set of experiments
were conducted on primary alcohols (entries 1–6), which afforded
AcO
AcO
AcO
AcO
1.5 equiv. EtOH
O
O
AcO
AcO
1.5 equiv. I2
1.5 equiv. Cu(OAc)2
O
3
1
2-deoxy-2-iodo-glycosides in excellent yields with high
stereoselectivity.
a-
Entry
Solvent
Condition
Time (h)
Yield (%)
To further study the reaction, we carried out the experiments
using secondary and tertiary alcohols such as 2-propanol, 2-buta-
nol, cyclohexanol, tert-butanol, and menthol (entries 7–10, 21).
The desired products were afforded in good yields (80–84%) with
higher stereoselectivity than primary alcohols. In comparison with
the secondary alcohols, the reaction of the tertiary alcohol (entry
10) afforded the product in lower yield (51%) but provided im-
proved stereoselectivity. While the glycosylation with phenol (en-
try 11) yielded glycoside 14 in low yield (10%), the reactions of
benzyl alcohol and derivatives smoothly produced the correspond-
ing glycosides in excellent yields (entries 12–17). Glycoside deriv-
ative 25 (entry 20) was also subjected to the O-glycosylation as the
1
2
3
4
5
6
7
CH3CN
THF
DMF
Acetone
CH2Cl2
CH2Cl2
CH2Cl2
a
a
a
a
a
b
c
2
2
48
48
1
49
40
0
0
72
82
95
1
1
Condition a room temperature 30 °C, b 10–20 °C, c 10–20 °C and 4 Å MS.
ROH
AcO
AcO
AcO
AcO
O
O
alcohol nucleophile, which smoothly produced the pure a-anomer
I2–Cu(OAc)2
AcO
23 in 82% yield. Alcohols with functional groups such as propargyl
alcohol and 2-bromoethanol (entries 18 and 19) were also exam-
ined in the present conditions. It was found that the alkyne and
halogen-functionality were retained under these conditions. In all
ROH
I2
OR
1
4
Scheme 2.
cases, a noteworthy point is that the a-anomer is the predominant
product, which can be attributed to the anomeric effect and the
size of alcohol; the selectivity is particularly high when a bulky
alcohol was used as the nucleophile.
I
O
I2
I
AcO
AcO
AcO
AcO
O
AcO
AcO
O
In conclusion, we have developed an efficient method for selec-
tive synthesis of 2-deoxy-2-iodo-glycosides. Attractive features of
this method are the simple experimental procedure, good yields,
high stereoselectivity, and its adaptability for the synthesis of a di-
verse set of 2-deoxy-2-iodo-glycosides. This approach can be fur-
ther applied to the synthesis of 2-deoxy-glycosides, which are
the units of biologically important natural products and they could
be potential imaging or therapeutic imaging agents.
+ HI
OR
2-deoxy-2-iodoglycoside
AcO
AcO
AcO
ROH
Cu(OAc)2
ROH
Cu(OAc)2 + 2 HI
CuI2
+ 2 AcOH
AcO
AcO
AcO
AcO
O
O
AcO
AcO
O
O
H3C
OR
2,3-unsaturated glycoside
1. Experimental
O
ROH
H
I
1.1. General methods
Figure 1. Proposed mechanism.
Proton NMR spectra were recorded on a BRUKER AVANC
(400 MHz). All spectra were measured in CDCl3 solvent and chem-
ical shifts are reported as d values in parts per million (ppm) rela-
tive to tetramethylsilane (d 0.00) or CDCl3 (d 7.26) as the internal
standard. Data are reported as follows: chemical shift (multiplicity,
integration intensity, coupling constants in Hz, assignment). Car-
bon NMR spectra were recorded on a BRUKER AVANC (100 MHz).
All spectra were measured in CDCl3 solvent and chemical shifts
are reported as d values in parts per million (ppm) relative to CDCl3
(d 77.0) as internal standard. High-resolution FAB mass spectra
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 (cmꢀ1). 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 PF254 [E. Merck, Darmstadt, Germany].
selected as the model reaction to examine reaction conditions in
various solvents such as CH2Cl2, CH3CN, THF, DMF, and acetone.
In all cases studied, glycoside 3 was obtained; the best yield was
obtained when CH2Cl2 was used as the solvent. The yield of prod-
uct was significantly increased to nearly quantitative yield when
the reaction was performed at lower temperature (10–20 °C) and
the addition of 4 Å molecular sieves (entry 6 and 7). The use of
CH3CN or THF delivered 40–49% yields of desired product (entries
1and 2), and no reaction was observed when DMF and acetone
were employed as solvents (entries 3 and 4).
It is interesting to note that this glycosylation method using
Cu(OAc)2 did not produce any of other glycoside product, com-
pared to iodine-catalyzed O-glycosylation, which is known to pro-
vide 2,3-unsaturated glycoside 4 (Scheme 2).14 Thus, the selective
formation of 2-deoxy-2-iodo-glycoside can be successfully
achieved in the presence of additives such as Cu(OAc)2.
A proposed mechanism for the glycosylation is summarized in
Figure 1. The reaction of D-glucal and an alcohol in the presence of
iodine without an additive can produce HI, which is believed to pro-
mote Ferrier rearrangement leading to the formation of the 2,3-
unsaturated glycoside. However, in the presence of cupric acetate,
hydroiodic acid (HI) will generate AcOH and CuI2. Without HI, the
reaction proceeds exclusively through the cyclic iodonium interme-
diate, resulting in the formation of the 2-deoxy-2-iodo-glycoside.
1.2. General procedure for synthesis of 2-deoxy-
2-iodo-glycosides
To
a solution of 3,4,6-tri-O-acetoxy-D-glucal (1, 0.1354 g,
0.50 mmol), alcohol (0.75 mmol), cupric acetate (0.1360 g,

U. Sirion et al. / Carbohydrate Research 345 (2010) 2401–2407
2403
Table 2
O-Glycosylation of D-glucal 1 with various alcohols using Cu(OAc)2
I
AcO
AcO
1.5 equiv. ROH
AcO
AcO
AcO
AcO
O
O
O
I
+
1.5 equiv. I2–Cu(OAc)2
CH2Cl2, 4Å MS
AcO
AcO
OR
AcO
1
OR
Entry
1
Nucleophile
Time (h)
1
Major productsc
Yielda (%) (
a
:b)b
I
AcO
O
AcO
AcO
MeOH
98 (5:1)
5
OMe
I
I
I
I
AcO
AcO
O
O
O
O
HO
2
3
4
1
2
2
3
95 (7:1)
92 (7:1)
90 (7:1)
AcO
O
O
O
O
AcO
AcO
6
AcO
HO
HO
HO
AcO
AcO
AcO
7
AcO
AcO
8
AcO
5
6
2
2
90 (6:1)
85 (7:1)
6
(
)
6
I
I
AcO
AcO
O
O
9
HO
HO
AcO
O
O
AcO
AcO
10
AcO
7
8
2
3
80 (9:1)
I
I
AcO
AcO
O
O
OH
AcO
11
12
13
80 (9:1)d
O
O
AcO
AcO
AcO
9
3
3
84 (8:1)
OH
I
I
AcO
AcO
O
AcO
10
51 (14:1)
HO
O
AcO
AcO
O
O
11
12
24
5
10 (only
76 (9:1)
a)
AcO
14
OH
O
O
AcO
AcO
15
OH
I
AcO
AcO
O
MeO
BnO
OBn
OMe
OH
13
24
AcO
80 (7:1)
16
O
(continued on next page)

2404
U. Sirion et al. / Carbohydrate Research 345 (2010) 2401–2407
Table 2 (continued)
Entry
Nucleophile
Time (h)
12
Major productsc
Yielda (%) (
88 (9:1)
a
:b)b
I
AcO
O
AcO
AcO
OH
NO2
14
15
17
O2N
O
O
I
AcO
AcO
O
OH
AcO
6
3
98 (6:1)
18
NO2
NO2
I
AcO
AcO
O
OH
AcO
16
17
98 (11:1)
19
O
O
OCH
OCH3
I
AcO
AcO
O
O
AcO
3
95 (8:1)d
20
21
OH
Br
I
I
AcO
AcO
HO
AcO
18
19
2
3
60 (12:1)
57 (9:1)
O
Br
AcO
AcO
O
O
HO
AcO
22
O
O
I
AcO
AcO
AcO
HO
BnO
BnO
O
23
BnO
20
24
82 (only a)
OBn
O
25
OMe
BnO
OBn
OMe
I
AcO
AcO
O
AcO
HO
21
5
64 (12:1)
O
24
a
Isolated yields as diastereomeric mixtures.
Determined by 1H NMR spectroscopy.
Major product can be separated by simple column chromatography.
Diastereomeric mixture from racemic alcohol.
b
c
d
0.75 mmol), and molecular sieves 4 Å (0.1354 g) in anhydrous
CH2Cl2 (5.0 mL) was added iodine powder (0.1900 g, 0.75 mmol)
at 10–20 °C. The mixture was stirred for 1 h. After TLC showed
the complete conversion, the molecular sieves were removed by
filtration. The filtrate solution was diluted with dichloromethane,
washed with satd aq Na2S2O3, then dried over with Na2SO4
anhydrous, and concentrated in vacuo. The residue was purified
by silica gel column chromatography to give the 2-deoxy-2-iodo-
glycoside product.
H-10b), 4.05 (ddd, 1H, J = 9.5, 5.0, 2.5 Hz, H-5), 4.16 (dd, 1H,
J = 12.0, 2.5 Hz, H-6a), 4.25 (dd, 1H, J = 12.0, 5.0 Hz, H-6b), 4.54
(dd, 1H, J = 4.5, 1.0 Hz, H-2), 4.68 (dd, 1H, J = 9.5, 4.5 Hz, H-3),
5.20 (br s, 1H, H-1), 5.39 (t, 1H, J = 9.5 Hz, H-4). 13C NMR
(100 MHz, CDCl3): d 14.98, 20.67, 20.75, 20.97, 29.80, 62.29,
64.11, 67.66, 69.05, 69.12, 101.10, 169.53, 169.89, 170.75. HRMS:
C
14H21IO8 (M++Na), Calcd 467.0175, Found 467.0183.
1.4. Methyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (5)
1.3. Ethyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (3)
IR (CHCl3): 2940, 2838, 1747, 1369, 1231, 1052, 967, 902,
602 cmꢀ1 1H NMR (400 MHz, CDCl3): d 2.02 (s, 3H, Ac), 2.05 (s,
.
½
a 2D8
ꢁ
+7.89 (c 1.02, CHCl3). IR (CHCl3): 2980, 2930, 1748, 1370,
3H, Ac), 2.09 (s, 3H, Ac), 3.38 (s, 3H, H-10), 3.97 (ddd, 1H, J = 9.5,
5.0, 2.5 Hz, H-5), 4.13 (dd, 1H, J = 12.0, 2.5 Hz, H-6a), 4.20 (dd,
1H, J = 12.0, 5.0 Hz, H-6b), 4.50 (dd, 1H, J = 4.5, 1.0 Hz, H-2), 4.59
(dd, 1H, J = 9.5, 4.5 Hz, H-3), 5.05 (br s, 1H, H-1), 5.33 (t, 1H,
1231, 1052 cmꢀ1 1H NMR (400 MHz, CDCl3): d 1.26 (t, 3H,
.
J = 7.0 Hz, H-20), 2.07 (s, 3H, Ac), 2.10 (s, 3H, Ac), 2.14 (s, 3H, Ac),
3.56 (dq, 1H, J = 10.0, 7.0 Hz, H-10a), 3.75 (dq, 1H, J = 10.0, 7.0 Hz,

U. Sirion et al. / Carbohydrate Research 345 (2010) 2401–2407
2405
J = 9.5 Hz, H-4). 13C NMR (100 MHz, CDCl3): d 20.60, 20.69, 20.88,
(100 MHz, CDCl3): d 11.02, 11.12, 20.68, 20.74, 20.97, 23.23,
29.22, 55.38, 62.25, 67.52, 69.0, 69.18, 102.28, 169.48, 169.81,
23.30, 29.77, 40.93, 62.35, 67.62, 69.19, 69.20, 70.97, 101.55,
169.55, 169.88, 170.71. HRMS:
523.0805, Found. 523.0687.
170.68. HRMS:
453.0031.
C
13H19IO8 (M++Na), Calcd 453.0022, Found.
C
18H29IO8 (M++Na), Calcd
1.5. Propyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–
D-
1.9. i-Propyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (6)
mannopyranoside (10)
½
a 2D8
ꢁ
+1.64 (c 1.01, CHCl3). IR (CHCl3): 2959, 2936, 1745, 1432,
½
a 2D8
ꢁ
+1.83 (c 1.01, CHCl3), IR (CHCl3): 2972, 2925, 1742, 1433,
1366, 1220, 1019, 743 cmꢀ1 1H NMR (400 MHz, CDCl3): d 0.96 (t,
.
1367, 1220, 1113, 1032, 736 cmꢀ1 1H NMR (400 MHz, CDCl3): d
.
3H, J = 7.4 Hz, H-30), 1.57–1.73 (m, 2H, H-20), 2.07 (s, 3H, Ac), 2.10
(s, 3H, Ac), 2.13 (s, 3H, Ac), 3.45 (dt, 1H, J = 9.6, 6.8 Hz, H-10a),
3.64 (dt, 1H, J = 9.6, 6.8 Hz, H-10b), 4.04 (ddd, 1H, J = 9.6, 5.0,
2.8 Hz, H-5), 4.16 (dd, 1H, J = 12.0, 2.8 Hz, H-6a), 4.24 (dd, 1H,
J = 12.0, 5.0 Hz, H-6b), 4.55 (dd, 1H, J = 4.4, 1.2 Hz, H-2), 4.66 (dd,
1H, J = 9.6, 4.4 Hz, H-3), 5.19 (br s, 1H, H-1), 5.38 (t, 1H,
J = 9.6 Hz, H-4). 13C NMR (100 MHz, CDCl3): d 10.60, 20.67, 20.75,
20.97, 22.65, 29.78, 62.30, 67.65, 69.07, 69.16, 70.25, 101.29,
1.17 (d, 3H, J = 6.0 Hz, H-20a), 1.23 (d, 3H, J = 6.0 Hz, H-20b), 2.05
(s, 3H, Ac), 2.08 (s, 3H, Ac), 2.10 (s, 3H, Ac), 3.80–4.00 (m, 1H, H-
10), 4.08 (ddd, 1H, J = 9.5, 5.0, 2.4 Hz, H-5), 4.14 (dd, 1H, J = 12.0,
2.4 Hz, H-6a), 4.22 (dd, 1H, J = 12.2, 5.0 Hz, H-6b), 4.48 (d, 1H,
J = 4.3 Hz, H-2), 4.66 (dd, 1H, J = 9.5, 4.3 Hz, H-3), 5.26 (br s, 1H,
H-1), 5.36 (t, 1H, J = 9.7 Hz, H-4). 13C NMR (100 MHz, CDCl3): d
20.62, 20.68, 20.92, 21.60, 23.03, 30.56, 62.30, 67.75, 69.05,
69.08, 71.06, 99.61, 169.47, 169.77, 170.60. HRMS: C15H23IO8
(M++Na), Calcd 481.0336, Found. 481.0324.
169.54, 169.88, 170.73. HRMS:
481.0336, Found. 481.0339.
C
15H23IO8 (M++Na), Calcd
1.10. s-Butyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–
D-
1.6. Butyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (12) (mixture of diastereomers)
mannopyranoside (7)
½
a 2D8
ꢁ
+1.90 (c 1.05, CHCl3), IR (CHCl3): 2970, 2936, 1748, 1369,
½
a 2D8
ꢁ
+14.75 (c 1.08, CHCl3). IR (CHCl3): 2959, 2874, 1742, 1433,
1230, 1040, 599 cmꢀ1 1H NMR (400 MHz, CDCl3): d 0.77–0.93
.
1366, 1219, 1117, 1038, 673 cmꢀ1 1H NMR (400 MHz, CDCl3): d
.
(m, 6H, H-40, isomer A, isomer B), 1.07 (d, 3H, J = 5.0 Hz, H-20, iso-
mer A), 1.14 (d, 3H, J = 5.3 Hz, H-20, isomer B), 1.31–1.63 (m, 4H, H-
30, isomer A, isomer B), 1.99 (s, 3H, Ac), 2.01 (s, 3H, Ac), 2.04 (s, 3H,
Ac), 3.55–3.68 (m, 2H, H-10, isomer A, isomer B), 3.98–4.19 (m, 6H,
H-5, H-6, isomer A, isomer B), 4.42 (d, 1H, J = 4.5 Hz, H-2, isomer A),
4.41 (d, 1H, J = 4.5 Hz, H-2, isomer B), 4.53–4.63 (m, 2H, H-3, iso-
mer A, isomer B), 5.19 (br s, 1H, H-1, isomer A), 5.21 (br s, 1H, H-
1, isomer B), 5.29 (t, 2H, J = 9.7 Hz, H-4, isomer A, isomer B). 13C
NMR (100 MHz, CDCl3): d 9.57, 10.17, 18.59, 20.45, 20.65, 20.69,
20.94, 28.99, 29.76, 30.42, 30.65, 62.37, 67.74, 67.82, 69.13,
69.19, 69.25, 75.22, 77.68, 98.92, 101.00, 169.51, 169.80, 170.63.
HRMS: C16H25IO8 (M++Na), Calcd 495.0492, Found. 495.0499.
0.94 (t, 3H, J = 7.1 Hz, H-40), 1.34–1.45 (m, 2H, H-30), 1.54–1.65
(m, 2H, H-20), 2.06 (s, 3H, Ac), 2.09 (s, 3H, Ac), 2.12 (s, 3H, Ac),
3.47 (dt, 1H, J = 9.0, 6.6 Hz, H-10a), 3.68 (dt, 1H, J = 9.0, 6.7 Hz, H-
10b), 4.02 (ddd, 1H, J = 9.5, 4.5, 2.0 Hz, H-5), 4.15 (dd, 1H, J = 12.1,
2.0 Hz, H-6a), 4.23 (dd, 1H, J = 12.1, 4.5 Hz, H-6b), 4.53 (d, 1H
J = 4.0 Hz, H-2), 4.65 (dd, 1H, J = 9.5, 4.0 Hz, H-3), 5.17 (br s, 1H,
H-1), 5.37 (t, 1H, J = 9.5 Hz, H-4). 13C NMR (100 MHz, CDCl3): d
13.79, 19.29, 20.67, 20.75, 20.97, 29.79, 31.40, 62.31, 67.63,
69.41, 69.07, 69.14, 101.29, 169.52, 169.86, 170.70. HRMS:
C
16H25IO8 (M++Na), Calcd 495.0492, Found. 495.0481.
1.7. Octyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (8)
1.11. Cylohexyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (12)
½
a 2D8
ꢁ
+16.79 (c 1.02, CHCl3). IR (CHCl3): 3056, 2929, 1748, 1455,
1423, 1368, 1265, 1229, 1047, 739 cmꢀ1 1H NMR (400 MHz,
.
½
a 2D8
ꢁ
+22.03 (c 1.05, CHCl3), IR (CHCl3): 2933, 2857, 1743, 1449,
CDCl3): d 0.89 (t, 3H, J = 6.8 Hz, H-80), 1.22–1.40 (m, 10H, H-30, H-
40, H-50, H-60, H-70), 1.57–1.64 (m, 2H, H-20), 2.06 (s, 3H, Ac), 2.09
(s, 3H, Ac), 2.12 (s, 3H, Ac), 3.45 (ddd, 1H, J = 13.2, 6.0, 3.0 Hz, H-
1a0), 3.67 (ddd, 1H, J = 13.2, 6.0, 3.0 Hz, H-1b0), 4.02 (ddd, 1H,
J = 9.8, 4.8, 2.4 Hz, H-5), 4.15 (dd, 1H, J = 12.1, 2.4 Hz, H-6a), 4.23
(dd, 1H, J = 12.1, 4.8 Hz, H-6b), 4.54 (dd, 1H, J = 4.4, 1.1 Hz, H-2),
4.65 (dd, 1H, J = 9.8, 4.4 Hz, H-3), 5.17 (br s, 1H, H-1), 5.37 (t, 1H,
J = 9.8 Hz, H-4). 13C NMR (100 MHz, CDCl3): d 14.08, 20.67, 20.75,
20.97, 22.63, 26.06, 29.18, 29.29, 29.33, 29.80, 31.79, 62.29,
67.63, 68.74, 69.06, 69.15, 101.29, 169.52, 169.86, 170.71. HRMS:
1366, 1219, 1114, 1033, 672 cmꢀ1 1H NMR (400 MHz, CDCl3): d
.
1.05–1.55 (m, 6H, H-30, H-40, H-50), 1.60–1.85 (m, 4H, H-20, H-60),
1.99 (s, 3H, Ac), 2.01 (s, 3H, Ac), 2.04 (s, 3H, Ac), 3.52 (tt, 1H,
J = 9.3, 3.9 Hz, H-10), 4.04 (ddd, 1H, J = 9.6, 4.9, 2.5 Hz, H-5), 4.08
(dd, 1H, J = 12.1, 2.5 Hz, H-6a), 4.14 (dd, 1H, J = 12.1, 4.9 Hz, H-
6b), 4.42 (dd, 1H, J = 4.3, 1.2 Hz, H-2), 4.60 (dd, 1H, J = 9.5, 4.3 Hz,
H-3), 5.23 (br s, 1H, H-1), 5.29 (t, 1H, J = 9.6 Hz, H-4). 13C NMR
(100 MHz, CDCl3): d 20.68, 20.74, 20.99, 23.84, 24.10, 25.44,
30.68, 31.58, 33.19, 62.37, 67.84, 69.14, 69.20, 76.93, 99.58,
169.57, 169.90, 170.72. HRMS:
521.0649, Found. 521.0643.
C
18H27IO8 (M++Na), Calcd
C
20H33IO8 (M++Na), Calcd 551.1118, Found. 551.0984.
1.8. 30-Ethyl-butyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–
D-
1.12. t-Butyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (9)
mannopyranoside (13)
½
a 2D8
ꢁ
+2.03 (c 1.06, CHCl3). IR (CHCl3): 3056, 2964, 1747, 1458,
½
a 2D8
ꢁ
+18.19 (c 1.02, CHCl3), IR (CHCl3): 2977, 2937, 1748, 1370,
1368, 1266, 1229, 1045, 738 cmꢀ1 1H NMR (400 MHz, CDCl3): d
.
1231, 1046, 882, 602 cmꢀ1 1H NMR (400 MHz, CDCl3): d 1.27 (s,
.
0.90 (t, 6H, J = 7.2 Hz, H-40, H-60), 1.34–1.41 (m, 4H, H-30, H-50),
1.40–1.50 (m, 1H, H-20), 2.07 (s, 3H, Ac), 2.10 (s, 3H, Ac), 2.12 (s,
3H, Ac), 3.36 (dd, 1H, J = 9.4, 5.6 Hz, H-10a), 3.61 (dd, 1H, J = 9.4,
5.6 Hz, H-10b), 4.01 (ddd, 1H, J = 9.8, 5.0, 2.4 Hz, H-5), 4.16 (dd,
1H, J = 12.2, 2.4 Hz, H-6a), 4.23 (dd, 1H, J = 12.2, 5.0 Hz, H-6b),
4.55 (d, 1H, J = 4.4 Hz, H-2), 4.64 (dd, 1H, J = 9.8, 4.3 Hz, H-3),
5.16 (br s, 1H, H-1), 5.37 (t, 1H, J = 9.8 Hz, H-4). 13C NMR
9H, H-20), 2.06 (s, 3H, Ac), 2.09 (s, 3H, Ac), 2.10 (s, 3H, Ac), 4.09–
4.26 (m, 3H, H-5, H-6), 4.41 (d, 1H, J = 4.0 Hz, H-2), 4.70 (dd, 1H,
J = 9.5, 4.0 Hz, H-3), 5.36 (t, 1H, J = 9.5 Hz, H-4), 5.42 (br s, 1H, H-
1). 13C NMR (100 MHz, CDCl3): d 20.66, 20.71, 20.97, 28.38,
32.03, 62.47, 67.98, 68.74, 69.19, 76.86, 96.21, 169.55, 169.90,
170.70. HRMS:
495.0490.
C
16H25IO8 (M++Na), Calcd 495.0492, Found.

2406
U. Sirion et al. / Carbohydrate Research 345 (2010) 2401–2407
1.13. Phenyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–
D
-
1.17. 3-Nitro-benzyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (14)
mannopyranoside (18)
½
a 2D8
ꢁ
+39.49 (c 1.04, CHCl3), IR (CHCl3): 2922, 2852, 1743, 1596,
½
a 2D8
ꢁ
+27.45 (c 1.02, CHCl3), IR (CHCl3): 3055, 2986, 1747, 1607,
1493, 1367, 1211, 1115, 1059, 691 cmꢀ1 1H NMR (400 MHz,
.
1532, 1351, 1265, 1230, 1045, 738 cmꢀ1 1H NMR (400 MHz,
.
CDCl3): d 2.07 (s, 3H, Ac), 2.08 (s, 3H, Ac), 2.15 (s, 3H, Ac), 4.10–
4.19 (m, 2H, H-5, H-6a), 4.23 (dd, 1H, J = 12.1, 4.9 Hz, H-6b), 4.76
(dd, 1H, J = 4.5, 1.3 Hz, H-2), 4.87 (dd, 1H, J = 9.5, 4.5 Hz, H-3),
5.47 (t, 1H, J = 9.5 Hz, H-4), 5.87 (br s, 1H, H-1), 7.05–7.15 (m,
3H, Ph), 7.32 (dd, 2H, J = 8.8, 7.3 Hz, Ph). 13C NMR (100 MHz,
CDCl3): d 20.66, 20.68, 20.99, 28.81, 61.93, 67.30, 68.96, 69.78,
99.70, 116.48, 123.06, 129.66, 155.53, 169.53, 169.94, 170.62.
HRMS: C18H21IO8 (M++Na), Calcd 515.0179, Found. 515.0167.
CDCl3): d 2.07 (s, 3H, Ac), 2.11 (s, 3H, Ac), 2.15 (s, 3H, Ac), 4.05
(ddd, 1H, J = 9.7, 5.0, 2.4 Hz, H-5), 4.16 (dd, 1H, J = 12.2, 2.4 Hz,
H-6b), 4.26 (dd, 1H, J = 12.2, 5.0 Hz, H-6a), 4.62 (d, 1H, J = 4.4 Hz,
H-2), 4.64 (d, 1H, J = 12.5 Hz, H-1a0), 4.66 (dd, 1H, J = 9.7, 4.3 Hz,
H-3), 4.82 (d, 1H, J = 12.5 Hz, H-1b0), 5.29 (br s, 1H, H-1), 5.42 (t,
1H, J = 9.7 Hz, H-4), 7.59 (t, 1H, J = 8.6 Hz, Ph), 7.71 (d, 1H,
J = 8.6 Hz, Ph), 8.21 (s, 1H, Ph), 8.22 (d, 1H, J = 8.6 Hz, Ph). 13C
NMR (100 MHz, CDCl3): d 20.63, 20.74, 20.91, 28.70, 62.15, 67.44,
68.69, 68.93, 69.66, 100.89, 122.79, 123.26, 129.71, 133.82,
138.40, 148.39, 169.43, 169.82, 170.62. HRMS:
C19H22INO10
1.14. Benzyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (15)
(M++Na), Calcd 574.0186, Found. 574.0034.
1.18. 3-Methoxy-benzyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (19)
½
a 2D8
ꢁ
+35.76 (c 1.09, CHCl3), IR (CHCl3): 3055, 2986, 1746, 1455,
1422, 1368, 1265, 1121, 1042, 896, 738 cmꢀ1 1H NMR (400 MHz,
.
CDCl3): d 2.06 (s, 3H, Ac), 2.10 (s, 3H, Ac), 2.14 (s, 3H, Ac), 4.05
(ddd, 1H, J = 9.5, 4.7, 2.4 Hz, H-5), 4.10 (dd, 1H, J = 12.2, 2.4 Hz,
H-6a), 4.24 (dd, 1H, J = 12.2, 4.7 Hz, H-6b), 4.57 (d, 1H,
J = 11.8 Hz, H-10a), 4.58 (dd, 1H, J = 4.4, 1.0 Hz, H-2), 4.69 (dd, 1H,
J = 9.5, 4.4 Hz, H-3), 4.72 (d, 1H, J = 11.8 Hz, H-10b), 5.27 (br s, 1H,
H-1), 5.41 (t, 1H, J = 9.5 Hz, H-4), 7.29–7.50 (m, 5H, Ph). 13C NMR
(100 MHz, CDCl3): d 20.67, 20.78, 20.96, 29.55, 62.16, 67.55,
69.10, 69.33, 70.03, 100.53, 128.21, 128.30, 128.62, 136.34,
½
a 2D8
+33.04 (c 1.08, CHCl3), IR (CHCl3): 3055, 2986, 1747, 1588,
ꢁ
1490, 1457, 1368, 1265, 1231, 1042, 738 cmꢀ1. 1H NMR (400 MHz,
CDCl3): d 2.07 (s, 3H, Ac), 2.10 (s, 3H, Ac), 2.15 (s, 3H, Ac), 3.84 (s,
3H, H-80), 4.06 (ddd, 1H, J = 9.8, 4.6, 2.3 Hz, H-5), 4.12 (dd, 1H,
J = 12.2, 2.3 Hz, H-6b), 4.24 (dd, 1H, J = 12.2, 4.6 Hz, H-6a), 4.54
(d, 1H, J = 12.0 Hz, H-10a), 4.58 (dd, 1H, J = 4.3, 1.2 Hz, H-2), 4.69
(d, 1H, J = 12.0 Hz, H-10b), 4.70 (dd, 1H, J = 9.8, 4.3 Hz, H-3), 5.26
(br s, 1H, H-1), 5.41 (t, 1H, J = 9.8 Hz, H-4), 6.88 (d, 1H, J = 7.6 Hz,
Ph), 6.90 (s, 1H, Ph), 6.93 (d, 1H, J = 7.6 Hz, Ph), 7.30 (t, 1H,
J = 7.6 Hz, Ph). 13C NMR (100 MHz, CDCl3): d 20.67, 20.78, 20.96,
29.50, 55.28, 62.19, 67.56, 69.10, 69.35, 69.81, 100.43, 113.65,
113.76, 120.39, 129.68, 137.86, 159.80, 169.52, 169.85, 170.74.
HRMS: C20H25IO9 (M++Na), Calcd 559.0441, Found. 559.0309.
169.50, 169.85, 170.71. HRMS:
529.0335, Found. 529.0323.
C
19H23IO8 (M++Na), Calcd
1.15. 4-Benzyloxy-3-methoxy-benzyl 3,4,6-tri-O-acetyl-2-
deoxy-2-iodo– -mannopyranoside (16)
D
½
a 2D8
ꢁ
+42.06 (c 0.98, CHCl3), IR (CHCl3): 3055, 2988, 1749, 1605,
1.19. 2-Phenyl-propyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (20) (mixture of isomers)
1590, 1421, 1369, 1266, 1122, 1037, 735 cmꢀ1 1H NMR
.
(400 MHz, CDCl3): d 2.07 (s, 3H, Ac), 2.10 (s, 3H, Ac), 2.15 (s, 3H,
Ac), 3.93 (s, 3H, OMe), 4.05 (ddd, 1H, J = 9.5, 4.7, 2.4 Hz, H-5),
4.13 (dd, 1H, J = 12.2, 2.4 Hz, H-6a), 4.25 (dd, 1H, J = 12.2, 4.7 Hz,
H-6b), 4.49 (d, 1H, J = 11.6 Hz, H-10a), 4.55 (dd, 1H, J = 4.3, 1.0 Hz,
H-2), 4.64 (d, 1H, J = 11.6 Hz, H-10b), 4.69 (dd, 1H, J = 9.5, 4.3 Hz,
H-3), 5.18 (s, 2H, OCH2Ph), 5.23 (br s, 1H, H-1), 5.41 (t, 1H,
J = 9.5 Hz, H-4), 6.83 (dd, 1H, J = 8.0, 2.0 Hz, Ph), 6.88 (d, 1H,
J = 8.0 Hz, Ph), 6.90 (d, 1H, J = 2 Hz, Ph), 7.25–7.34 (m, 1H, Ph),
7.39 (t, 2H, J = 7.2 Hz, Ph), 7.45 (d, 2H, J = 7.2 Hz, Ph). 13C NMR
(100 MHz, CDCl3): d 20.67, 20.79, 20.97, 29.62, 56.09, 62.19,
67.59, 69.11, 69.30, 69.80, 71.05, 100.07, 112.12, 113.78, 121.02,
127.25, 127.90, 128.59, 129.27, 136.98, 148.26, 149.77, 169.52,
½
a 2D9
ꢁ
+20.28 (c 1.01, CHCl3), IR (CHCl3): 3058, 2967, 2938, 1747,
1493, 1455, 1368, 1266, 1230, 1117, 1040, 738 cmꢀ1 1H NMR
.
(400 MHz, CDCl3): d 0.77 (t, 3H, J = 7.4 Hz, H-30, isomer A), 0.84
(t, 3H, J = 7.4 Hz, H-30, isomer B), 1.66 (m, 2H, H-20, isomer B),
1.84 (m, 2H, H-20, isomer B), 1.90, 1.95, 2.00, 2.01, 2.05 (6s, 18H,
Ac, isomer A and B), 3.39 (dd, 1H, J = 12.5, 2.0 Hz, H-6a, isomer
A), 3.49 (m, 1H, H-5, isomer A), 3.84 (dd, 1H, J = 12.5, 4.0 Hz, H-
6b, isomer A), 4.08 (m, 1H, H-5, isomer B), 4.12 (dd, 1H, J = 12.5,
2.0 Hz, H-6a, isomer B), 4.18 (dd, 1H, J = 12.5, 5.0 Hz, H-6b, isomer
B), 4.30 (t, 1H, J = 6.5, H-10, isomer A), 4.37 (m, 1H, H-2, isomer A),
4.39 (t, 1H, J = 6.5, H-10, isomer B), 4.55 (m, 1H, H-2, isomer B),
4.52–4.56 (m, 1H, H-3, isomer B), 4.65 (dd, 1H, J = 9.5, 4.5 Hz, H-
3, isomer A), 4.86 (br s, 1H, H-1, isomer B), 5.24 (t, 1H, J = 10.0,
H-4, isomer B), 5.30 (br s, 1H, H-1, isomer A), 5.31 (t, 1H, J = 9.5,
H-4, isomer A), 7.16–7.31 (m, 5H, Ph). 13C NMR (100 MHz, CDCl3):
d 9.99, 10.05, 10.62, 20.56, 20.70, 20.91, 20.96, 29.79, 30.00, 30.70,
61.48, 62.45, 67.32, 67.81, 69.23, 69.33, 69.38, 69.46, 80.67, 84.13,
98.34, 102.11, 102.16, 126.68, 127.00, 127.87, 128.21, 128.37,
128.64, 140.16, 141.65, 169.29, 169.45, 169.81, 170.51, 170.55.
HRMS: C21H27IO8 (M++Na), Calcd 557.0648, Found. 557.0511.
169.89, 170.73. HRMS:
Found. 665.0841.
C
27H31IO10 (M++Na), Calcd 665.0860,
1.16. 4-Nitro-benzyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (17)
½
a 2D8
ꢁ
+35.57 (c 1.08, CHCl3), IR (CHCl3): 3055, 2987, 1748, 1607,
1522, 1348, 1265, 1230, 1047, 738 cmꢀ1 1H NMR (400 MHz,
.
CDCl3): d 2.08 (s, 3H, Ac), 2.12 (s, 3H, Ac), 2.15 (s, 3H, Ac), 4.05
(ddd, 1H, J = 9.7, 4.7, 2.5 Hz, H-5), 4.16 (dd, 1H, J = 12.3, 2.5 Hz,
H-6b), 4.26 (dd, 1H, J = 12.3, 4.7 Hz, H-6a), 4.63 (d, 1H, J = 4.4 Hz,
H-2), 4.65 (d, 1H, J = 13.0 Hz, H-1a0), 4.66 (dd, 1H, J = 9.7, 4.4 Hz,
H-3), 4.84 (d, 1H, J = 13.0 Hz, H-1b0), 5.29 (br s, 1H, H-1), 5.43 (t,
1H, J = 9.7 Hz, H-4), 7.54 (d, 2H, J = 8.4 Hz, Ph), 8.26 (d, 2H,
J = 8.4 Hz, Ph). 13C NMR (100 MHz, CDCl3): d 20.63, 20.74, 20.93,
28.59, 62.12, 67.41, 68.53, 68.95, 69.69, 100.97, 123.87, 128.17,
1.20. 2-Bromoethyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (21)
½
a 2D9
+20.33 (c 0.97, CHCl3), IR (CHCl3): 3056, 2985, 1735, 1373,
ꢁ
1266, 1244, 1046, 909, 738 cmꢀ1. 1H NMR (400 MHz, CDCl3): d 2.05
(s, 3H, Ac), 2.08 (s, 3H, Ac), 2.11 (s, 3H, Ac), 3.50 (t, 1H, J = 5.0 Hz, H-
20), 3.86 (dt, 1H, J = 11.0, 5.0 Hz, H-10a), 3.97 (dt, 1H, J = 11.0, 5.0 Hz,
H-10b), 4.15 (m, 1H, H-5), 4.16 (dd, 1H, J = 12.0, 2.5 Hz, H-6a), 4.21
143.62, 148.13, 169.42, 169.89, 170.61. HRMS:
C19H22INO10
(M++Na), Calcd 574.0186, Found. 573.9964.

U. Sirion et al. / Carbohydrate Research 345 (2010) 2401–2407
2407
(dd, 1H, J = 12.0, 5.0 Hz, H-6b), 4.55 (dd, 1H, J = 4.4, 1.2 Hz, H-2),
4.66 (dd, 1H, J = 9.5, 4.5 Hz, H-3), 5.23 (br s, 1H, H-1), 5.36 (t, 1H,
J = 9.5 Hz, H-4). 13C NMR (100 MHz, CDCl3): d 20.63, 20.72, 20.91,
28.95, 29.72, 62.15, 67.40, 68.44, 68.94, 69.64, 101.54, 169.47,
169.78, 170.61. HRMS: HRMS:
544.9284, Found. 544.9145.
H-80, H-800), 1.15–1.39 (m, 2H, menthol ring), 1.48–1.75 (m, 3H,
menthol ring), 1.99 (s, 3H, Ac), 2.01 (s, 3H, Ac), 2.04 (s, 3H, Ac),
3.30 (dt, 1H, J = 10.6, 4.2 Hz, H-10), 4.02–4.18 (m, 3H, H-5, H-6),
4.44 (d, 1H, J = 4.1 Hz, H-2), 4.59 (dd, 1H, J = 9.1, 4.1 Hz, H-3),
5.18 (br s, 1H, H-1), 5.27 (t, 1H, J = 9.0 Hz, H-4). 13C NMR
(100 MHz, CDCl3): d 16.33, 20.67, 20.76, 20.92, 20.95, 22.29,
23.33, 25.96, 30.28, 31.60, 34.15, 42.48, 48.26, 62.59, 67.87,
69.12, 69.32, 82.77, 103.03, 169.56, 169.91, 170.69. HRMS:
C
14H20BrIO8 (M++Na), Calcd
1.21. Propargyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (22)
C
22H35IO8 (M++Na), Calcd 577.1274, Found. 577.1274.
½
a 2D8
ꢁ
+38.19 (c 1.01, CHCl3), IR (CHCl3): 3301, 3056, 2986, 2123,
Acknowledgments
1748, 1423, 1368, 1227, 1124, 1046, 970, 897, 738 cmꢀ1 1H NMR
.
(400 MHz, CDCl3): d 2.06 (s, 3H, Ac), 2.09 (s, 3H, Ac), 2.12 (s, 3H,
Ac), 2.50 (t, 1H, J = 2.4 Hz, H-30), 4.06 (ddd, 1H, J = 10.0, 4.5,
2.0 Hz, H-5), 4.15 (dd, 1H, J = 12.0, 2.0 Hz, H-6b), 4.23 (dd, 1H,
J = 12.0, 4.5 Hz, H-6a), 4.27 (d, 1H, J = 2.3 Hz, H-10a), 4.28 (d, 1H,
J = 2.3 Hz, H-10b), 4.56 (dd, 1H, J = 4.4, 1.2 Hz, H-2), 4.63 (dd, 1H,
J = 10.0, 4.5 Hz, H-3), 5.38 (br s, 1H, H-1), 5.40 (t, 1H, J = 10.0 Hz,
H-4). 13C NMR (100 MHZ, CDCl3): d 20.58, 20.69, 20.86, 28.81,
54.95, 62.00, 67.37, 68.78, 69.56 , 75.59, 78.01, 99.92, 169.37,
169.71, 170.60. HRMS: C15H19IO8 (M++Na), Calcd 477.0022, Found.
476.9917.
We thank Burapha-NRCT Annual grants, Thailand Research
Fund (TRF) and PERCH-CIC for financial support. Special thanks
to Professor Keiji Tanino (Hokkaido Univ., Japan) for helpful discus-
sion on the reaction mechanism.
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.carres.2010.08.020.
References
1.22. Methyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-mannopyr-
anosyl-(1?6)-3,4,6-tri-O-benzyl– -glucopyranoside (23)
D
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+52.41 (c 1.08, CHCl3), IR (CHCl3): 2925, 2850, 1744, 1600,
ꢁ
2. He, X.; Agnihotri, G.; Liu, H.-W. Chem. Rev. 2000, 100, 4615–4661.
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10. Kirsching, A. Eur. J. Org. Chem. 1998, 2267–2274.
½
1496, 1454, 1366, 1223, 1086, 1028, 697 cmꢀ1. 1H NMR (400 MHz,
CDCl3): d 1.94 (s, 3H, Ac), 1.97 (s, 3H, Ac), 2.00 (s, 3H, Ac), 3.30 (s,
3H, OMe), 3.40 (t, 1H, J = 9.4 Hz, H-40), 3.47 (dd, 1H, J = 9.6, 3.6 Hz,
H-20), 3.57 (d, 1H, J = 10.1 Hz, H-60a), 3.65–3.78 (m, 2H, H-60b, H-
50), 3.83–4.00 (m, 3H, H-5, H-6, H-30), 4.43–4.55 (m, 4H, H-2, H-3,
H-10, O-CH2Ph), 4.60 (d, 1H, J = 12.0 Hz, O-CH2Ph), 4.72 (d, 2H,
J = 11.5 Hz, 2 ꢂ O-CH2Ph), 4.90 (d, 1H, J = 11.2 Hz, O-CH2Ph), 4.92
(d, 1H, J = 10.8 Hz, O-CH2Ph), 5.13 (br s, 1H, H-1), 5.26 (t, 1H,
J = 9.6 Hz, H-4), 7.00–7.50 (m, 15H, Ph). 13C NMR (100 MHz, CDCl3):
d 20.66, 20.73, 20.97, 29.27, 55.24, 62.01, 66.74, 67.40, 69.00, 69.19,
69.69, 73.42, 74.91, 75.82, 77.58, 80.08, 82.12, 97.97, 101.42,
127.46, 127.69, 127.79, 127.98, 128.04, 128.13, 128.44, 128.45,
128.52, 138.08, 138.20, 138.57, 169.45, 169.79, 170.67. HRMS:
C
40H47IO13 (M++Na), Calcd 885.1959, Found. 885.1980.
11. Gammon, D. W.; Kinfe, H. H.; De Vos, D. E.; Jacobs, P. A.; Sels, B. F. Tetrahedron
Lett. 2004, 45, 9533–9536.
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13. Sanseverino, A. M.; Silva, F. M. D.; Jones, J.; Mattos, M. C. S. J. Braz. Chem. Soc.
2000, 11, 381–386.
1.23. Menthyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo–D-
mannopyranoside (24)
½
a 2D8
+64.18 (c 1.01, CHCl3), IR (CHCl3): 3055, 2959, 1748, 1456,
ꢁ
14. Koreeda, M.; Houston, T. A.; Shull, B. K.; Klenke, E.; Thinman, R. S. Synlett 1995,
90–92.
1369, 1233, 1115, 1032, 896, 738 cmꢀ1. 1H NMR (400 MHz, CDCl3):
d 0.70 (d, 3H, J = 7.0 Hz, H-90), 0.73–1.05 (m, 10H, menthol ring,