Synthesis of Phenolic Glycosides: Glycosylation of Sugar Lactols with Aryl Bromides via Dual Photoredox/Ni Catalysis

Article abstract of DOI:10.1021/acs.joc.8b02129

Multifarious sugar lactols were efficiently transformed into the corresponding phenolic glycosides by treating with aryl bromides in acetonitrile with Ir[dF(CF₃)ppy]₂(dtbbpy)(PF₆) as a photocatalyst under visible light irr

Full text of DOI:10.1021/acs.joc.8b02129

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Article
Synthesis of Phenolic Glycosides: Glycosylation of Sugar
Lactols with Aryl Bromides via Dual Photoredox/Ni Catalysis
Hui Ye, Cong Xiao, Quan-Quan Zhou, Peng George Wang, and Wen-Jing Xiao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02129 • Publication Date (Web): 10 Oct 2018
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Synthesis of Phenolic Glycosides: Glycosylation of
Sugar Lactols with Aryl Bromides via Dual
Photoredox/Ni Catalysis
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Hui Ye,1,2,# Cong Xiao,3,# Quan-Quan Zhou,1 Peng George Wang3,* and Wen-Jing Xiao1,2,*
1 CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides and Chemical Biology, Ministry
of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan
430079, China
2 Hubei Key Laboratory for Processing and Application of Catalytic Materials, Huanggang Normal
University, Huanggang 438000, China
3 Department of Chemistry, Georgia State University, Atlanta GA 30302-4098, USA
*Email: pwang11@gsu.edu; wxiao@mail.ccnu.edu.cn
#These two authors contributed equally to this work.
Ir
Ni
O
O
H
(PgO)n
Ar-Br
O
Ar
(PgO)n
O
22 examples
up to 93% yield
Multifarious sugar lactols were efficiently transformed into the corresponding phenolic glycosides by
treating with aryl bromides in acetonitrile with Ir[dF(CF3)ppy]2(dtbbpy)(PF6) as photocatalyst under
visible light irradiation. Both pyranoses and furanoses or even disaccharide could all suffer this
glycosylation protocol under mild reaction conditions. A variety of phenyl glycoside can be produced in
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moderate to good yields (up to 93% yield). And a gram scale process of this protocol was also well
established.
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INTRODUCTION
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Phenolic glycosides are compounds with carbohydrate units attached to aryl units through the C-O bond
linkage. It is a class of important organic compounds and encompass a vast number of secondary
metabolites, such as vancomycin and chromomycin.1 Since phenolic glycoside was firstly reported in
1879,2 a massive effort has been devoted toward their synthesis by varying different glycosyl donors
(i.e., anomeric acetates, glycosyl halides, trichloroacetimidates and thioglycosides, et al.) and
corresponding activation conditions3 because of their diverse biological activities and pharmaceutical
potentials4. The previous strategies of glycosylation were commonly built upon the electrophilic/cationic
species by releasing somewhat leaving group, such as bromides, trichloroacetimidates, thioglycosides, et
al. (Scheme 1a). Lately, Ye and co-workers have also been dedicated to the continuous development of
highly efficient aromatic O-glycosylation with 1,2-anhydro-sugar and aryl boronic acids (Scheme 1b).5a
In the same year, Olofsson et al. disclosed a novel methodology for O-functionalization of carbohydrate
derivatives using bench-stable and easily prepared iodonium (III) reagents (Scheme 1c).5b However,
because of the electron-withdrawing properties of aromatic rings, phenols are often difficult to be
glycosylated. The existing methods suffer from some drawbacks such as needing pre-preparation of
reactive substrates or reagents (Scheme 1a and 1c) or limited substrate scope (Scheme 1b). Thus, the
development of efficient and alternavtive protocols towards phenolic glycosides are still highly desired.
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Scheme 1. Synthetic Methods for Phenolic Glycoside (Pg = protecting group, L = leaving group)
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(a) Glycosylation by leaving group formation (Koenigs and Knorr, 1901; Schmidt,
1980; van der Marel, 2005; Yu, 2001, 2008; et al.)
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O
O
O
promoter
HO Ar
(Pg)n
(Pg)n
(Pg)n
O
Ar
OH
L
(b) Glycosylation with 1,2-anhydro sugar (Ye, 2016)
ArB(OH)2, KOtBu
O
O
OAr
(Pg)n
(Pg)n
THF, 50 C
OH
O
(c) Glycosylation via substitution reaction (Olofsson, 2016)
Ar
I
O
Ph
O
(Pg)n
OH
(Pg)n
O
Ar
OH is used directly
(d) This work: visible light induced free radical reaction
Ir
Ni
O
O
(Pg)n
O
Ar
(Pg)n
Ar-Br
OH
blue LEDs
OH is used directly
Dual catalysis by merging visible light photoredox catalysis and transition metal catalysis has
enjoyed an increasing popularity in organic synthesis since the pioneering work of Osawa and Sanford,
et al.6 In 2015, MacMillan group developed a highly efficient and general coupling reaction to forge
C-O bond through synergistic photoredox and nickel catalysis.7 In view of the appealing attributes of (i)
the synthesis of phenolic glycosides via C-O coupling and (ii) the mild conditons of dual visible-light
photoredox/Ni catalysis via SET process, we recently decided to pursue the possibility that the two
technologies could be merged to enable the synthesis of phenolic glycosides from readily available
starting materials. At present, only few photo-induced reactions about carbohydrate have been reported,8
maybe due to the complexity of the carbohydrate structures and the lack of general synthetic methods.
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Based on the importance of phenolic glycoside, we developed a dual photoredox and nickel-catalyzed
cross coupling of sugar lactols and aryl bromide under mild conditions (Scheme 1d). This protocol
provides a novel and straightforward method for the synthesis of phenyl glycoside.
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Table 1. Condition Optimization for the Model Reactiona
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Ir[dF(CF3)ppy]2(dtbbpy)(PF6) (1 mol % )
[Ni] (5 mol %), dtbbpy (5 mol %)
amine reductant (10 mol %)
OBn
O
Br
OBn
O
BnO
BnO
O
BnO
BnO
OH
O
K2CO3 (1.0 equiv)MeCN
light source, Ar, 40 C, 48 h
BnO
OBn
O
3aa
1a
2a
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Entry
1c
[Ni] source
NiCl2·glyme
Ni(OTf)2
photocatalysts
Amine reductants
quinuclidine
quinuclidine
quinuclidine
quinuclidine
quinuclidine
quinuclidine
quinuclidine
quinuclidine
DABCO
Yield [%]b
Ir[dF(CF3)ppy]2(dtbbpy)PF6
Ir[dF(CF3)ppy]2(dtbbpy)PF6
Ir[dF(CF3)ppy]2(dtbbpy)PF6
Ru(bpy)3(PF6)2
42
15
2c
3c
Ni(acac)2
trace
NA
NA
trace
NA
53
4c
NiCl2·glyme
NiCl2·glyme
NiCl2·glyme
NiCl2·glyme
NiCl2·glyme
NiCl2·glyme
NiCl2·glyme
NiCl2·glyme
-
5c
Ir(ppy)2(dtbby)PF6
6c
4CzIPN
7c
fac-Ir(ppy)3
8d
Ir[dF(CF3)ppy]2(dtbbpy)PF6
Ir[dF(CF3)ppy]2(dtbbpy)PF6
Ir[dF(CF3)ppy]2(dtbbpy)PF6
Ir[dF(CF3)ppy]2(dtbbpy)PF6
Ir[dF(CF3)ppy]2(dtbbpy)PF6
-
9d
81
10d
11d
12d,e
13d,f
14d.g
15d,h
i-Pr2NEt
49
DBU
17
DABCO
0
NiCl2·glyme
NiCl2·glyme
NiCl2·glyme
DABCO
0
Ir[dF(CF3)ppy]2(dtbbpy)PF6
Ir[dF(CF3)ppy]2(dtbbpy)PF6
-
0
DABCO
0
aReaction conditions: 1a (0.20 mmol), 2a (0.40 mmol), Ir[dF(CF3)ppy]2(dtbbpy)PF6 (1 mol %), [Ni] (5 mol %),
dtbbpy (5 mol %), amine reductant (10 mol %) and K2CO3 (0.20 mmol) in MeCN (2 mL) at 40 ℃ under argon
b
c
d
atmosphere and the irradiation of visible light for 48 h; isolated yield; 7 W blue LEDs; 2*3 W blue LEDs
eWithout [Ni] salt. Without Ir[dF(CF3)ppy]2(dtbbpy)PF6. gWithout amine reductants. hWithout visible light
f
irradiation. dtbbpy: 4,4’-di-tert-butyl-2,2’-bipyridine.
RESULTS AND DISCUSSION
Initially, we chose 2,3,4,6-tetra-O-benzyl-D-glucopyranose 1a and 4'-bromoacetophenone 2a as model
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substrates and Ir[dF(CF3)ppy]2(dtbbpy)PF6 as a photocatalyst (E*1/2 = 1.21 V vs SCE in MeCN) to test
the glycosylation reaction under the irradiation of a 7 W blue LEDs. As depicted in Table 1, this reaction
did indeed proceed with Ir[dF(CF3)ppy]2(dtbbpy)PF6 (1 mol %) and NiCl2·glyme (5 mol %)/dtbbpy (5
mol %) in MeCN at 40℃, affording the desired phenolic glycoside 3aa in 42% yield (Table 1, entry 1).
Other nickel catalysts were then examined to improve the reaction efficiency (Table 1, entries 1-3).
NiCl2·glyme was still determined to be the most suitable catalyst (Table 1, entry 1). Further study
revealed that Ir[dF(CF3)ppy]2(dtbbpy)PF6 was superior than others, such as Ru(bpy)3(PF6)2,
Ir(ppy)2(dtbby)PF6 , 4CzIPN and fac-Ir(ppy)3 (Table 1, entries 4-7). The yield was promoted to 53%
when the reaction was irradiated by 2*3 W blue LEDs (Table 1, entry 8). Screening of light sources,
solvents, bases and ligands did not further improve the reaction yield (for more details, see the
Supporting Information). It has been reported in the literature that amines, such as DABCO, i-Pr2NEt,
etc., can be used as reductive reagents to participate in the single electron transfer process.9 So, other
amine reductants (Table 1, entries 9-11) were tested for this reaction. A significant improvement has
been reached (Table 1, entry 9: 81% yield) when using DABCO (1,4-diazabicyclo[2.2.2]octane) as the
amine reductant. Control experiments indicated that nickel catalyst, photocatalyst, amine reductants and
visible light were all essential in this dual photoredox and nickel-catalyzed cross coupling reaction
(Table 1, entries 12-15).
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Scheme 2. Variation of the Sugar Lactolsa,b
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Ir[dF(CF3)ppy]2(dtbbpy)(PF6) (1 mol %)
NiCl2 glyme (5 mol %), dtbbpy (5 mol %)
DABCO (10 mol %), K2CO3 (1.0 equiv)
Br
O
O
(BnO)n
O
(BnO)n
OH
O
MeCN, 2*3 W blue LEDs
O
Ar, 40 C, 48 h
3aa-3ja
1a-1j
2a
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OBn
BnO
OBn
O
O
BnO
BnO
O
BnO
O
OBn
BnO
O
O
3ba
3aa
81%,   8:1
82%,   2:1
OBn
O
O
BnO
BnO
BnO
BnO
BnO
BnO
O
O
O
O
3da
3ca
93%,  only
88%,   10:1
O
O
OBn
O
O
O
BnO
BnO
O
BnO
OBn
3ea
56%,  only
OBn
3fa
59%,  only
O
O
OBn
O
O
O
BnO
O
OBn
OBn
OBn
BnO
OBn
3ga
54%,  only
3ha
65%,  noly
OBn
O
BnO
BnO
BnO
OBn
O
O
BnO
O
O
BnO
BnO
O
OBn
O
BnO
3ja
O
3ia
60%,  only
46%,   2:1
OAc
O
OMe
O
AcO
AcO
MeO
MeO
O
O
AcO
MeO
O
O
3la
0%
3ka
82%,   2:1
a Unless otherwise noted, 1 (0.20 mmol), 2a (0.40 mmol), Ir[dF(CF3)ppy]2(dtbbpy)PF6 (1 mol %), NiCl2·glyme (5 mol
%), dtbbpy (5 mol %), DABCO (10 mol %) and K2CO3 (0.20 mmol) in MeCN (2 mL) at 40℃ under argon atmosphere
and the irradiation of 2*3 W blue LEDs for 48 h; b isolated yield and the α/β ratio was determined by 1H NMR analysis.
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With the optimal conditions in hand, we probed the generality of this phenolic glycosidation
protocol. As highlighted in Scheme 2, a variety of structurally diverse armed sugar lactols (Bn protecting
group) proved to be suitable for this reaction. Both pyranoses and furanoses 1a-i were well tolerated,
and the corresponding products were obtained in moderate to good isolated yields (Scheme 2, 3aa-3ia,
54-93% yield). The pyranoses of D-configuration 1a and 1c-1d were converted smoothly in good yields
(81-93%) with high α-stereoselectivity (3aa, α/β = 8:1; 3ca, α/β = 10:1; 3da, α only). The reaction of 1b
and 4'-bromoacetophenone 2a gave the corresponding glycoside in 82% yield but moderate
α-stereoselectivity (α/β = 2:1). In addition, the furanose of D configuration D-ribose 1i could also
participate in this coupling reaction under the optimized condition (Scheme 2, 3ia, 60% yield, α only). It
is worthy to note that variation of configuration of the sugar substrates has been proven feasible.10
Therefore, when the sugar substrates were changed to L configuration, phenolic glycosides were given
in acceptable yields (Scheme 2, 3ea: 56% yield, β only; 3fa-3ha, 54-65% yield, α only). Moreover,
disaccharide substrate 1j was also examined and could be successfully transformed into phenolic
glycoside products 3ja in modest yields and α-stereoselectivity (46%, α/β = 2:1). Meanwhile, armed
sugar lactol 1k with methyl protecting group could also tolerate this glycosylation protocol, affording
the desired proeuct 3ka in good yield (81%) and moderate α-stereoselectivity (α/β = 2:1). However,
disarmed sugar lactol 1l with Ac protecting group was ineffective under our standard conditions. Most
of the products are mainly in α configuration, probably because the anomeric effect and long reaction
time (48 h) facilitate the formation of a more stable α-anomer.11
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Next, we investigated the photochemical glycosylation reactions of sugar lactol 1 with a variety of
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aryl bromides. As summarized in Scheme 3, this dual catalytic system exhibited a certain substrate scope
with respect to sugar lactols. In addition to 1, a set of representative aryl bromides with diverse
electron-withdrawing substituents (e.g., CN, MeSO2, CO2Et) on the phenyl ring proved to be suitable for
the reaction; and the expected products 3ab, 3cb, 3fb, 3ac, 3bc and 3ad were obtained in 32-71% yields
and moderate to good α-stereoselectivity (3ab, 55%, α/β = 1:0.6; 3cb, 45%, α/β = 5:1; 3fb, 32%, α only;
3ac, 71%, α/β = 1:0.4; 3bc, 43%, α/β = 1:0.3; 3ad, 35%, α/β = 1:0.75). The moderate yield of 3ae
resulted from the low conversion of 2e, which contained a disubstituted phenyl ring (3ae, 53%, α/β =
3:1). Moreover, as shown in the synthesis of 3af and 3bf, nitrogen-containing aromatic rings such as
pyridine could also be well accommodated (3af, 35%, α/β = 1:0.3; 3bf, 39%, α/β > 10:1). Note that aryl
bromides with electron-neutral substituents (bromobenzene 2g and 2-bromonaphthalene 2h) could also
suffer this glycosylation protocol in acceptable yield and good α-stereoselectivity (3ag, 33%, α/β = 5:1;
3ah, 26%, α/β = 2:1). Unfortunately, this reaction could not occur when we replaced 2a with
4-bromotoluene (2i), which contained an electron-donating group.
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To further demonstrate the synthetic potential of this protocol, we performed a gram-scale process
to the model reaction of 1a and 2a under standard conditions (Scheme 4). Delightedly, the reaction
proceeded well to afford phenolic glycoside 3aa in good yield with high α-stereoselectivity (82%, α/β =
8:1).
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Scheme 3. Variation of Aryl Bromide Scopea,b
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Ir[dF(CF3)ppy]2(dtbbpy)(PF6) (1 mol % )
NiCl2 glyme (5 mol %), dtbbpy (5 mol %)
DABCO (10 mol %), K2CO3 (1.0 equiv)
X
O
X
O
Br
Y
(BnO)n
O
Y
(BnO)n
OH
MeCN, 2*3 W blue LEDs
2
3
1
Ar, 40 C, 48 h
OBn
O
OBn
O
BnO
BnO
BnO
BnO
BnO
O
CN
O
CN
BnO
3ab
3cb
45%,   5:1
55%,   1:0.6
OBn
O
O
O
CN
O
S
BnO
BnO
BnO
O
BnO
BnO
3ac
71%,   1:0.4
OBn
3fb
32%,  only
O
OBn
O
OBn
O
BnO
BnO
O
BnO
BnO
O
CO2Et
O
S
BnO
BnO
O
3ad
3bc
35%,   1:0.75
43%,   1:0.3
OBn
O
OBn
O
F
BnO
BnO
BnO
BnO
O
O
CN
BnO
3ae
BnO
3af
N
CF3
53%,   3:1
35%,   1:0.3
OBn
O
OBn
O
BnO
BnO
BnO
BnO
O
CN
O
BnO
BnO
3ag
N
3bf
33%,   5:1
39%,   10:1
OBn
O
OBn
O
BnO
BnO
BnO
BnO
O
O
Me
BnO
3ah
26%,   1:1
BnO
3ai
0%
aUnless otherwise noted, 1 (0.20 mmol), 2 (0.40 mmol), Ir[dF(CF3)ppy]2(dtbbpy)PF6 (1 mol %), NiCl2·glyme (5 mol
%), dtbbpy (5 mol %), DABCO (10 mol %) and K2CO3 (0.20 mmol) in MeCN (2 mL) at 40℃ under argon atmosphere
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and the irradiation of 2*3 W blue LEDs for 48 h; bisolated yield and the α/β ratio was determined by 1H NMR analysis.
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Scheme 4. Gram Scale Reaction
OBn
Ir[dF(CF3)ppy]2(dtbbpy)(PF6) (1 mol % )
NiCl2 glyme (5 mol %), dtbbpy (5 mol %)
DABCO (10 mol %), K2CO3 (1.0 equiv)
OBn
O
Br
O
BnO
BnO
O
BnO
BnO
OH
O
BnO
3aa
MeCN (30 mL), 2*3 W blue LEDs
OBn
O
Ar, 40 C, 48 h
1a
: 4 mmol
2.16 g
: 2.17 g
82% yield, / = 8:1
2a
: 8 mmol
1.58 g
On the basis of our observations and related literatures,7 a plausible mechanism for this
glycosylation reaction was proposed in Scheme 5. Initially, the aryl bromides 2 underwent an oxidative
addition to chiral Ni(0) catalyst and generated a Ni(II) aryl complex B. At this stage, ligand exchange
(displacement of the aryl bromide ion with the sugar lactols) would produce the Ni(II) aryl alkoxide (C).
In addition, visible light irradiation of iridium(III) photocatalyst Ir[dF(CF3)ppy]2(dtbbpy)PF6 could
produce the long-lived photoexcited *IrIII species. At this juncture, the nickel and photoredox cycles
would merge via SET process between the Ni(II) complex C and the excited state of Ir(III) photocatlyst,
generating Ni(III) aryl alkoxide D and the reduced state of Ir(II) photocatalyst. Intermediate D then
undergoes a reductive elimination to forge the desired C-O bond and provides the final product 3 and
Ni(I) complex E. Finally, reduction of Ni(I) to Ni(0) by Ir(II) species completed the catalytic cycles.
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Scheme 5. A Proposed Mechanism
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O
(BnO)n
(Su)
OH
Br
1
LnNiII Ar
B
Ar-Br
SuO NiIILn
2
Ar
C
LnNi0
A
*IrIII
IrIII
Photoredox
Catalysis
IrII
Br
LnNiI
Br
SuO NiIIILn
E
Ar
D
O
(BnO)n
O
Ar
3
CONCLUSIONS
In conclusion, a novel glycosylation reaction for phenolic glycosides has been developed via dual
photoredox/Ni catalysis using multifarious sugar lactols and aryl bromides as starting materials. Through
this method, a wide range of significant phenolic glycosides can be efficiently synthesized under mild
reaction conditions. It is believed that, this method represents a valuable addition to the existing modern
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synthetic arsenal to phenolic glycosides of interests, thereby facilitating their potential applications in
carbohydrate synthesis.
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EXPERIMENTAL SECTION
General Information. Unless otherwise noted, substrates 2 and other materials were purchased from
commercial suppliers and used without further purification. All solvents were treated using known
methods. Substrates 1a-1c were commercially available, and the other substrates (1d-1l) were prepared
according to the procedures in the literature.10,
NMR spectra were measured at 400 MHz
12-14
spectroscopies with CDCl3 as solvent. The chemical shifts (δ) are reported in parts per million using the
solvent resonance as the internal standard (CDCl3: 7.26 ppm). The data are reported as follows: chemical
shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublets, m =
13
multiplet), coupling constants (Hz), and integration. The C NMR spectra were recorded at 400 (100
MHz) with complete proton decoupling spectrophotometers (CDCl3: 77.0 ppm). High-resolution mass
spectra (HRMS) were equipped with an ESI source and a TOF detector. The IR spectra was determined
by IR instrument. The melting points were measured with a digital melting point detector.
General procedure for preparation of monosaccharide substrates.
allyl saccharide (4). Unprotected monosaccharide (6.7 mmol) was dissolved in allyl alcohol (8 mL),
Amberlite IR 120 (H+) (0.6 g) was added at room temperature. Then, the mixture was stirred at 90℃ for
4 h. The ion exchanger was filtered off, and the excess of allyl alcohol was removed by vacuum
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distillation. The crude product was purified by flash column chromatography (CH2Cl2:MeOH = 20:1) to
give 4 as a white solid.
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fully protected saccharide (5). NaH (60% in oil, 29.2 mmol) was added in small portions at 0℃ to
a solution of 4 (5.8 mmol) in anhydrous DMF (15 mL). After that, the mixture was stirred at 0℃ for 30
min. Then BnBr (29.2 mmol) was added dropwise and the mixture was stirred at ambient temperature
overnight. The reaction mixture was carefully quenched with H2O at 0℃, diluted with Et2O (50 mL) and
then washed with water (20 mL × 3). The organic layer was washed with brine, dried over anhydrous
Na2SO4, filtered and concentrated under reduced pressure. The crude residue was purified by flash
column chromatography on silica gel (petroleum:EtOAc = 10:1) to afford 5 as a colorless oil.
sugar lactol (1). To a mixture of 5 (3.3 mmol) in anhydrous MeOH (20 mL) was added PdCl2 (0.65
mmol), then the mixture was stirred vigorously for 5 h at room temperature until consumption of 5 was
observed by TLC. The mixture was then diluted with Et2O (20 mL), filtered through celite and
concentrated under reduced pressure. The crude residue was purified by flash column chromatography
on silica gel (petroleum ether:EtOAc = 20:1→5:1) to afford 1.
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2,3,4-Tri-O-benzyl-α/β-D-xylopyranose (1d). Colorless oil, α/β = 1:0.3; [α]20 = +19.1 (c 1.0,
D
CHCl3); 1H NMR (400 MHz, CDCl3) δ (ppm) = 7.36–7.27 (m, 23H), 5.10 (t, J = 3.4 Hz, 1H), 4.90–4.83
(m, 3.3H), 4.75 (t, J = 8.0 Hz, 2H), 4.69 (d, J = 8.0 Hz, 2H), 4.66–4.60 (m, 2H), 3.94 (dd, J = 11.6, 4.4
Hz, 0.3H), 3.86 (t, J = 8.0 Hz, 2H), 3.79 (t, J = 8.0 Hz, 2H), 3.66 (dd, J = 12.0, 4.0 Hz, 2H), 3.63–3.51
(m, 2H), 3.48 (dd, J = 8.0, 4.0 Hz, 1H), 3.40 (d, J = 5.6 Hz, 0.3H), 3.33–3.23 (m, 0.6H), 3.05 (d, J = 3.2
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ (ppm) = 138.8, 138.3, 137.9, 128.6, 128.6, 128.6, 128.5, 128.2,
128.2, 128.1, 128.1, 127.9, 127.9, 127.8, 97.9, 91.6, 83.3, 82.4, 79.6, 77.7, 77.6, 75.6, 74.9, 73.6, 73.4,
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73.3, 63.9, 60.5; IR (in KBr): 3445, 3129, 3014, 1637, 1542, 1400, 1093 cm-1; HRMS (ESI-TOF) m/z:
[M + Na]+ calcd for C26H28O5Na 443.1829, found 443.1824.
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2,3,4-Tri-O-benzyl-α/β-L-rhamnose (1f). Colorless oil, α/β = 1:1; [α]20D = -13.3 (c 1.0, CHCl3); 1H
NMR (400 MHz, CDCl3) δ (ppm) = 7.38–7.27 (m, 30H), 5.16–5.09 (m, 2H), 4.94 (dd, J = 11.2, 5.9 Hz,
2H), 4.79–4.51 (m, 10H), 3.92 (d, J = 11.7 Hz, 2H), 3.83 (d, J = 11.7 Hz, 2H), 3.66–3.56 (m, 4H), 3.36
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(s, 1H), 2.73 (s, 1H), 1.33 (t, J = 7.5 Hz, 6H); C NMR (100 MHz, CDCl3) δ (ppm) = 138.7, 138.7,
138.4, 138.4, 138.2, 138.1, 128.8, 128.7, 128.5, 128.5, 128.4, 128.2, 128.2, 128.1, 128.1, 128.0, 127.9,
127.8, 127.8, 127.8, 127.7, 93.5, 93.1, 83.2, 80.6, 80.1, 79.8, 77.4, 76.7, 75.6, 75.5, 75.1, 75.0, 73.0, 72.4,
71.7, 68.3, 18.2, 18.1; IR (in KBr): 3445, 3129, 3030, 2928, 2361, 2341, 1453, 1400, 1094, 747, 695
cm-1; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C27H30O5Na 457.1985, found 457.1980.
2,3,4-Tri-O-benzyl-α/β-L-fucose (1g). Colorless oil, α/β = 2.5:1; [α]20 = -24.0 (c 1.0, CHCl3); H
1
D
NMR (400 MHz, CDCl3) δ (ppm) = 7.40–7.27 (m, 21H), 5.26 (d, J = 3.4 Hz, 1H), 5.00–4.91 (m, 2H),
4.83–4.61 (m, 7.6H), 4.10 (dd, J = 12.0, 8.0 Hz, 1H), 3.89 (dd, J = 10.0, 2.4 Hz, 1H), 3.74 (t, J = 8.6 Hz,
0.5H), 3.66 (s, 1H), 3.58–3.51 (m, 1.3H), 3.27 (d, J = 7.1 Hz, 0.4H), 2.99 (s, 1H), 1.19 (d, J = 6.4 Hz,
13
1.3H), 1.14 (d, J = 6.5 Hz, 3H); C NMR (100 MHz, CDCl3) δ (ppm) = 138.8, 138.6, 138.3, 128.5,
128.5, 128.3, 128.3, 128.1, 128.0, 127.8, 127.8, 127.7, 127.7, 127.6, 97.8, 92.0, 82.6, 80.9, 79.2, 77.4,
77.4, 76.6, 76.5, 75.2, 74.9, 74.8, 73.6, 73.2, 73.1, 70.9, 66.8, 17.1, 16.9; IR (in KBr): 3367, 3131, 3032,
2935, 2361, 2340, 1453, 1400, 1365, 1140, 1106, 1054, 731, 696 cm-1; HRMS (ESI-TOF) m/z: [M +
Na]+ calcd for C27H30O5Na 457.1985, found 457.1985.
General procedure for preparation of disaccharide substrates 1j 10b
.
1,2,3,6,2',3',4',6'-octa-O-acetyl-D-maltose (6). D-(+)-Maltose monohydrate (2.1 g, 5.8 mmol) was
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suspended in dry pyridine (7.5 mL, 93.4 mmol) and acetic anhydride (6.6 mL, 70.1 mmol) and a
catalytic amount of 4-dimethylaminopyridine was added. The solution was stirred at ambient
temperature for 16 h. The reaction mixture was diluted with ethyl acetate and washed successively with
1 N HCl (20 mL) and saturated aq. NaHCO3 (20 mL). The resulting organic phase was dried (anhydrous
Na2SO4), filtered and the filtrate concentrated under reduced pressure to afford 6 (3.9 g, 98%) as a white
solid.
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Allyl 2,3,6,2',3',4',6'-hepta-O-acetyl-D-maltose (7). 6 (3.9 g, 5.7 mmol) was dissolved in
dichloromethane (30 mL), allyl alcohol (1.2 mL, 17.2 mmol) and boron trifluoride diethyl etherate (2.2
mL, 17.2 mmol) were added to the solution at 0 ℃ . The resulting solution was stirred at ambient
temperature under nitrogen atmosphere. The reaction was monitored by TLC and appeared to be
complete after 6 h. The reaction mixture was diluted with dichloromethane (20 mL) and successively
washed with saturated aq NaHCO3 (100 mL), 10% aq NaCl (30 mL), and water (30 mL). The resulting
organic phase was dried (anhydrous Na2SO4), filtered and the filtrate was concentrated under reduced
pressure to afford 7 (2.5 g, 65%) as a colorless oil.
Allyl 4-O-α-D-glucopyranosyl-α/β-D-glucopyranose (8). 7 (2.5 g, 3.7 mmol) was dissolved in dry
methanol (25 mL) followed by addition of MeONa (20 mg, 0.37 mmol) until the solution reached pH 9.
The reaction was monitored for completion using TLC. The reaction was neutralized by adding
Amberlite IR 120 H+ resin until the pH reached 7. Then resin was filtered away and the filtrate
concentrated under reduced pressure to afford the 8 (1.4 g, quantitative yield) as a white solid.
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The Preparation of Allyl 2,3,6-Tri-O-benzyl-4-O-(2',3',4',6'-tetra-O-benzyl-α-Dglucopyranosyl)-
α/β-D-glucopyranoside 9 and disaccharide substrates 1j were according to the general procedure for
preparation of monosaccharide substrates.
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2,3,6-Tri-O-benzyl-4-O-(2',3',4',6'-tetra-O-benzyl-a-Dglucopyranosyl)-α/β-D-glucopyranoside (1j).
α/β = 2:1, colorless oil; 1H NMR (400 MHz, CDCl3) δ (ppm) = 7.29-7.20 (m, 27H), 7.19-7.16 (m, 5H),
7.14-7.10 (m, 2H), 5.62 (d, J = 3.6 Hz, 1H), 5.22 (d, J = 3.6 Hz, 0.7H), 4.96–4.84 (m, 3H), 4.81-4.74 (m,
3H), 4.67–4.63 (m, 1H), 4.60–4.48 (m, 5.7H), 4.43 (dd, J = 10.8, 2.8 Hz, 1H), 4.32 (t, J = 12.4 Hz, 1H),
4.12 (d, J = 8.0 Hz,1H), 4.08–3.99 (m, 1.7H), 3.89 (dd, J = 16.0, 8.0 Hz, 1H), 3.84–3.71 (m, 2.7H), 3.69
13
– 3.61 (m, 3H), 3.57–3.39 (m, 3.7H), 3.09 (br, 0.7H); C NMR (100 MHz, CDCl3) δ (ppm) = 138.8,
138.7, 138.7, 138.4, 138.1, 138.0, 137.9, 137.9, 137.6, 128.5, 128.4, 128.4, 128.3, 128.3, 128.2, 128.2,
128.2, 128.1, 128.0, 127.9, 127.9, 127.8, 127.8, 127.8, 127.7, 127.7, 127.6, 127.6, 127.6, 127.5, 127.5,
127.2, 126.7, 126.6, 97.4, 97.0, 96.9, 90.8, 84.4, 83.1, 82.0, 81.4, 80.0, 79.4, 79.2, 77.6, 77.3, 75.6, 75.0,
75.0, 74.6, 74.3, 74.3, 73.9, 73.5, 73.3, 73.3, 73.2, 73.1, 72.9, 72.7, 71.2, 71.0, 69.8, 69.4, 69.1, 68.1;
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C61H64O11Na 995.4341, found 995.4346.
General Procedure for the Synthesis of product 3. NiCl2·glyme (2.2 mg, 0.01 mmol) and
4,4'-di-tert-butyl-2,2'-bipyridine (dtbbpy, 2.7 mg, 0.01 mmol) were dissolved in MeCN (2.0 mL) and the
mixture was stirred at room temperature for 10 min. Then aryl bromide 2 (0.4 mmol),
Ir[dF(CF3)ppy]2(dtbbpy)PF6 (2.2 mg, 0.002 mmol), 1,4-diazabicyclo[2.2.2]octane (DABCO, 2.2 mg,
0.02 mmol), K2CO3 (27.6 mg, 0.2 mmol) and sugar lactol 1 (0.2 mmol) were added, and the resulting
mixture was degassed via ‘freeze-pump-thaw’ procedure (3 times) under argon atmosphere. After that,
the solution was stirred at a distance of ~3 cm from a 2*3W blue LEDs (30 mW/cm2) at 40℃ about 48 h
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until the reaction was completed, as monitored by TLC analysis. After removing the solvent MeCN
under reduced pressure, the crude product was purified by flash chromatography on silica gel (petroleum
ether:EtOAc = 20:1→5:1) to give the desired product 3.
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4-Acetylphenyl 2,3,4,6-tetra-O-benzyl-α/β-D-glucopyranoside (3aa). 107 mg, 81% yield, α/β = 8:1,
1
white solid, m.p. 108-109 ℃; [α]20 = +96.6 (c = 1.0, CHCl3); H NMR (400 MHz, CDCl3) δ (ppm) =
D
7.96–7.87 (m, 2H), 7.44–7.21 (m, 21H), 7.15–7.05 (m, 4H), 5.49 (d, J = 3.5 Hz, 1H), 5.06 (d, J = 10.7
Hz, 1H), 4.96–4.77 (m, 4H), 4.65 (d, J = 12.1 Hz, 1H), 4.58 (d, J = 12.0 Hz, 1H), 4.47 (d, J = 10.7 Hz,
1H), 4.39 (d, J = 12.0 Hz, 1H), 4.20 (ddd, J = 9.1, 7.2, 1.5 Hz, 1H), 3.86–3.64 (m, 5H), 3.53 (dd, J =
13
10.7, 1.5 Hz, 1H), 2.56 (s, 3H); C NMR (100 MHz, CDCl3) δ (ppm) = 196.9, 196.9, 161.0, 160.4,
138.7, 138.4, 138.1, 138.0, 138.0, 137.9, 137.7, 131.9, 131.6, 130.6, 130.5, 128.6, 128.6, 128.5, 128.5,
128.5, 128.4, 128.3, 128.1, 128.1, 128.0, 128.0, 128.0, 128.0, 127.9, 127.8, 127.8, 127.8, 116.2, 100.8,
95.2, 84.6, 81.9, 81.9, 79.6, 77.6, 77.4, 76.0, 75.9, 75.3, 75.3, 75.2, 73.7, 73.6, 73.5, 71.2, 68.7, 68.0,
26.5; IR (in KBr): 3062, 3027, 2928, 1669, 1598, 1451, 1358, 1240, 1083, 736, 696 cm-1; HRMS
(ESI-TOF) m/z: [M + Na]+ calcd for C42H42O7Na 681.2823, found 681.2809.
4-Acetylphenyl 2,3,4,6-tetra-O-benzyl-α/β-D-galactopyranoside (3ba). 108 mg, 82% yield, α/β =
2:1. 3ba-α: white solid, m.p. 105-106 ℃; [α]20D = +33.2 (c = 0.33, CHCl3); 1H NMR (400 MHz, CDCl3)
δ (ppm) =7.95–7.85 (m, 2H), 7.48–7.20 (m, 18H), 7.16 (dd, J = 7.4, 2.2 Hz, 2H), 7.13–7.05 (m, 2H),
5.53 (d, J = 3.6 Hz, 1H), 4.98 (d, J = 11.3 Hz, 1H), 4.94–4.76 (m, 3H), 4.68 (d, J = 12.0 Hz, 1H), 4.59 (d,
J = 11.3 Hz, 1H), 4.33 (dd, J = 24.0, 11.6 Hz, 2H), 4.22 (dd, J = 10.0, 3.6 Hz, 1H), 4.14 (dd, J = 10.1,
2.7 Hz, 1H), 4.05 (d, J = 2.7 Hz, 1H), 4.00 (t, J = 6.5 Hz, 1H), 3.56 (dd, J = 9.3, 6.5 Hz, 1H), 3.46 (dd, J
= 9.3, 6.5 Hz, 1H), 2.55 (s, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm) = 197.0, 160.9, 138.7, 138.6,
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138.3, 137.8, 131.6, 130.5, 128.6, 128.5, 128.5, 128.4, 128.4, 128.1, 128.0, 127.9, 127.8, 127.7, 127.6,
116.5, 96.1, 79.0, 77.4, 76.1, 75.1, 74.8, 73.8, 73.5, 73.4, 70.5, 68.6, 26.6; IR (in KBr): 3447, 3128, 3030,
2920, 2866, 2361, 1679, 1600, 1400, 1240, 1100, 1063, 737, 698 cm-1; HRMS (ESI-TOF) m/z: [M +
Na]+ calcd for C42H42O7Na 681.2823, found 681.2818. 3ba-β: colorless oil; 1H NMR (400 MHz, CDCl3)
δ (ppm) = 7.94–7.84 (m, 2H), 7.44–7.21 (m, 20H), 7.13–7.00 (m, 2H), 5.06 (d, J = 7.7 Hz, 1H), 4.97 (dd,
J = 11.2, 9.8 Hz, 2H), 4.87 (d, J = 10.8 Hz, 1H), 4.77 (dd, J = 12.0, 12.0 Hz, 2H), 4.65 (d, J = 11.7 Hz,
1H), 4.42 (dd, J = 24.0, 11.6 Hz, 2H), 4.14 (dd, J = 9.7, 7.6 Hz, 1H), 3.96 (d, J = 2.8 Hz, 1H), 3.71 (t, J
= 6.2 Hz, 1H), 3.68–3.52 (m, 3H), 2.55 (s, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm) = 197.0, 161.1,
138.4, 138.3, 138.3, 137.9, 131.7, 130.6, 128.6, 128.5, 128.5, 128.4, 128.4, 128.0, 127.9, 127.9, 127.9,
127.7, 116.3, 101.1, 82.1, 79.1, 77.4, 75.7, 74.7, 74.3, 73.8, 73.2, 73.2, 69.0, 26.6; IR (in KBr): 3463,
3129, 3030, 2362, 2340, 1672, 1604, 1400, 1236, 1070, 736, 695 cm-1; HRMS (ESI-TOF) m/z: [M +
Na]+ calcd for C42H42O7Na 681.2823, found 681.2815.
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4-Acetylphenyl 2,3,4,6-tetra-O-benzyl-α/β-D-mannopyranoside (3ca). 115 mg, 88% yield, α/β =
10:1. 3ca-α: white solid, m.p. 106-107 ℃; [α]20D = +65.7 (c = 1.0, CHCl3); 1H NMR (400 MHz, CDCl3)
δ (ppm) = 7.88 (d, J = 8.5 Hz, 2H), 7.42–7.22 (m, 19H), 7.20–7.14 (m, 2H), 7.06 (d, J = 8.6 Hz, 2H),
5.65 (d, J = 1.9 Hz, 1H), 4.89 (d, J = 10.7 Hz, 1H), 4.80 (dd, J = 24.0, 12.4 Hz, 2H), 4.71 (dd, J = 24.0,
12.4 Hz, 2H),, 4.62 (d, J = 11.9 Hz, 1H), 4.53 (d, J = 10.7 Hz, 1H), 4.44 (d, J = 11.9 Hz, 1H), 4.18–4.06
(m, 2H), 3.97 (t, J = 2.5 Hz, 1H), 3.78 (m, 2H), 3.65 (d, J = 9.7 Hz, 1H), 2.53 (s, 3H); 13C NMR (100
MHz, CDCl3) δ (ppm) = 196.9, 160.0, 138.4, 138.4, 138.3, 138.1, 131.6, 130.6, 128.5, 128.5, 128.4,
128.1, 128.0, 127.9, 127.8, 127.8, 127.8, 127.6, 116.1, 96.3, 79.9, 77.4, 75.3, 74.6, 74.5, 73.4, 73.1, 72.8,
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72.6, 68.9, 26.5; IR (in KBr): 3420, 3131, 3030, 2361, 1671, 1596, 1400, 1247, 1102, 749, 697 cm-1;
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C42H42O7Na 681.2823, found 681.2828.
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4-Acetylphenyl 2,3,4-tri-O-benzyl-α-D-xylopyranoside (3da). 100 mg, 93% yield, α only, colorless
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oil; [α]20 = +45.7 (c = 0.33, CHCl3); H NMR (400 MHz, CDCl3) δ (ppm) = 7.93 (d, J = 8.4 Hz, 2H),
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7.46–7.22 (m, 16H), 7.08 (d, J = 8.5 Hz, 2H), 5.40 (d, J = 3.4 Hz, 1H), 4.97 (d, J = 20.0, 12.0 Hz, 1H),
4.84 (d, J = 12.0 Hz, 1H), 4.76 (d, J = 11.6 Hz, 1H), 4.64 (t, J = 12.3 Hz, 2H), 4.11 (t, J = 8.8 Hz, 1H),
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3.64 (m, 3H), 3.54 (m, 1H), 2.57 (s, 3H; C NMR (100 MHz, CDCl3) δ (ppm) = 197.0, 160.5, 138.8,
138.2, 138.0, 131.7, 130.5, 128.6, 128.6, 128.5, 128.1, 128.1, 128.0, 128.0, 127.8, 116.3, 95.3, 81.3, 79.4,
77.8, 76.0, 73.8, 73.8, 61.0, 26.6; IR (in KBr): 3480, 3124, 3031, 3005, 2869, 2360, 2341, 1679, 1600,
1401, 1239, 1092, 1028, 739, 699, 647 cm-1; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C34H34O6Na
561.2248, found 561.2245.
4-Acetylphenyl 2,3,4-tri-O-benzyl-β-L-arabinpyranoside (3ea). 60 mg, 56% yield, β only, white
solid, m.p. 82-83 ℃; [α]20D = -8.3 (c = 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ (ppm) = 7.92 (d, J =
8.7 Hz, 2H), 7.42–7.27 (m, 15H), 7.06 (d, J = 8.8 Hz, 2H), 5.09 (d, J = 6.5 Hz, 1H), 4.85 (dd, J = 20.0,
11.0 Hz, 2H), 4.76 (d, J = 12.5 Hz, 1H), 4.70–4.67 (m, 3H), 4.13–4.07 (m, 2H), 3.80 (s, 1H), 3.65 (dd, J
= 8.6, 3.2 Hz, 1H), 3.44 (dd, J = 12.5, 1.7 Hz, 1H), 2.55 (s, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm) =
197.0, 161.0, 138.2, 138.2, 138.0, 131.6, 130.5, 128.5, 128.5, 128.2, 128.1, 127.9, 127.9, 127.8, 127.8,
116.2, 100.4, 79.0, 78.2, 77.2, 75.2, 72.4, 71.9, 71.4, 62.8, 26.5; IR (in KBr): 3447, 3133, 3031, 2860,
2797, 2361, 2339, 1675, 1603, 1401, 1240, 1080, 736, 694 cm-1; HRMS (ESI-TOF) m/z: [M + Na]+
calcd for C34H34O6Na 561.2248, found 561.2244.
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4-Acetylphenyl 2,3,4-tri-O-benzyl-α-L-rhampyranoside (3fa). 65 mg, 59% yield, α only, white solid,
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m.p. 91-92 ℃. [α]20 = -54.1 (c = 1.0, CHCl3); H NMR (400 MHz, CDCl3) δ (ppm) = 7.90 (d, J = 8.0
D
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Hz, 2H), 7.41–7.27 (m, 15H), 7.01 (d, J = 8.0 Hz, 2H), 5.54 (d, J = 2.0 Hz, 1H), 4.96 (d, J = 10.7 Hz,
1H), 4.85 (d, J = 12.0 Hz, 1H), 4.77 (d, J = 12.0 Hz, 1H), 4.72 (d, J = 4.0 Hz, 1H), 4.66 (d, J = 8.0 Hz,
1H), 4.07–4.04 (m, 1H), 3.96 (dd, J = 3.1, 2.1 Hz, 1H), 3.81–3.64 (m, 2H), 2.55 (s, 3H), 1.29 (d, J = 5.3
Hz, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm) = 196.9, 160.0, 138.4, 138.0, 131.5, 130.6, 128.6, 128.6,
128.5, 128.1, 128.1, 128.0, 127.9, 127.8, 127.8, 115.9, 96.1, 80.3, 79.8, 75.6, 74.5, 73.3, 72.6, 69.2, 26.5,
18.1; IR (in KBr): 3485, 3117, 3032, 2918, 2362, 2341, 1672, 1600, 1399, 1271, 991, 735, 698 cm-1;
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C35H36O6Na 575.2404, found 575.2409.
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4-Acetylphenyl 2,3,4-tri-O-benzyl-α-L-fucopyranoside (3ga). 60 mg, 54% yield, α only, white solid,
m.p. 74-75 ℃; [α]20 = -46.9 (c = 0.50, CHCl3); H NMR (400 MHz, CDCl3) δ (ppm) = 7.93–7.91 (m,
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2H), 7.49–7.20 (m, 15H), 7.14–7.04 (m, 2H), 5.52 (d, J = 3.6 Hz, 1H), 5.03 (d, J = 11.4 Hz, 1H), 4.95 (d,
J = 11.7 Hz, 1H), 4.85 (dd, J = 16.0, 12.0 Hz, 1H), 4.68 (dd, J = 11.8, 3.6 Hz, 2H), 4.22 (dd, J = 10.1,
3.6 Hz, 1H), 4.14 (dd, J = 10.1, 2.8 Hz, 1H), 3.91 (dd, J = 12.0, 6.5 Hz, 1H), 3.73 (dd, J = 2.9, 1.2 Hz,
1H), 2.56 (s, 3H), 1.07 (d, J = 6.5 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm) = 197.0, 161.1, 138.8,
138.5, 138.3, 131.4, 130.5, 128.6, 128.5, 128.5, 128.4, 128.1, 127.9, 127.8, 127.7, 127.6, 116.3, 96.1,
79.2, 76.0, 75.1, 73.7, 73.5, 67.7, 26.6, 16.7; IR (in KBr): 3466, 3127, 3030, 2900, 2360, 2339, 1678,
1600, 1400, 1242, 1103, 738, 697 cm-1; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C35H36O6Na
575.2404, found 575.2411.
4-Acetylphenyl 2,3,4,6-tetra-O-benzyl-α-L-gulopyranoside (3ha). 85 mg, 65% yield, α only,
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colorless oil; [α]20 = +10.9 (c = 0.50, CHCl3); H NMR (400 MHz, CDCl3) δ (ppm) = 7.90–7.87 (m,
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2H), 7.43–7.26 (m, 18H), 7.11–7.08 (m, 4H), 5.55 (dd, J = 8.1, 2.4 Hz, 1H), 4.85 (dd, J = 12.1, 1.9 Hz,
1H), 4.68 (ddd, J = 16.9, 12.1, 1.9 Hz, 2H), 4.60 – 4.49 (m, 2H), 4.45 (dd, J = 11.8, 1.8 Hz, 1H),
4.39–4.23 (m, 3H), 3.91–3.88 (m, 1H), 3.83–3.81 (m, 1H), 3.67–3.57 (m, 2H), 3.53–3.51 (m, 1H), 2.55
(s, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm) = 197.0, 161.3, 138.4, 138.2, 138.1, 137.7, 131.5, 130.5,
128.5, 128.5, 128.5, 128.2, 128.1, 128.1, 128.0, 127.9, 127.8, 116.3, 98.4, 75.8, 74.7, 74.6, 73.6, 73.6,
72.8, 72.8, 69.0, 26.6; IR (in KBr): 3063, 3030, 2914, 2871, 2361, 2338, 1678, 1601, 1504, 1454, 1399,
1359, 1243, 1080, 837, 737, 699 cm-1; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C42H42O7Na
681.2823, found 681.2827.
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4-Acetylphenyl 2,3,5-tri-O-benzyl-α-D-ribofuranoside (3ia). 65 mg, 60% yield, α only, colorless oil;
[α]20D = +1.6 (c = 0.50, CHCl3); 1H NMR (600 MHz, CDCl3) δ (ppm) = 7.92 (d, J = 8.7 Hz, 2H), 7.41 (d,
J = 8.0 Hz, 2H), 7.35–7.24 (m, 13H), 7.06 (d, J = 8.5 Hz, 2H), 5.56 (d, J = 6.9 Hz, 1H), 4.84 (d, J = 8.9
Hz, 3H), 4.73 (d, J = 12.1 Hz, 1H), 4.58 (dd, J = 20.0, 12.0 Hz, 2H), 4.17 (s, 1H), 4.00 (t, J = 10.2 Hz,
1H), 3.84 (dd, J = 11.0, 4.5 Hz, 1H), 3.65–3.61 (m, 1H), 3.56 (dd, J = 8.0, 4.0 Hz, 1H), 2.55 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ (ppm) = 197.0, 160.9, 138.7, 138.3, 138.0, 131.7, 130.6, 128.6, 128.5, 128.4,
128.0, 127.9, 127.9, 127.8, 127.7, 116.1, 98.4, 77.7, 75.2, 74.7, 74.1, 73.1, 71.7, 62.5, 26.6; IR (in KBr):
3112, 3030, 3005, 2880, 2361, 2340, 1718, 1601, 1505, 1400, 1358, 1249, 1072, 958, 837, 735, 698, 592
cm-1; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C34H34O6Na 561.2248, found 561.2250.
4-Acetylphenyl
O-(2’,3’,4’,6’-tetra-O-benzyl-α-D-glucopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-
α/β-D-glucopyranoside (3ja). 100 mg, 46% yield, α/β = 2:1. 3ja-α: colorless oil; [α]20 = +25.8 (c =
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0.33, CHCl3); 1H NMR (400 MHz, CDCl3) δ (ppm) = 7.92 (d, J = 8.3 Hz, 2H), 7.30–7.18 (m, 33H), 7.12
(d, J = 8.3 Hz, 2H), 7.07 (t, J = 4.0 Hz, 2H), 5.68 (d, J = 3.5 Hz, 1H), 5.45 (d, J = 3.4 Hz, 1H), 5.09 (d, J
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= 11.4 Hz, 1H), 4.90 (t, J = 10.0 Hz, 2H), 4.81–4.69 (m, 3H), 4.63–4.47 (m, 4H), 4.45–4.36 (m, 3H),
4.32–4.23 (m, 2H), 4.18 (t, J = 9.3 Hz, 1H), 3.91 (t, J = 9.4 Hz, 2H), 3.86–3.69 (m, 3H), 3.66 (d, J = 9.1
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Hz, 1H), 3.57–3.45 (m, 3H), 3.38 (d, J = 10.6 Hz, 1H), 2.57 (s, 3H); C NMR (100 MHz, CDCl3) δ
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(ppm) = 197.0, 160.6, 138.9, 138.8, 138.4, 138.1, 138.0, 137.9, 137.8, 131.7, 130.6, 128.6, 128.5, 128.5,
128.4, 128.4, 128.3, 128.2, 128.2, 128.0, 127.9, 127.8, 127.8, 127.7, 127.6, 127.3, 127.3, 126.9, 116.4,
97.1, 95.0, 82.1, 81.8, 80.0, 79.4, 77.7, 77.4, 75.7, 75.1, 74.7, 73.7, 73.6, 73.5, 73.1, 72.5, 71.1, 70.8,
68.7, 68.2, 26.6; IR (in KBr): 3463, 3127, 3030, 2925, 2864, 2361, 2340, 1680, 1600, 1454, 1400, 1239,
1099, 735, 697 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ calcd for C69H70O12Na 1113.4759, found
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1113.4769. 3ja-β: colorless oil; H NMR (400 MHz, CDCl3) δ (ppm) = 7.91 (d, J = 8.4 Hz, 2H),
7.36–7.13 (m, 33H), 7.13–7.03 (m, 4H), 5.65 (d, J = 3.6 Hz, 1H), 5.11 (d, J = 7.3 Hz, 1H), 4.95 (dd, J =
11.3, 6.6 Hz, 2H), 4.89 (d, J = 10.7 Hz, 1H), 4.85–4.76 (m, 3H), 4.72 (d, J = 10.8 Hz, 1H), 4.64–4.56 (m,
2H), 4.54 (s, 1H), 4.50 (s, 2H), 4.44 (d, J = 10.3 Hz, 1H), 4.35 (d, J = 12.2 Hz, 1H), 4.10 (t, J = 8.2 Hz,
1H), 3.89 (dd, J = 16.0, 9.2 Hz, 2H), 3.83–3.74 (m, 5H), 3.66 (t, J = 9.3 Hz, 1H), 3.58 (dd, J = 9.9, 3.6
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Hz, 1H), 3.52 (dd, J = 9.9, 3.6 Hz, 1H), 3.46 (d, J = 10.4 Hz, 1H), 2.57 (s, 3H); C NMR (100 MHz,
CDCl3) δ (ppm) = 197.0, 161.0, 138.7, 138.6, 138.3, 138.2, 137.9, 137.9, 137.8, 131.9, 130.7, 128.5,
128.5, 128.5, 128.4, 128.4, 128.3, 128.2, 128.2, 128.2, 128.1, 128.0, 128.0, 127.9, 127.8, 127.8, 127.7,
127.7, 127.6, 127.6, 127.3, 126.7, 116.3, 100.8, 97.2, 84.7, 82.1, 81.9, 79.3, 77.7, 77.4, 75.7, 75.2, 75.1,
75.1, 74.3, 73.6, 73.5, 73.4, 73.0, 71.3, 69.1, 68.2, 26.6; IR (in KBr): 3463, 3127, 3030, 2925, 2864,
2361, 2340, 1680, 1600, 1454, 1400, 1239, 1099, 735, 697 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ calcd
for C69H70O12Na 1113.4759, found 1113.4761.
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4-Acetylphenyl 2,3,4,6-tetra-O-methyl-α/β-D-glucopyranoside (3ka). 58 mg, 82% yield, α/β = 2:1.
3ka-α: colorless oil; 1H NMR (400 MHz, CDCl3) δ (ppm) = 7.93 (d, J = 8.9 Hz, 2H), 7.17 (d, J = 8.9 Hz,
2H), 5.71 (d, J = 3.5 Hz, 1H), 3.75–3.68 (m, 4H), 3.64–3.58 (m, 2H), 3.57 (s, 3H), 3.54–3.52 (m, 4H),
3.46 (dd, J = 10.7, 2.1 Hz, 1H), 3.42–3.34 (m, 5H), 2.56 (s, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm) =
197.0, 160.4, 131.8, 130.6, 116.3, 94.7, 83.4, 81.4, 78.9, 71.2, 70.6, 61.1, 60.7, 59.3, 59.3, 26.6; IR (in
KBr): 3128, 3030, 2928, 1669, 1600, 1454, 1400, 1239, 1099, 735, 697 cm-1; HRMS (ESI-TOF) m/z:
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[M+Na]+ calcd for C18H26O7Na 377.1571, found 377.1566. 3ka-β: colorless oil; H NMR (400 MHz,
CDCl3) δ (ppm) = 7.97–7.85 (m, 2H), 7.08–6.97 (m, 2H), 4.91 (d, J = 7.4 Hz, 1H), 3.67–3.63 (m, 7H),
3.61–3.56 (m, 1H), 3.55 (s, 3H), 3.46–3.42 (m, 1H), 3.37 (s, 3H), 3.34–3.28 (m, 1H), 3.28–3.23 (m, 2H),
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2.55 (s, 3H); C NMR (100 MHz, CDCl3) δ (ppm) = 196.9, 161.1, 131.9, 130.6, 116.2, 100.7, 86.4,
83.5, 79.1, 75.1, 71.2, 61.1, 60.8, 60.6, 59.5, 26.5; IR (in KBr): 3129, 3030, 2925, 1672, 1600, 1454,
1400, 1236, 1099, 736, 695 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ calcd for C18H26O7Na 377.1571,
found 377.1569.
4-Cyanophenyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranoside (3ab). 71 mg, 55% yield, α/β = 1:0.6,
colorless oil; 1H NMR (400 MHz, CDCl3) δ (ppm) = 7.56 (d, J = 8.6 Hz, 2H), 7.55 (d, J = 8.0 Hz, 1.2H),
7.39–7.24 (m, 32H), 7.19–7.17 (m, 1.2H), 7.13–7.06 (m, 4H), 5.41 (d, J = 3.5 Hz, 1H), 5.04 (d, J = 10.7
Hz, 1.6H), 4.96–4.80 (m, 6H), 4.60 (d, J = 12.0 Hz, 1H), 4.57 (dd, J = 23.2, 12.0 Hz, 2H), 4.51–4.46 (m,
1.6H), 4.40 (d, J = 11.3 Hz, 1H), 4.16 (t, J = 9.1 Hz, 1H), 3.80–3.64 (m, 8H), 3.52 (d, J = 10.5 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ (ppm) = 160.3, 159.8, 138.6, 138.3, 138.0, 137.8, 137.6, 134.0, 134.0,
128.6, 128.5, 128.4, 128.1, 128.1, 128.0, 128.0, 127.9, 127.9, 127.8, 127.8, 127.7, 118.9, 117.2, 105.9,
105.6, 100.7, 95.4, 84.5, 81.8, 79.6, 77.2, 77.1, 75.9, 75.8, 75.3, 75.2, 75.1, 73.7, 73.5, 73.4, 71.3, 68.6,
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68.0; IR (in KBr): 3447, 3123, 3030, 2922, 2865, 2361, 2341, 2226, 1722, 1604, 1505, 1400, 1244, 1101,
1073, 738, 698, 548 cm-1; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C41H39NO6Na 664.2670, found
664.2676.
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4-Cyanophenyl 2,3,4,6-tetra-O-benzyl-α/β-D-mannopyranoside (3cb). 58 mg, 45% yield, α/β = 5:1,
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colorless oil; [α]20 = +47.8 (c = 0.50, CHCl3); H NMR (400 MHz, CDCl3) δ (ppm) = 7.54 (d, J = 8.5
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Hz, 2.4H), 7.40–7.27 (m, 22H), 7.15 (dd, J = 7.0, 2.5 Hz, 2.4H), 7.06 (d, J = 8.6 Hz, 2H), 5.61 (s, 1H),
4.89 (d, J = 10.6 Hz, 1H), 4.80 (dd, J = 24.0, 12.4 Hz, 2.2H), 4.70 (dd, J = 20.0, 12.4 Hz, 2.2H), 4.63 (d,
J = 12.0 Hz, 1.2H), 4.51 (d, J = 10.7 Hz, 1.2H), 4.45 (d, J = 11.9 Hz, 1.2H), 4.13 (t, J = 9.4 Hz, 1.2H),
4.06 (dd, J = 9.2, 2.7 Hz, 1H), 3.95 (s, 1H), 3.79–3.73 (m, 2.4H), 3.64 (d, J = 9.6 Hz, 1.2H), 3.21–3.17
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(m, 0.2H), 3.14 (d, J = 15.2 Hz, 0.2H); C NMR (100 MHz, CDCl3) δ (ppm) = 159.3, 138.3, 138.2,
138.1, 138.0, 134.1, 128.6, 128.5, 128.5, 128.4, 128.4, 128.1, 128.0, 128.0, 127.9, 127.9, 127.8, 127.8,
127.8, 127.7, 119.0, 117.1, 105.6, 96.4, 79.7, 77.4, 75.3, 74.4, 74.2, 73.4, 73.1, 72.9, 72.6, 68.7; IR (in
KBr): 3111, 3089, 3064, 3031, 2913, 2865, 2361, 2340, 2226, 1725, 1604, 1505, 1454, 1400, 1245,
1098, 984, 837, 737, 698 cm-1; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C41H39NO6Na 664.2670,
found 664.2670.
4-Cyanophenyl 2,3,4-tri-O-benzyl-α-L-rhampyranoside (3fb). 34 mg, 32% yield, α only, colorless
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oil; [α]20 = -33.8 (c = 1.0, CHCl3); H NMR (400 MHz, CDCl3) δ (ppm) = 7.55 (d, J = 8.6 Hz, 2H),
D
7.41–7.29 (m, 15H), 7.02 (d, J = 8.6 Hz, 2H), 5.49 (d, J = 2.0 Hz, 1H), 4.96 (d, J = 10.7 Hz, 1H), 4.85 (d,
J = 12.3 Hz, 1H), 4.76 (d, J = 12.0 Hz, 1H), 4.68 (dd, J = 22.0, 10.0 Hz, 3H), 4.02 (dd, J = 8.0, 2.0 Hz,
1H), 3.94 (t, J = 2.6 Hz, 1H), 3.74–3.64 (m, 2H), 1.29 (d, J = 5.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
δ (ppm) = 159.4, 138.3, 138.3, 137.9, 134.1, 128.6, 128.6, 128.5, 128.1, 128.1, 128.0, 127.9, 127.9,
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127.8, 119.1, 116.8, 105.4, 96.3, 80.1, 79.6, 75.6, 74.4, 73.3, 72.6, 69.4, 18.1; IR (in KBr): 3111, 3089,
3064, 3031, 2913, 2865, 2361, 2340, 2226, 1725, 1604, 1505, 1454, 1400, 1245, 1098, 984, 837, 737,
698 cm-1; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C34H33NO5Na 558.2251, found 558.2263.
4-Methylsulfonylphenyl 2,3,4,6-tetra-O-benzyl-α/β-D-glucopyranoside (3ac). 98 mg, 71% yield,
α/β = 1:0.4, colorless oil; [α]20D = +27.8 (c = 0.33, CHCl3); 1H NMR (400 MHz, CDCl3) δ (ppm) = 7.85
(d, J = 8.6 Hz, 2.8H), 7.41–7.23 (m, 28H), 7.21–7.17 (m, 3.4H), 7.14–7.11 (m, 2.8H), 5.46 (d, J = 3.4
Hz, 1H), 5.06 (t, J = 10.9 Hz, 1.4H), 4.98–4.92 (m, 1.2H), 4.89–4.82 (m, 3.6H), 4.60–4.54 (m, 1.6H),
4.49 (t, J = 11.8 Hz, 1.4H), 4.40 (d, J = 12.0 Hz, 1H), 4.18 (t, J = 9.1 Hz, 1H), 3.83–3.66 (m, 6.4H), 3.53
(d, J = 10.7 Hz, 1H), 3.02 (s, 3H), 3.01 (s, 1.2H); 13C NMR (100 MHz, CDCl3) δ (ppm) = 160.7, 138.6,
138.0, 137.9, 137.9, 137.8, 137.6, 133.9, 129.6, 129.5, 128.6, 128.6, 128.5, 128.5, 128.5, 128.3, 128.2,
128.2, 128.1, 128.0, 128.0, 128.0, 127.9, 127.9, 127.9, 127.8, 127.8, 117.0, 117.0, 100.8, 95.5, 84.6, 81.8,
81.8, 79.5, 77.4, 77.0, 76.0, 75.9, 75.3, 75.2, 73.8, 73.5, 71.3, 68.6, 67.9, 44.8, 44.8; IR (in KBr): 3125,
3030, 2924, 2865, 2360, 1634, 1594, 1541, 1496, 1454, 1401, 1316, 1242, 1148, 738, 698 cm-1; HRMS
(ESI-TOF) m/z: [M + Na]+ calcd for C41H42O8SNa 717.2493, found 717.2496.
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4-Methylsulfonylphenyl 2,3,4,6-tetra-O-benzyl-α/β-D-galactopyranoside (3bc). 60 mg, 43% yield,
α/β = 1:0.3, colorless oil; [α]20D = +34.8 (c = 0.67, CHCl3); 1H NMR (400 MHz, CDCl3) δ (ppm) = 7.83
(d, J = 8.0 Hz, 2.4H), 7.44–7.23 (m, 28H), 7.20–7.17 (m, 5H), 5.51 (d, J = 3.5 Hz, 1H), 5.05 (d, J = 7.6
Hz, 0.2H), 4.98 (d, J = 11.3 Hz, 1.4H), 4.90 (d, J = 12.0 Hz, 1H), 4.82 (dd, J = 24.0, 11.7 Hz, 2.2H),
4.68 (d, J = 11.3 Hz, 1.2H), 4.59 (d, J = 8.0 Hz, 1.2H), 4.41–4.30 (m, 2.8H), 4.23 (dd, J = 10.0, 3.5 Hz,
1.2H), 4.17–4.11 (m, 1.4H), 4.06 (s, 1.2H), 3.97 (t, J = 6.3 Hz, 1.2H), 3.72 (t, J = 6.3 Hz, 0.2H),
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3.66–3.59 (m, 0.4H), 3.55 (dd, J = 9.2, 7.1 Hz, 1.4H), 3.45 (dd, J = 9.3, 5.9 Hz, 1H), 2.99 (s, 4H); C
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NMR (100 MHz, CDCl3) δ (ppm) = 161.2, 161.1, 138.6, 138.4, 138.3, 138.2, 138.2, 138.2, 137.7, 133.9,
133.7, 129.5, 129.5, 128.6, 128.6, 128.5, 128.5, 128.5, 128.5, 128.4, 128.4, 128.4, 128.3, 128.3, 128.1,
128.0, 128.0, 128.0, 127.9, 127.9, 127.9, 127.8, 127.8, 127.7, 127.7, 127.6, 117.3, 117.0, 101.0, 96.4,
82.0, 78.9, 78.8, 77.4, 76.0, 75.7, 75.0, 74.7, 74.6, 74.2, 73.9, 73.7, 73.5, 73.3, 73.1, 73.0, 70.7, 68.8,
44.9, 44.8; IR (in KBr): 3125, 3030, 2923, 2867, 2361, 2340, 1720, 1593, 1495, 1454, 1400, 1314, 1243,
1148, 1096, 738, 698 cm-1; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C41H42O8SNa 717.2493, found
717.2492.
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4-Ethyl 2,3,4,6-tetra-O-benzyl-α/β-D-glucopyranosyl phenylacetate (3ad). 48 mg, 35% yield, α/β =
1:0.75, colorless oil; 1H NMR (400 MHz, CDCl3) δ (ppm) = 8.01–7.98 (m, 3.5H), 7.41–7.24 (m, 40H),
7.13–7.06 (m, 6H), 5.47 (d, J = 3.4 Hz, 1H), 5.08–5.04 (m, 1.5H), 4.99 (t, J = 8.0 Hz, 0.75H), 4.93 (d, J
= 12.0 Hz, 1H), 4.89–4.82 (m, 4.2H), 4.72–4.45 (m, 7.5H), 4.42–4.33 (m, 5H), 4.20 (t, J = 8.6 Hz, 1H),
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3.88–3.66 (m, 8.5H), 3.52 (d, J = 10.7 Hz, 1H), 1.41–1.37 (m, 5.25H); C NMR (100 MHz, CDCl3) δ
(ppm) = 166.4, 166.3, 160.8, 160.2, 138.8, 138.4, 138.1, 138.1, 138.0, 137.9, 137.7, 131.7, 131.5, 128.7,
128.7, 128.6, 128.6, 128.5, 128.5, 128.4, 128.3, 128.3, 128.2, 128.2, 128.1, 128.1, 128.1, 128.1, 128.0,
128.0, 127.9, 127.9, 127.8, 127.8, 124.8, 124.5, 116.1, 100.9, 95.2, 84.7, 82.0, 79.7, 77.6, 77.4, 76.0,
75.3, 73.7, 71.1, 68.7, 68.0, 60.9, 60.9, 14.5; IR (in KBr): 3447, 3125, 3030, 2924, 2360, 2339, 1634,
1594, 1496, 1454, 1401, 1316, 1242, 1148, 955, 738, 698, 541, 521 cm-1; HRMS (ESI-TOF) m/z: [M +
Na]+ calcd for C43H44O8Na 711.2928, found 711.2924.
5-(1’-Fluoro-3’-trifluorophenyl) 2,3,4,6-tetra-O-benzyl-α/β-D-glucopyranoside (3ae). 74 mg, 53%
yield, α/β = 3:1, white solid, m.p. 49-50 ℃; [α]20D = +68.9 (c = 1.0, CHCl3); 1H NMR (400 MHz, CDCl3)
δ (ppm) = 7.40–7.22 (m, 25H), 7.18–7.11 (m, 4H), 7.02–6.93 (m, 2.5H), 5.35 (d, J = 3.5 Hz, 1H), 5.04
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(d, J = 10.8 Hz, 1H), 4.99–4.83 (m, 5H), 4.61 (t, J = 12.0 Hz, 2H), 4.59–4.52 (m, 1H), 4.48 (d, J = 10.5
Hz, 1H), 4.41 (d, J = 12.0 Hz, 1H), 4.15 (t, J = 8.7 Hz, 1H), 3.82–3.64 (m, 6H), 3.55 (d, J = 10.6 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ (ppm) = 163.2 (d, J = 240.0 Hz), 158.8 (d, J = 10.0 Hz), 158.3 (d, J
= 10.0 Hz), 138.7, 138.4, 138.1, 138.1, 138.0, 137.9, 137.7, 133.0 (dq, J = 70, 40, 10.0 Hz), 129.7, 128.7,
128.6, 128.6, 128.5, 128.5, 128.3, 128.2, 128.2, 128.2, 128.1, 128.0, 128.0, 128.0, 127.9, 127.9, 127.9,
127.9, 127.8, 123.3 (d, J = 270, 10.0 Hz), 110.2 (m), 109.9 (m), 107.8 (d, J = 30.0 Hz), 107.7 (d, J =
30.0 Hz), 106.8 (d, J = 10.0 Hz), 106.5 (d, J = 10.0 Hz), 101.4, 96.1, 84.7, 81.9, 81.9, 79.7, 77.4, 77.2,
76.0, 75.9, 75.3, 75.2, 73.9, 73.6, 71.5, 68.5, 68.0; IR (in KBr): 3113, 3067, 3032, 2921, 2867, 2361,
2340, 1731, 1605, 1497, 1454, 1400, 1349, 1132, 1096, 895, 859, 737, 697 cm-1; HRMS (ESI-TOF) m/z:
[M + Na]+ calcd for C41H38O6F4Na 725.2497, found 725.2515.
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5-(2’-Cyanopyridyl) 2,3,4,6-tetra-O-pyridyl-α/β-D-glucopyranoside (3af). 48 mg, 35% yield, α:β =
1:0.3, colorless oil; 1H NMR (400 MHz, CDCl3) δ (ppm) = 8.48 (d, J = 4.0 Hz, 1H), 8.39 (d, J = 1.0 Hz,
0.3H), 7.59 (d, J = 13.1, 8.6 Hz, 1H), 7.55 (d, J = 8.6 Hz, 1H), 7.45–7.22 (m, 28H), 7.2 –7.15 (m, 1H),
7.15–7.05 (m, 2H), 5.37 (d, J = 3.4 Hz, 1H), 5.04 (d, J = 10.7 Hz, 1H), 4.96–4.83 (m, 5H), 4.62 (d, J =
10.7 Hz, 1H), 4.58 – 4.53 (m, 1.6H), 4.49–4.46 (m, 1.3H), 4.40 (d, J = 12.0 Hz, 1H), 4.15 (t, J = 9.3 Hz,
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1H), 3.82–3.64 (m, 6.3H), 3.51 (d, J = 10.3 Hz, 1H); C NMR (100 MHz, CDCl3) δ (ppm) = 155.5,
155.1, 153.3, 141.6, 141.5, 140.7, 138.5, 138.2, 137.9, 137.8, 137.8, 137.7, 137.5, 129.7, 129.6, 128.7,
128.6, 128.6, 128.6, 128.5, 128.4, 128.4, 128.3, 128.2, 128.2, 128.1, 128.1, 128.0, 128.0, 128.0, 127.9,
127.9, 127.1, 126.9, 123.2, 123.0, 117.4, 100.8, 96.2, 84.6, 81.7, 79.5, 77.4, 76.1, 76.0, 75.5, 75.4, 75.3,
74.1, 73.6, 71.8, 68.5, 67.9; IR (in KBr): 3445, 3130, 3030, 2919, 2865, 2361, 2339, 2233, 1719, 1636,
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