Gold(III)-catalyzed glycosidations for 1,2- trans and 1,2- cis furanosides

Article abstract of DOI:10.1021/jo501052y

Stereoselective synthesis of furanosides is still a daunting task, unlike the pyranosides, for which several methods exist. Herein, a unified stereoselective strategy for the synthesis of 1,2-trans and 1,2-cis furanosides is revealed for seven out of eight possible isomers of pentoses. The identified protocol gives access to diastereoselective synthesis of α- and β-araf, ribf, lyxf, and α-xylf furanosides. 1,2-trans glycosides were synthesized by the use of propargyl 1,2-orthoesters under gold-catalyzed glycosidation conditions, and subsequently, they are converted into 1,2-cis glycosides through oxidation-reduction as the key functional group transformation. All the reactions are found to be fully diastereoselective, mild, and high yielding.

Full text of DOI:10.1021/jo501052y

Article
pubs.acs.org/joc
Gold(III)-Catalyzed Glycosidations for 1,2-trans and 1,2-cis
Furanosides
Shivaji A. Thadke, Bijoyananda Mishra, and Srinivas Hotha*
Department of Chemistry, Indian Institute of Science Education and Research, Pune, Maharashtra 411008, India
S
* Supporting Information
ABSTRACT: Stereoselective synthesis of furanosides is still a daunting task, unlike the pyranosides, for which several methods
exist. Herein, a unified stereoselective strategy for the synthesis of 1,2-trans and 1,2-cis furanosides is revealed for seven out of
eight possible isomers of pentoses. The identified protocol gives access to diastereoselective synthesis of α- and β-araf, ribf, lyxf,
and α-xylf furanosides. 1,2-trans glycosides were synthesized by the use of propargyl 1,2-orthoesters under gold-catalyzed
glycosidation conditions, and subsequently, they are converted into 1,2-cis glycosides through oxidation−reduction as the key
functional group transformation. All the reactions are found to be fully diastereoselective, mild, and high yielding.
alcohol.7 But Fischer glycosidation for stereoselective synthesis
INTRODUCTION
■
is not really suitable for the synthesis of higher oligosaccharides.
The glycosidation is a reaction wherein a glycosyl donor and
hydroxyl-bearing glycosyl acceptor are involved.8 Glycosyl
donors often possess an appendage at the anomeric position
that in the presence of an activator departs resulting in an
intermediate oxocarbenium ion that will be attacked by a
suitable hydroxyl-bearing glycosyl acceptor.8 Hence, the
chemistry of glycosyl donors is of paramount importance in
the development of any glycosidation reaction. Many furanosyl
donors with a range of appendages at the anomeric position viz.
halides,9a,b silyl glycosides,9c alkyl glycosides,9d anomeric
esters,9e thioglycosides,9f,g trichloroacetamidates,9h n-pentenyl
glycosides,9f orthoesters,9i,j 1,2-anhydro sugars,9k and o-
carboxybenzyl glycosides9l are developed over the past few
decades for the synthesis of furanosides. Development of these
methods greatly benefited the synthetic carbohydrate chemists
in synthesizing furanosyl oligosaccharides.9f,10 Yet, there is no
uniform method that enables synthesis of both 1,2-cis and 1,2-
trans isomers of all four pentosyl sugars in a stereoselective
manner. In this premise, we hypothesized to utilize gold-
catalyzed glycosylation for the synthesis of both the isomers of
all the four pentosyl sugars stereoselectively. Our hypothesis
stems from a recent observation that Mycobacterium tuberculosis,
the etiological agent for tuberculosis, synthesizes 1,2-cis
arabinofuranoside indirectly through an oxidation−reduction
Glycoconjugates are known to play pivotal roles in a plethora of
intracellular and extracellular biological events.1 Most often,
saccharide constituents are in hexopyranosyl form, but
sometimes, hexofuranosyl and pentofuranosyl residues are
also noticed.2 Furanose residues were less prevalent in
mammalians and humans, though they are found frequently
in many parasitical, fungal, bacterial and plant glycans.2b
Therefore, biomolecules with furanosyl residues have attracted
special attention in order to elucidate their function,
metabolism, viability, and virulence.3 However, glycans are
difficult to isolate from nature as they are available in minute
quantities as micro and heterogeneous forms.4 1,2-trans and
1,2-cis are the two linkages that are possible in glycosides, and
as a result the stereocontrolled synthesis of them is of a great
significance. More methods are identified for the stereoselective
synthesis of pyranosides than for the furanosides either due to
the less frequent occurrence or complexity in their synthesis.5a
Furthermore, pyranosides can be advantageously synthesized
by exploiting the anomeric effect and the neighboring group
participation for the 1,2-cis and 1,2-trans pyranosides,
respectively.5b The anomeric effect is almost negligible and
the steric interactions play a major role in defining the outcome
of the stereoselectivity in furanosides. In addition, the furanose
form is thermodynamically disfavored, whereas the pyranosyl
form is more stable due to lesser steric crowding.6 As a
consequence, locking of aldose as a furanoside is the first
challenge, which is often achieved through a kinetically
controlled Fischer glycosidation in the presence of acid and
Received: May 14, 2014
© XXXX American Chemical Society
A
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Scheme 1. Synthesis of Propargyl 1,2-Orthoesters
Table 1. Gold-Catalyzed Glycosidation for the Synthesis of 1,2-trans Furanosides
a
ND denotes not determined.
at the C-2 position of a decaprenyl 1,2-trans ribofuranoside.11
RESULTS AND DISCUSSION
■
Initial attempts of utilizing propargyl furanosides for the
stereoselective synthesis were not very encouraging.9d Non-
regioselective mixture of 1,2-cis and 1,2-trans furanosides were
observed in araf and xylf donors while performing the gold
catalyzed glycosidation, though the propargyl ribf and lyxf
donors gave full 1,2-trans diastereoselectivity. As a result, in a
preliminary investigation, propargyl 1,2-orthoesters were
considered for showing the diastereoselective synthesis of
both isomers of arabinofuranosides by gold-catalyzed glyco-
sidation.12 In continuation, propargyl 1,2-orthoesters were
considered next to develop a uniform strategy that would be
applicable for the synthesis of all 1,2-trans and 1,2-cis
furanosides stereoselectively. Accordingly, synthesis of prop-
argyl 1,2-orthoesters of all the four pentose sugars is
investigated.
Locking of pentosyl aldose in furanosyl conformation was
carried out under modified Fischer glycosidation7c conditions
using AcCl, MeOH at 0−25 °C followed by the per-O-
benzoylation to obtain methyl per-O-benzoyl furanosides 1−4.
D-Arabinose required 7 h, D-lyxose and D-xylose required 3 h
whereas D-ribose was more reactive and took 30 min for the
complete conversion to afford methyl furanosides.13 Methyl
per-O-benzoyl furanosides 1 and 2 were conveniently trans-
formed into furanosyl bromides with AcBr−MeOH and then
treated with propargyl alcohol, 2,6-lutidine in CH2Cl2 to afford
required 1,2-orthoester of arabinose (5a) and lyxose (6a) in 47
and 43% yield over four steps (Scheme 1). The methyl per-O-
benzoyl furanosides of ribose (3) and xylose (4) were
converted to anomeric bromides using 33% HBr·AcOH in
AcOH for 10 min followed by the addition of propargyl alcohol
B
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Scheme 2. Conversion of 1,2-trans Furanosides into 1,2-cis Furanosides
and 2,6-lutidine in CH2Cl2 to afford orthoesters 7a and 8a in 55
and 52%, respectively (Scheme 1).13
ribofuranoside into decaprenylphosphatidyl 2-ribulose which
upon the stereoselective reduction assisted by DprE2 affords
the 1,2-cis arabinofuranosides.11
Propargyl 1,2-orthoesters are known to undergo gold-
catalyzed glycosidation reaction to afford 1,2-trans pyrano-
sides.14 Synthesis of propargyl orthobenzoates in furanosyl
form (5a, 6a, 7a and 8a) opened the possibility for the 1,2-trans
stereoselective synthesis of furanosides as well.12 Hence,
orthoesters (5a−8a) were subjected to standard gold-catalyzed
glycosidation conditions [ROH, AuCl3, 4 Å MS powder,
CH2Cl2, 25 °C] with a selected panel of hydroxyl-bearing
glycosyl acceptors 9−18. In all the cases, the 1,2-trans
stereoselectivity was observed (Table 1).13 Propargyl 1,2-
orthoester 5a underwent gold-catalyzed furanosylation reaction
with hydroxyl-bearing glycosyl acceptors 9−18 giving α-
arabinofuranosides 19a−19j in very good yields (Table 1).12
Similarly, propargyl 1,2-orthoester of lyxofuranose 6a afforded
α-lyxofuranosides 20a−20h in very good yields. In continu-
ation, propargyl 1,2-orthoester of ribofuranose (7a) and
xylofuranose (8a) resulted in the formation of β-ribofurano-
sides (21a−21j) and β-xylofuranosides (22a−22j) respectively
(Table 1).13 Singlets between δH 4.90−5.35 ppm for the
anomeric protons in the 1H NMR spectrum were observed and
anomeric carbons were identified between δC 104.5−108.0
ppm in the 13C NMR spectrum.13
Stereoselective synthesis of 1,2-trans furanosides of all the
four pentoses encouraged delving into the development of a
facile procedure for the 1,2-cis furanosides as well. Two recent
independent reports confirmed that the Mycobacterium tuber-
culosis indirectly synthesizes 1,2-cis arabinofuranosides present
in the cell surface glycan exploiting decaprenylphosphatidyl
ribofuranosyl enzymes DprE1 and DprE2.11 Further, 1,2-cis
arabinofuranosides are synthesized in two steps from 1,2-trans
ribofuranosides. DprE1 converts the decaprenylphosphatidyl
1,2-trans ribofuranosides can be easily obtained in a fully
diastereoselective fashion by the gold-catalyzed glycosidation of
propargyl 1,2-orthoesters. Now the challenge is to transform
thus obtained 1,2-trans ribofuranoside into 1,2-cis arabinofur-
anoside. Synthesis of β-mannopyranosides from β-glucopyrano-
sides through oxidation−reduction process at C-2 position is
well-known in the literature.15a,b However, similar approaches
for furanosides has a rare parallel−except the oxidation−
reduction strategy on a highly substituted L-arabinofuranose
was one of the key steps in a total synthesis effort.15c
Oxidation−reduction process was found to be beneficial for
the synthesis of hexarabinofuranosyl motif of Mycobacterial
tuberculosis cell wall.12
To test, we require orthoester that would enable us to free
the C2-OH group in an orthogonal fashion after the gold-
catalyzed furanosylation reaction. Hence, ribf-orthoester 7a was
converted into the per-O-benzyl ribf-orthoester 7b in two
steps.12 Saponification under Zemplen
debenzoylation con-
́
ditions (NaOMe/MeOH) followed by per-O-benzylation with
NaH/BnBr/DMF/TBAI/0−25 °C afforded the required
orthoester 7b in good yield. Menthol and glucose-derived
alcohol were selected as the model substrates in order to probe
the diastereoselective reduction. Accordingly, gold-catalyzed
furanosylation reaction under aforementioned conditions was
performed using hydroxyl-bearing glycosyl acceptors 14 and
menthol to obtain 1,2-trans ribofuranosides which were
́
subjected to Zemplen debenzoylation to afford C2-OH free
ribofuranosides 23a,b in very high yields. Oxidation of the C-2-
OH group was conveniently carried out using Dess−Martin
periodinane in CH2Cl2 at 25 °C and the resulting C-2 ulose
C
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Figure 1. Explanation for the diastereoselectivity.
derivative without further purification was reduced with NaBH4
to observe fully diastereoselective conversion of 1,2-trans
ribofuranosides 23a,b into 1,2-cis arabinofuranosides 24a,b in
a excellent yields (Scheme 2).
into 1,2-cis furanosides through oxidation−reduction as key
steps. All the key reactions were found to be fully
diastereoselective. The strategy identified in this endeavor is
observed to be not suitable for the synthesis of 1,2-cis-
xylofuranoside.
The diastereoselective conversion was confirmed by means
of NMR spectral analysis. Anomeric carbons of ribofuranoside
23a were noticed at δ 97.9, 107.8 ppm, whereas those of
arabinofuranoside 24a were found at δ 98.0 and 102.4 ppm. In
addition, 1JC−H values of ribf 23a were found to be 171 and 176
EXPERIMENTAL SECTION
■
General Methods. Unless otherwise noted, materials were
obtained from commercial suppliers and were used without further
purification. Unless otherwise reported all reactions were performed
under argon atmosphere. Removal of solvent in vacuo refers to
distillation using a rotary evaporator attached to an efficient vacuum
pump. Products obtained as solids or syrups were dried under a high
vacuum. All gold and transition metal salts were purchased from
multinational commercial vendors. Analytical thin-layer chromatog-
raphy was performed on precoated silica plates (F254, 0.25 mm
thickness); compounds were visualized by UV light or by staining with
anisaldehyde spray. Optical rotations were measured on a digital
polarimeter. IR spectra were recorded on a FT-IR spectrometer. NMR
spectra were recorded either on a 400 or a 500 MHz with CDCl3 as
the solvent and TMS as the internal standard. High resolution mass
spectroscopy (HRMS) was performed using a ESI-ESI-TOF mass
analyzer. Low resolution mass spectroscopy (LRMS) was performed
on UPLC-MS.
1
Hz, whereas JC−H values of araf 24a were noticed to be 174
and 183 Hz.12
Subsequently, 1,2-cis ribf, which was also equally challenging,
was envisioned from 1,2-trans araf. Accordingly, orthoester 5a
was converted into orthoester 5b under aforementioned
conditions in two steps. Gold-catalyzed furanosylation with
menthol and 14 afforded easily 1,2-trans arabinofuranosides
25a,b. Oxidation by Dess−Martin periodinane and subsequent
reduction with NaBH4 gave 1,2-cis ribofuranosides 26a,b in a
fully diastereoselective manner (Scheme 2). A doublet at δ 4.64
(J = 3.7 Hz) ppm and a singlet at δ 5.10 and δ 98.2, 109.5 ppm
1
were noticed for anomeric protons and for carbons in the H
and 13C NMR spectrum of 25a respectively, whereas in
compound 26a, two doublets at 4.59 (J = 3.6 Hz) and 5.06 (J =
4.7 Hz) ppm and δ 98.0 and 101.8 were noticed for anomeric
(a). Experimental Procedure12 for the Synthesis Of 3,5-Di-O-
benzoyl-β-D-arabinofuranoside prop-2-ynyl-1,2-orthobenzoate
(5a). Acetyl chloride (12 mL, 0.17 mol) was treated with methanol
(10 mL) at 0 °C for 30 min, and to this solution was added a CH3OH
(125 mL) solution of arabinose (20.0 g, 0.13 mol) at 0 °C and warmed
to room temperature. Progress of the reaction was monitored by the
TLC until disappearance of the aldose (∼7 h). The reaction mixture
was quenched with pyridine (40 mL) and concentrated in vacuo, and
the crude residue of α,β methyl furanoside was redissolved in
anhydrous pyridine (200 mL), cooled to 0 °C, and slowly treated with
benzoyl chloride (60 mL, 0.53 mol). Further, the reaction mixture was
stirred for 12 h at room temperature, and few pieces of ice were added
to the reaction mixture, which was stirred for another 30 min at room
temperature and then extracted with dichloromethane (2 × 500 mL).
The extract was washed with 3 N H2SO4, aq. sat. sodium bicarbonate
solution, and the organic layer was collected, dried over anhydrous
sodium sulfate, and concentrated in vacuo to yield crude residue of α,β
methyl 2,3,5-tri-O-benzoyl arabinofuranoside 1.
In continuation, arabinofuranosides 1 (31.0 g, 0.065 mol) prepared
vide supra were redissolved in anhydrous CH2Cl2 (150 mL) and
cooled to 0 °C. Acetyl bromide (26.7 mL, 0.36 mol) was added to the
reaction mixture followed by the dropwise addition of methanol
(11.85 mL, 0.29 mol) with constant stirring at 0 °C. Additionally, the
reaction mixture was stirred for 2 h at 0 °C before diluting with
CH2Cl2 (500 mL). The reaction mixture was poured into the ice−
water mixture, and aqueous layer was extracted with CH2Cl2 (2 × 250
mL), and organic layer was washed with cold saturated sodium
bicarbonate solution, dried over sodium sulfate, and concentrated
under reduced pressure to give arabinofuranosyl bromide as white
solid, which was immediately used in the next step without additional
purification. The crude arabinofuranosyl bromide was redissolved in
200 mL of anhydrous CH2Cl2, propargyl alcohol (5.6 mL, 0.10 mol)
and 2,6-lutidine (15.1 mL, 0.13 mol). Tetra-n-butyl ammonium iodide
(1.44 g, 3.9 mmol) was added to the solution and stirred for 4 h at
room temperature. The reaction mixture was diluted with CH2Cl2
1
protons and carbons, respectively, in the H NMR and 13C
NMR.13
In continuation, 1,2-cis lyxofuranosides 28a,b were obtained
by a similar set of reactions from 1,2-trans xylofuranosides
27a,b. Similarly, 1,2-cis xylofuranosides are envisaged from 1,2-
trans lyxofuranosides 29a,b, which can be conveniently
synthesized from orthoester 6a. However, the oxidation with
Dess−Martin periodinane followed by the reduction using
NaBH4 resulted into the isolation of starting 1,2-trans
lyxofuranosides 29a,b but not the required 1,2-cis xylofurano-
sides (Scheme 2).13
The stereochemical outcome can be explained based on the
differential steric crowding around the carbonyl group of the
C2-ulose derivative. The 5-O-benzyl and C-1 glycoside prevent
the hydride to attack from the exo-face in the case of β-ribf →
β-araf conversion, and hence, hydride prefers the endo-attack on
the ketone to give β-araf only (Figure 1). Similarly, endo-attack
in the α-araf → α-ribf conversion is sterically not favorable, and
hence, the product resulting from the exo-attack was observed.
Also, in case of β-xylf → β-lyxf conversion, the exo-attack is
sterically demanding which forces the hydride to attack in the
endo- fashion. However, in case of α-lyxf → α-xylf, and the 3,5-
di-O-benzyl groups make the exo-attack completely unavailable
for the hydride attack on the ketone giving back the starting
material (Figure 1).
In conclusion, a facile procedure for the fully diastereose-
lective synthesis of seven out of eight possible pentosyl
furanosides is identified. Gold-catalyzed glycosidation afforded
the 1,2-trans furanosides, which were subsequently converted
D
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(250 mL) and water (500 mL), and the aqueous layer was extracted
with CH2Cl2 (2×), and the organic extract was washed with saturated
oxalic acid solution, saturated sodium bicarbonate solution. The
organic phase was collected, dried over sodium sulfate, and
concentrated in vacuo. The crude residue of orthoester was purified
by silica gel column chromatography (EtOAc:petroleum ether 20:80)
to obtain 5a (25.0 g, 47% over four steps) as white solid.
The same procedure was added for the synthesis of orthoester 6a.
(b). 3,5-Di-O-benzoyl-α-D-ribofuranoside prop-2-ynyl-1,2-ortho-
benzoate (7a). Compound 3 was synthesized by adopting the
procedure delineated for compound 1. Subsequently, compound 3
(25.0 g, 52.5 mmol) was treated with 33% of HBr:AcOH (100.0 mL)
in acetic acid (100.0 mL) at 0 °C, gently warmed to room
temperature, and stirred for 10 min to obtain the ribofuranosyl
bromide. Rest of the procedure was followed as delineated above to
get 2,5-di-O-benzoyl-α-D-ribofuranoside-prop-2-ynyl-1,2-orthoben-
zoate 7a (18.3 g, 55% over four steps) as thick syrup.
The same procedure was added for the synthesis of orthoester 8a.
(c). General Procedure12 for the Synthesis of 3,5-Di-O-benzyl-β or
α-D-furanosyl propargyl 1,2-O-orthoester. 3,5-Di-O-benzoyl-β- or α-
D-furanosyl propargyl 1,2-O-orthoester (5.00 g, 10 mmol) and sodium
methoxide (0.15 g, 2.5 mmol) were stirred in anhydrous
CH2Cl2:methanol for 2 h at room temperature. After completion of
the reaction, the reaction mixture was concentrated in vacuo,
redissolved in water and EtOAc, and extracted with EtOAc (2 × 50
mL). The collected extract was dried over sodium sulfate and
concentrated in vacuo. The resultant crude residue was stirred in the
presence of petroleum ether (for removal of methyl benzoate) for 10
min, and the petroleum ether was decanted to afford pure diol
orthoester (2.8 g) in quantitative yield and directly used without any
further purification and analytical characterizations. Diol orthoester
(2.5 g, 8.6 mmol) was dissolved in anhydrous dimethylformamide
(DMF) (20 mL) and cooled to 0 °C in ice bath. Sodium hydride (60%
dispersion in mineral oil) (1.5 equiv per −OH) was added portion-
wise and the reaction mixture became cake like solid. Benzyl bromide
(1.1 equiv per −OH) was added slowly, and after 2 h at 0 °C, MeOH
(1 mL) and water (100 mL) were added to reaction mixture, and the
compound was extracted with EtOAc (2 × 100 mL). The organic layer
was washed with brine solution, dried over sodium sulfate, and
concentrated. The concentrated crude residue was purified by silica gel
column chromatography (EtOAc:petroleum ether, 15:85) to give 3,5-
di-O-benzyl-β or α-D-furanosyl propargyl 1,2-O-orthoester in good
yield.
(d). General Procedure for 1,2-trans Glycosylation. To a CH2Cl2
solution (5 mL) containing glycosyl donor (0.20 mmol) and glycosyl
acceptor (0.20 mmol)) with 4 Å MS powder (100 mg) was added a
catalytic amount of AuCl3 (14 μmol), and the mixture was stirred at
room temperature. After 2 h, the reaction mixture was neutralized by
the addition of Et3N (1 mL), filtered through Celite, and concentrated
in vacuo. The resulting residue was purified by silica gel column
chromatography using ethyl acetate:petroleum ether to obtain 1,2-
trans furanosides in very good yield.
(e). General Procedure for 1,2-cis Furanosylation. To a CH2Cl2
solution (5 mL) containing orthoester donor (0.42 mmol) and
hydroxyl-bearing glycosyl acceptor (0.42 mmol)) with 4 Å molecular
sieves powder (100 mg) was added a catalytic amount of AuCl3 (29
μmol), and the mixture was stirred at room temperature. After 2 h, the
reaction mixture was neutralized by the addition of Et3N, filtered
through Celite, and concentrated in vacuo to obtain a reddish brown
residue, which was redissolved in CH3OH (5 mL). NaOCH3 (20
μmol) was added, and the mixture was stirred at 25 °C for 2 h and
concentrated in vacuo. The crude residue was purified by silica gel
column chromatography using ethyl acetate-petroleum ether to obtain
1,2-trans furanosides with C-2-OH in very good yield.
anhydrous Na2SO4, and concentrated in vacuo to 2-ribuloside, which
was subsequently redissolved in CH3OH (5 mL) and treated with
NaBH4 (0.26 mmol for Glc and 0.42 mmol for Men) in three portions
at 0 °C. After 30 min, the reaction mixture was poured over ice and
extracted with ethyl acetate, washed with brine, and dried over
anhydrous Na2SO4. The solution was decanted and concentrated in
vacuo to get a pale yellow residue, which upon purification by silica gel
column chromatography gave 1,2-cis furanosides in very good yield.
3,5-Di-O-benzoyl-β-D-arabinofuranoside (prop-2-yn-1-yl)-
1,2-orthobenzoate (5a).12 [α]D25 (CHCl3, c 1.5) −15.3; IR (cm−1,
1
CHCl3) 3293, 3071, 2974, 1723, 1594, 1450, 1268, 1107, 717; H
NMR (399.78 MHz, CDCl3) δ 2.41 (t, J = 2.3 Hz, 1H), 3.98 (d, J =
2.3 Hz, 2H), 4.30 (d, J = 7.2 Hz, 2H), 4.67 (t, J = 7.2 Hz, 1H), 5.20 (d,
J = 4.2 Hz, 1H), 5.55 (s, 1H), 6.41 (d, J = 4.2 Hz, 1H), 7.33−7.46 (m,
7H), 7.54 (dt, J = 21.2, 7.3 Hz, 2H), 7.70 (dd, J = 6.5, 2.9 Hz, 2H),
8.03 (d, J = 7.7 Hz, 4H); 13C NMR (100.53 MHz, CDCl3) δ 51.9,
63.6, 73.8, 77.5, 79.2, 84.3, 84.7, 106.5, 122.7, 126.3, 126.3, 128.2,
128.2, 128.4, 128.4, 128.4, 128.4, 128.8, 129.5, 129.6, 129.6, 129.7,
129.7, 130.0, 132.9, 133.5, 134.0, 165.1, 165.7; HRMS (ESI-TOF) m/z
calcd for [C29H24O8+Na]+ 523.1369, found 523.1379.
3,5-Di-O-benzoyl-β-D-lyxofuranoside (prop-2-yn-1-yl)-1,2-
orthobenzoate (6a). This compound is prepared using the above-
mentioned general procedure using D-lyxose (7.5 g, 50.0 mmol) as the
starting material. Yield: (10.8 g, 43% over four steps); [α]2D5 (CHCl3, c
1.2) −44.7; IR (cm−1, CHCl3) 3290, 3065, 2918, 1723, 1591, 1445,
1
1269, 1099, 713; H NMR (399.78 MHz, CDCl3) δ 2.38 (t, J = 2.5
Hz, 1H), 3.97 (d, J = 2.5 Hz, 2H), 4.33 (dd, J = 11.9, 7.7 Hz, 1H), 4.56
(dd, J = 11.9, 5.3 Hz, 1H), 4.77 (td, J = 7.5, 5.3 Hz, 1H), 5.31 (dd, J =
5.7, 4.3 Hz, 1H), 5.51 (dd, J = 7.4, 5.8 Hz, 1H), 6.26 (d, J = 4.2 Hz,
1H), 7.29−7.73 (m, 11H), 7.84−8.04 (m, 4H); 13C NMR (100.53
MHz, CDCl3) δ 51.9, 63.6, 71.8, 73.8, 78.0, 78.4, 79.2, 105.4, 123.6,
126.4, 126.4, 128.2, 128.2, 128.4, 128.4, 128.5, 128.5, 128.7, 129.6,
129.6, 129.6, 129.9, 129.9, 129.9, 133.0, 133.5, 134.5, 165.4, 165.9;
HRMS (ESI-TOF) m/z calcd for [C29H24O8+Na]+ 523.1369, found
523.1377.
3,5-Di-O-benzoyl-α-D-ribofuranoside (prop-2-yn-1-yl)-1,2-
orthobenzoate (7a). This compound is prepared using the above-
mentioned general procedure using D-ribose (10 g, 66.6 mmol) as the
starting material. Yield: (18.3 g, 55% over four steps); [α]2D5 (CHCl3, c
2.6) +123.1; IR (cm−1, CHCl3) 3291, 3066, 2930, 1725, 1602, 1451,
1
1271, 1099, 710; H NMR (399.78 MHz, CDCl3) δ 2.40 (t, J = 2.4
Hz, 1H), 4.07 (dABq, J = 15.2, 2.4 Hz, 2H), 4.17−4.29 (m, 1H), 4.39
(dd, J = 12.3, 4.8 Hz, 1H), 4.62 (dd, J = 12.3, 3.3 Hz, 1H), 5.07 (dd, J
= 9.3, 5.3 Hz, 1H), 5.33 (dd, J = 5.1, 4.3 Hz, 1H), 6.25 (d, J = 4.2 Hz,
1H), 7.24−7.81 (m, 11H), 7.89−8.10 (m, 4H); 13C NMR (100.53
MHz, CDCl3) δ 51.5, 62.4, 72.8, 73.8, 76.2, 77.7, 79.1, 104.7, 123.5,
126.3, 126.3, 128.3, 128.3, 128.3, 128.3, 128.5, 128.5, 128.8, 129.4,
129.6, 129.7, 129.7, 129.9, 129.9, 133.2, 133.6, 135.8, 165.5, 166.0;
HRMS (ESI-TOF) m/z calcd for [C29H24O8+Na]+ 523.1369, found
523.1364.
3,5-Di-O-benzoyl-α-D-xylofuranoside (prop-2-yn-1-yl)-1,2-
orthobenzoate (8a). This compound is prepared using the above-
mentioned general procedure using D-xylose (10.0 g, 66.6 mmol) as
the starting material. Yield: (17.34 g, 52% over four steps); [α]D25
(CHCl3, c 1.1) −4.2; IR (cm−1, CHCl3) 3290, 3068, 2930, 1725, 1591,
1447, 1268, 1105, 706; 1H NMR (399.78 MHz, CDCl3) δ 2.40 (t, J =
2.4 Hz, 1H), 4.12−3.93 (m, 2H), 4.64−4.43 (m, 1H), 4.56 (dd, J =
7.1, 5.9 Hz, 2H), 5.04 (d, J = 4.1 Hz, 1H), 5.66 (d, J = 3.1 Hz, 1H),
6.37 (d, J = 4.1 Hz, 1H), 7.79−7.32 (m, 11H), 8.16−7.88 (m, 4H);
13C NMR (100.53 MHz, CDCl3) δ 51.8, 61.5, 73.8, 76.0, 77.8, 79.2,
84.0, 105.2, 122.8, 126.2, 126.2, 128.3, 128.3, 128.4, 128.4, 128.6,
128.6, 128.7, 129.3, 129.6, 129.6, 129.7, 129.8, 129.9, 133.1, 133.7,
134.9, 165.0, 165.9; HRMS (ESI-TOF) m/z calcd for
[C29H24O8+Na]+ 523.1369, found 523.1395.
Obtained C-2-OH (0.13 mmol for Glc and 0.21 mmol for Men)
was redissolved in CH2Cl2, Dess−Martin periodinane (0.26 mmol for
Glc and 0.42 mmol for Men) was added, and the mixture was stirred at
25 °C for 2 h. The reaction mixture was diluted with CH2Cl2 and
washed with sodium thiosulfate and sodium bicarbonate solutions.
Combined organic layers were washed with brine solution, dried over
3,5-Di-O-benzyl-β-D-arabinofuranoside (prop-2-yn-1-yl)-1,2-
orthobenzoate (5b).12 This compound is prepared using the above-
mentioned general procedure using 5a (5.0 g, 10.0 mmol) as the
starting material. Yield: (3.78 g, 80% over two steps); [α]2D5 (CHCl3, c
1.1) −16.0; IR (cm−1, CHCl3) 3291, 3033, 2928, 2867, 1721, 1592,
1453, 1275, 1111, 701; 1H NMR (399.78 MHz, CDCl3) δ 2.38 (t, J =
E
dx.doi.org/10.1021/jo501052y | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
2.3 Hz, 1H), 3.20 (dd, J = 9.8, 7.9 Hz, 1H), 3.33 (dd, J = 9.8, 6.4 Hz,
1H), 3.97 (dd, J = 9.9, 2.4 Hz, 1H), 4.02 (s, 1H), 4.23 (d, J = 12.0 Hz,
1H), 4.35 (d, J = 12.3 Hz, 1H), 4.40 (t, J = 7.3 Hz, 1H), 4.55−4.66 (m,
1H), 4.58 (d, J = 2.6 Hz, 2H), 5.02 (d, J = 4.5 Hz, 1H), 6.25 (d, J = 4.4
Hz, 1H), 7.11−7.17 (m, 2H), 7.31 (m, 11H), 7.54−7.59 (m, 2H); 13C
NMR (100.53 MHz, CDCl3) δ 51.7, 69.8, 71.5, 73.2, 73.6, 79.4, 82.6,
85.1, 85.1, 106.5, 122.4, 122.4, 126.4, 122.4, 127.6, 127.6, 127.8, 128.0,
128.0, 128.3, 128.3, 128.3, 128.3, 128.5, 128.5, 129.7, 135.2, 137.0,
137.8; HRMS (ESI-TOF) m/z calcd for [C29H28O6+Na]+ 495.1784,
found 495.1787.
3,5-Di-O-benzyl-β-D-lyxofuranoside (prop-2-yn-1-yl)-1,2-or-
thobenzoate (6b). This compound is prepared using the above-
mentioned general procedure using 6a (5.0 g, 10.0 mmol) as the
starting material. Yield: (3.54 g, 75% over two steps); [α]2D5 (CHCl3, c
1.0) −31.0; IR (cm−1, CHCl3) 3290, 3070, 2927, 1592, 1453, 1275,
1115, 715; 1H NMR (399.78 MHz, CDCl3) δ, 2.42 (t, J = 2.1 Hz, 1H),
3.54 (dd, J = 11.3, 2.2 Hz, 1H), 3.71 (d, J = 11.3 Hz, 1H), 4.00−3.88
(m, 2H), 4.07 (d, J = 1.7 Hz, 2H), 4.47 (d, J = 12.2 Hz, 1H), 4.57 (d, J
= 13.4 Hz, 2H), 4.81−4.72 (m, 1H), 4.93 (dd, J = 5.6, 2.6 Hz, 1H),
6.11 (d, J = 4.1 Hz, 1H), 7.48−7.14 (m, 13H), 7.85−7.56 (m, 2H);
13C NMR (100.53 MHz, CDCl3) δ 51.7, 67.3, 72.1, 73.3, 73.5, 76.9,
128.5, 128.5, 128.5, 128.9, 129.0, 129.1, 129.1, 129.3, 129.7, 129.7,
129.7, 129.7, 129.7, 129.7, 129.7, 129.9, 129.9, 129.9, 129.9, 130.0,
130.0, 132.9, 133.0, 133.3, 133.3, 133.5, 133.5, 165.0, 165.3, 165.8,
165.8, 165.9, 166.2; HRMS (ESI-TOF) m/z calcd for
[C54H46O16+Na]+ 973.2684, found 973.2706.
(Pent-4-enyl) 2,3,5-tri-O-benzoyl-α-D-arabinofuranoside
(19b).12 This compound is prepared using the above-mentioned
general procedure using 5a (0.100 g, 0.2 mmol) as the starting
material. Yield: (0.098 g, 92%); [α]2D5 (CHCl3, c 1.1) −4.6; IR (cm−1,
1
CHCl3) 3068, 2929, 1725, 1593, 1266, 1109, 700; H NMR (399.78
MHz, CDCl3) δ 1.76 (quintet, J = 6.7 Hz, 2H), 2.19 (q, J = 4.4 Hz,
2H), 3.56 (dt, J = 9.5, 6.2 Hz, 1H), 3.82 (dt, J = 9.5, 6.6 Hz, 1H), 4.58
(q, J = 4.8 Hz, 1H), 4.68 (dd, J = 11.9, 5.0 Hz, 1H), 4.83 (dd, J = 11.9,
3.5 Hz, 1H), 4.96 (dq, J = 10.0, 1.4 Hz, 1H), 5.02 (dq, J = 17.1, 1.6 Hz,
1H), 5.28 (s, 1H), 5.52 (d, J = 1.0 Hz, 1H), 5.58 (d, J = 4.7 Hz, 1H),
5.83 (ddt, J = 16.9, 10.2, 6.6 Hz, 1H), 7.30 (t, J = 7.8 Hz, 2H), 7.39 (t,
J = 7.8 Hz, 2H), 7.46 (t, J = 7.7 Hz, 2H), 7.49−7.54 (m, 1H), 7.55−
7.64 (m, 2H), 8.00 (dd, J = 8.1, 1.1 Hz, 2H), 8.05 (dd, J = 8.0, 1.0 Hz,
2H), 8.09 (dd, J = 8.3, 1.0 Hz, 2H); 13C NMR (100.53 MHz, CDCl3)
δ 28.7, 30.3, 63.8, 66.8, 77.0, 77.9, 81.0, 82.0, 105.7, 115.0, 128.3,
128.3, 128.5, 128.5, 128.5, 129.0, 129.1, 129.7, 129.7, 129.7, 129.8,
129.8, 129.9, 129.9, 133.0, 133.5, 133.5, 138.0, 165.5, 165.8, 166.2;
HRMS (ESI-TOF) m/z calcd for [C31H30O8+Na]+ 553.1838, found
553.1844.
77.4, 78.3, 79.6, 104.7, 123.2, 126.4, 126.4, 127.6, 127.6, 127.6, 127.8,
128.0, 128.0, 128.2, 128.2, 128.3, 128.3, 128.4, 128.4, 129.5, 135.3,
137.3, 137.8; HRMS (ESI-TOF) m/z calcd for [C29H28O6+Na]+
495.1784, found 495.1780.
Benzyl 2,3,5-tri-O-benzoyl-α-D-arabinofuranoside (19c).12
This compound is prepared using the above-mentioned general
procedure using 5a (0.100 g, 0.2 mmol) as the starting material. Yield:
(0.092 g, 83%); [α]D25 (CHCl3, c 1.5) +5.8; IR (cm−1, CHCl3) 3066,
3,5-Di-O-benzyl-α-D-ribofuranoside (prop-2-yn-1-yl)-1,2-or-
thobenzoate (7b).12 This compound is prepared using the above-
mentioned general procedure using 7a (5.0 g, 10.0 mmol) as the
starting material. Yield: (3.87 g, 82% over two steps); [α]2D5 (CHCl3, c
0.7) +21.3; IR (cm−1, CHCl3) 3290, 3060, 2928, 1722, 1590, 1450,
1
2928, 1724, 1596, 1452, 1266, 1108, 708; H NMR (399.78 MHz,
CDCl3) δ 4.61 (q, J = 4.6 Hz, 1H), 4.66 (d, J = 12.1 Hz, 1H), 4.69
(dd,, J = 12.7, 5.0 Hz, 1H), 4.84 (dd, J = 11.9, 3.5 Hz, 1H), 4.88 (d, J =
12.0 Hz, 1H), 5.40 (s, 1H), 5.60(d, J = 5.2 Hz, 1H), 5.61 (s, 1H),
7.26−7.70 (m, 14H), 7.98−8.08 (m, 6H); 13C NMR (100.53 MHz,
CDCl3) δ 63.8, 68.8, 77.8, 81.3, 81.9, 104.9, 127.7, 127.7, 127.8, 128.3,
128.3, 128.4, 128.4, 128.5, 128.5, 128.5, 128.5, 129.0, 129.1, 129.7,
129.8, 129.8, 129.9, 129.9, 130.0, 130.0, 133.1, 133.5, 133.5, 137.3,
165.4, 165.8, 166.2; HRMS (ESI-TOF) m/z calcd for
[C33H28O8+Na]+ 575.1682, found 575.1681.
1
1262, 1110, 707; H NMR (399.78 MHz, CDCl3) δ 2.40 (t, J = 2.1
Hz, 1H), 3.46−3.58 (m, 1H), 3.69 (d, J = 11.3 Hz, 1H), 3.84−3.98
(m, 2H), 4.01−4.08 (m, 2H), 4.45 (d, J = 12.2 Hz, 1H), 4.54 (d, J =
13.4 Hz, 2H), 4.76 (d, J = 11.5 Hz, 1H), 4.90 (t, J = 4.1 Hz, 1H), 6.09
(dd, J = 4.1, 1.4 Hz, 1H), 7.11−7.46 (m, 13H), 7.62−7.84 (m, 2H);
13C NMR (100.53 MHz, CDCl3) δ 51.6, 67.3, 72.1, 73.3, 73.5, 76.9,
77.4, 78.3, 79.6, 104.7, 123.2, 126.4, 126.4, 127.6, 127.6, 127.6, 128.0,
128.0, 128.0, 128.2, 128.2, 128.3, 128.3, 128.4, 128.4, 129.5, 135.3,
137.3, 137.8; HRMS (ESI-TOF) m/z calcd for [C29H28O6+Na]+
495.1784, found 495.1789.
3,5-Di-O-benzyl-α-D-xylofuranoside (prop-2-yn-1-yl)-1,2-or-
thobenzoate (8b). This compound is prepared using the above-
mentioned general procedure using 8a (5.0 g, 10.0 mmol) as the
starting material. Yield: (3.78 g, 80% over two steps); [α]2D5 (CHCl3, c
1.3) −9.4; IR (cm−1, CHCl3) 3293, 3070, 2925, 1594, 1450, 1270,
1103, 710; 1H NMR (399.78 MHz, CDCl3) δ 2.39 (t, J = 2.5 Hz, 1H),
3.72 (d, J = 6.1 Hz, 2H), 4.00 (d, J = 3.3 Hz, 1H), 4.02 (dABq, J =
15.5, 2.5 Hz, 2H), 4.13−4.23 (m, 1H), 4.46 (d, J = 11.9 Hz, 1H), 4.50
(d, J = 12.0 Hz, 1H), 4.55 (d, J = 11.9 Hz, 1H), 4.68 (d, J = 12.0 Hz,
1H), 4.95 (d, J = 4.1 Hz, 1H), 6.23 (d, J = 4.1 Hz, 1H), 7.15−7.50 (m,
13H), 7.54−7.75 (m, 2H); 13C NMR (100.53 MHz, CDCl3) δ 51.8,
67.2, 72.0, 73.4, 73.6, 79.5, 79.9, 81.1, 82.9, 105.4, 122.4, 126.2, 126.2,
127.6, 127.6, 127.6, 127.7, 127.7, 128.0, 128.3, 128.3, 128.3, 128.4,
128.4, 128.5, 129.7, 135.1, 137.2, 137.8; HRMS (ESI-TOF) m/z calcd
for [C29H28O6+Na]+ 495.1784, found 495.1780.
Cholesteryl 2,3,5-tri-O-benzoyl-α-D-arabinofuranoside
(19d).12 This compound is prepared using the above-mentioned
general procedure using 5a (0.100 g, 0.2 mmol) as the starting
material. Yield: (0.136 g, 82%); [α]2D5 (CHCl3, c 1) +3.7; IR (cm−1,
1
CHCl3) 3034, 2940, 1726, 1596, 1455, 1267, 1108, 709; H NMR
(399.78 MHz, CDCl3) δ 0.68 (s, 3H), 0.86 (d, J = 1.7 Hz, 3H), 0.87
(d, J = 1.7 Hz, 3H), 0.92 (d, J = 6.5 Hz, 3H), 0.93−1.71 (m, 24H),
1.78−1.85 (m, 1H), 1.88 (dt, J = 12.8, 3.0 Hz, 1H), 1.99 (td, J = 11.8,
11.2, 4.8 Hz, 3H), 2.41 (d, J = 7.3 Hz, 2H), 3.63 (dtd, J = 11.2, 7.2, 6.5,
4.3 Hz, 1H), 4.62 (q, J = 4.8 Hz, 1H), 4.68 (dd, J = 11.8, 5.0 Hz, 1H),
4.82 (dd, J = 11.8, 3.4 Hz, 1H), 5.35 (d, J = 4.6 Hz, 1H), 5.45 (s, 1H),
5.49 (s, 1H), 5.57 (d, J = 5.0 Hz, 1H), 7.30 (t, J = 7.8 Hz, 2H), 7.39 (t,
J = 7.8 Hz, 2H), 7.47 (t, J = 7.8 Hz, 2H), 7.49−7.68 (m, 3H), 8.01 (d,
J = 7.4 Hz, 2H), 8.05 (d, J = 7.2 Hz, 2H), 8.09 (d, J = 7.5 Hz, 2H); 13C
NMR (100.53 MHz, CDCl3) δ 11.8, 18.7, 19.4, 21.0, 22.6, 22.8, 23.8,
24.3, 27.7, 28.0, 28.2, 31.8, 31.9, 35.8, 36.1, 36.7, 37.0, 39.5, 39.7, 40.0,
42.3, 50.0, 56.1, 56.7, 63.8, 76.6, 77.9, 80.7, 82.5, 103.8, 121.9, 128.3,
128.3, 128.5, 128.5, 128.5, 128.5, 129.1, 129.2, 129.7, 129.8, 129.8,
129.8, 129.8, 129.9, 129.9, 133.0, 133.4 133.5, 140.6, 165.5, 165.8,
166.2; HRMS (ESI-TOF) m/z calcd for [C53H66O8+Na]+ 853.4655,
found 853.4664
Methyl-2,3,4-tri-O-benzoyl-6-O-(2,3,5-tri-O-benzoyl-α-D-ara-
binofuranosyl)-α-D-glucopyranoside (19a).12 This compound is
prepared using the above-mentioned general procedure using 5a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.148 g, 78%);
[α]2D5 (CHCl3, c 1.0) +28.5; IR (cm−1, CHCl3) 3062, 2928, 1727,
Benzyl-N-(benzyloxycarbonyl)-O-(2,3,5-tri-O-benzoyl-α-D-
arabinofuranosyl)-L-serinate (19e).12 This compound is prepared
using the above-mentioned general procedure using 5a (0.100 g, 0.2
mmol) as the starting material. Yield: (0.139 g, 90%); [α]2D5 (CHCl3, c
1.3) −5.3; IR (cm−1, CHCl3) 3064, 2926, 1723, 1594, 1450, 1261,
1
1596, 1453, 1269, 1104, 710; H NMR (399.78 MHz, CDCl3) δ 3.44
(s, 3H), 3.79 (d, J = 11.0 Hz, 1H), 4.05 (dd, J = 11.0, 4.1 Hz, 1H), 4.29
(d, J = 8.6 Hz, 1H), 4.61 (dd, J = 11.6, 4.9 Hz, 1H), 4.66−4.70 (m,
1H), 4.74 (dd, J = 11.5, 2.8 Hz, 1H), 5.25 (d, J = 3.5 Hz, 1H), 5.30
(dd, J = 10.1, 3.6 Hz, 1H), 5.35 (s, 1H), 5.54 (d, J = 4.3 Hz, 1H), 5.61
(s, 1H), 5.73 (t, J = 9.9 Hz, 1H), 6.14 (t, J = 9.8 Hz, 1H), 7.14−7.67
(m, 18H), 7.74 (d, J = 8.1 Hz, 2H), 7.93 (dd, J = 17.2, 8.0 Hz, 4H),
7.97−8.01 (m, 4H), 8.22 (d, J = 7.8 Hz, 2H); 13C NMR (100.53 MHz,
CDCl3) δ 55.5, 63.7, 65.0, 68.4, 68.9, 70.6, 72.0, 77.7, 81.3, 81.9, 97.0,
105.4, 128.2, 128.2, 128.2, 128.2, 128.4, 128.4, 128.4, 128.4, 128.5,
1
1120, 703; H NMR (399.78 MHz, CDCl3) δ 4.09 (qd, J = 10.2, 2.8
Hz, 2H), 4.50 (q, J = 4.4 Hz, 1H), 4.61 (dd, J = 12.0, 5.3 Hz, 1H), 4.65
(dt, J = 2.6, 8.9 Hz, 1H), 4.76 (dd, J = 11.9, 3.5 Hz, 1H), 5.04 (ABq, J
= 12.3 Hz, 2H), 5.20 (ABq, J = 12.3 Hz, 2H), 5.22 (s, 1H), 5.42 (s,
1H), 5.53 (d, J = 4.3 Hz, 1H), 5.80 (d, J = 8.7 Hz, 1H), 7.20−7.43 (m,
16H), 7.50 (q, J = 7.5 Hz, 2H), 7.57 (tt, J = 15.0, 7.3, 1.3 Hz,1H), 7.98
F
dx.doi.org/10.1021/jo501052y | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(d, J = 7.3 Hz, 2H), 8.03 (d, J = 7.6 Hz, 4H); 13C NMR (100.53 MHz,
CDCl3) δ 54.3, 63.6, 66.9, 67.4, 67.4, 68.0, 81.4, 81.8, 105.8, 128.0,
128.0, 128.1, 128.2, 128.2, 128.2, 128.2, 128.4, 128.4, 128.4, 128.5,
128.5, 128.5, 128.5, 128.5, 128.5, 128.5, 128.7, 128.8, 129.5, 129.7,
129.7, 129.8, 129.8, 129.8, 133.0, 133.5, 133.5, 135.1, 136.0, 155.8,
165.2, 165.5, 166.1, 169.7. ; HRMS (ESI-TOF) m/z calcd for
[C44H39O12+Na]+ 796.2370, found 796.2372.
165.1, 165.8, 166.2; HRMS (ESI-TOF) m/z calcd for
[C58H58O13+Na]+ 985.3775, found 985.3784.
Propargyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-α-D-
arabinofuranosyl)-α-D-glucopyranoside (19i).12 This compound
is prepared using the above-mentioned general procedure using 5a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.151 g, 81%);
[α]2D5 (CHCl3, c 1.1) +24.9; IR (cm−1, CHCl3) 3293, 3031, 2925,
1724, 1595, 1446, 1266, 1104, 706; 1H NMR (399.78 MHz, CDCl3) δ
2.42 (t, J = 2.4 Hz, 1H), 3.64 (dd, J = 9.7, 3.7 Hz, 1H), 3.70 (t, J = 9.0
Hz, 1H), 3.79 (dd, J = 11.3, 1.6 Hz, 1H), 3.86 (qd, J = 10.0, 3.4, 1.9
Hz, 1H), 4.01 (t, J = 9.3 Hz, 1H), 4.10 (dd, J = 11.3, 3.7 Hz, 1H), 4.27
(ddd, J = 18.3, 15.9, 2.3 Hz, 2H), 4.48 (q, J = 4.7 Hz, 1H), 4.61 (d, J =
4.8 Hz, 1H), 4.62 (d, J = 10.9 Hz, 1H), 4.53−4.71 (m, 1H), 4.74 (d, J
= 5.3 Hz, 1H), 4.72−4.77 (m, 1H), 4.79 (d, J = 10.9 Hz, 1H), 4.84 (d,
J = 10.9 Hz, 1H), 5.00 (d, J = 10.8 Hz, 1H), 5.08 (d, J = 3.6 Hz, 1H),
5.41 (s, 1H), 5.54 (d, J = 4.5 Hz, 1H), 5.60 (d, J = 0.9 Hz, 1H), 7.10−
7.69 (m, 24H), 7.91−8.13 (m, 6H); 13C NMR (100.53 MHz, CDCl3)
δ 54.4, 63.7, 65.8, 70.4, 73.0, 74.8, 74.9, 75.0, 75.6, 77.5, 77.8, 78.8,
79.5, 81.7, 81.8, 95.0, 106.1, 127.4, 127.4, 127.5, 127.7, 127.8, 127.9,
127.9, 128.1, 128.1, 128.2, 128.2, 128.3, 128.3, 128.4, 128.4, 128.4,
128.4, 128.5, 128.5, 128.5, 128.5, 128.9, 128.9, 129.6, 129.7, 129.7,
129.8, 129.8, 129.8, 129.8, 133.0, 133.5, 133.5, 137.9, 138.1, 138.7,
165.2, 165.6, 166.1; HRMS (ESI-TOF) m/z calcd for
[C56H52O13+Na]+ 955.3306, found 955.3319.
Propargyl 3,5-di-O-benzyl-2-O-(2,3,5-tri-O-benzoyl-α-D-ara-
binofuranosyl)-α-D-ara-binofuranoside (19j).12 This compound
is prepared using the above-mentioned general procedure using 5a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.117 g, 72%);
[α]2D5 (CHCl3, c 1.0) +22.3; IR (cm−1, CHCl3) 3297, 3067, 2927,
1724, 1593, 1453, 1267, 1108, 706; 1H NMR (399.78 MHz, CDCl3) δ
2.32 (t, J = 2.4 Hz, 1H), 3.66 (dABq, J = 14.0, 10.7 Hz, 2H), 3.97 (dd,
J = 6.4, 2.7 Hz, 1H), 4.20−4.26 (m, 1H), 4.28 (d, J = 2.4 Hz, 2H),
4.28−4.30 (m, 1H), 4.56 (ABq, J = 15.7 Hz, 2H), 4.58−4.65 (m, 1H),
4.62 (d, J = 13.3 Hz, 1H), 4.69 (dd, J = 11.7, 4.7 Hz, 2H), 4.78 (dd, J =
11.9, 3.8 Hz, 1H), 5.22 (s, 1H), 5.37 (s, 1H), 5.46 (d, J = 1.3 Hz, 1H),
5.59 (d, J = 4.0 Hz, 1H), 7.09−7.35 (m, 10H), 7.38−7.67 (m, 9H),
7.94−8.16 (m, 6H); 13C NMR (100.53 MHz, CDCl3) δ 54.0, 63.6,
69.5, 72.4, 73.4, 74.5, 77.5, 79.0, 81.00, 81.4, 82.2, 83.2, 86.5, 104.7,
105.5, 127.6, 127.7, 127.7, 127.7, 127.9, 127.9, 128.3, 128.3, 128.3,
128.3, 128.3, 128.3, 128.5, 128.5, 128.5, 128.5, 128.9, 129.0, 129.6,
129.7, 129.7, 129.9, 129.9, 129.9, 129.9, 133.1, 133.5, 133.6, 137.6,
137.9, 165.3, 165.6, 166.1; HRMS (ESI-TOF) m/z calcd for
[C48H44O12+Na]+ 835.2730, found 835.2722.
Methyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-α-D-ara-
binofuranosyl)-α-D-glucopyranoside (19f).12 This compound is
prepared using the above-mentioned general procedure using 5a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.149 g, 82%);
[α]2D5 (CHCl3, c 1.0) +17.7; IR (cm−1, CHCl3) 3038, 2924, 1724,
1
1591, 1450, 1266, 1104, 706; H NMR (399.78 MHz, CDCl3) δ 3.33
(s, 3H), 3.58 (dd, J = 9.6, 3.5 Hz, 1H), 3.67 (t, J = 9.3 Hz, 1H), 3.73−
3.85 (m, 2H), 3.99 (t, J = 9.2 Hz, 1H), 4.10 (dd, J = 11.0, 3.5 Hz, 1H),
4.47 (q, J = 4.5 Hz, 1H), 4.57 (dd, J = 12.0, 5.0 Hz, 1H), 4.60 (s, 1H),
4.62 (d, J = 6.6 Hz, 1H), 4.67 (d, J = 12.1 Hz, 1H), 4.73 (dd, J = 12.0,
3.3 Hz, 1H), 4.77 (d, J = 1.8 Hz, 1H), 4.80 (s, 1H), 4.82 (d, J = 11.0
Hz, 1H), 4.98 (d, J = 10.9 Hz, 1H), 5.41 (s, 1H), 5.52 (d, J = 4.4 Hz,
1H), 5.59 (s, 1H), 7.14−7.44 (m, 21H), 7.45−7.51 (m, 2H), 7.57 (t, J
= 7.5 Hz, 1H), 7.97 (d, J = 5.3 Hz, 2H), 7.99 (d, J = 5.1 Hz, 2H), 8.04
(d, J = 7.4 Hz, 2H); 13C NMR (100.53 MHz, CDCl3) δ 55.1, 63.7,
66.0, 69.8, 73.4, 75.0, 75.6, 77.8, 77.8, 80.0, 81.7, 81.8, 81.9, 98.0,
106.1, 127.4, 127.4, 127.5, 127.7, 127.9, 127.9, 127.9, 128.1, 128.1,
128.2, 128.2, 128.3, 128.3, 128.4, 128.4, 128.4, 128.4, 128.5, 128.5,
128.5, 128.5, 128.9, 129.0, 129.6, 129.7, 129.7, 129.8, 129.8, 129.8,
129.8, 133.0, 133.5, 133.5, 138.1, 138.2, 138.8, 165.2, 165.6, 166.2;
HRMS (ESI-TOF) m/z calcd for [C54H52O13+Na]+ 931.3306, found
931.3332.
Methyl 2,3,6-tri-O-benzyl-4-O-(2,3,5-tri-O-benzoyl-α-D-ara-
binofuranosyl)-α-D-glucopyranoside (19g).12 This compound is
prepared using the above-mentioned general procedure using 5a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.145 g, 80%);
[α]2D5 (CHCl3, c 1.5) +2.4; IR (cm−1, CHCl3) 3020, 2925, 1725, 1596,
1
1453, 1268, 1105, 758; H NMR (399.78 MHz, CDCl3) δ 3.43 (s,
3H), 3.56 (dd, J = 9.6, 3.4 Hz, 1H), 3.66 (dd, J = 9.1, 3.0 Hz, 1H), 3.70
(t, J = 8.3 Hz, 1H), 3.84 (s, 1H), 3.85 (d, J = 4.9 Hz, 1H), 4.06 (t, J =
9.1 Hz, 1H), 4.27 (q, J = 4.4 Hz, 1H), 4.40 (d, J = 12.1 Hz, 1H), 4.48
(dd, J = 18.7, 6.9 Hz, 1H), 4.49 (s, 1H), 4.57 (dd, J = 11.8, 3.8 Hz,
1H), 4.63 (dd, J = 7.8, 4.3 Hz, 2H), 4.76 (d, J = 7.3 Hz, 1H), 4.79 (d, J
= 6.1 Hz, 1H), 5.00 (d, J = 10.9 Hz, 1H), 5.47 (d, J = 4.4 Hz, 1H), 5.55
(s, 1H), 5.82 (s, 1H), 6.93−7.71 (m, 24H), 7.85 (d, J = 7.6 Hz, 2H),
7.97 (d, J = 7.4 Hz, 2H), 8.05−8.10 (m, 2H); 13C NMR (100.53 MHz,
CDCl3) δ 55.3, 63.7, 69.0, 69.5, 73.3, 73.4, 73.9, 75.4, 77.9, 79.9, 81.7,
81.7, 81.9, 97.9, 106.7, 127.2, 127.5, 127.5, 127.5, 127.5, 127.5, 127.9,
128.1, 128.1, 128.1, 128.1, 128.2, 128.2, 128.2, 128.2, 128.3, 128.3,
128.4, 128.4, 128.5, 128.5, 128.8, 129.1, 129.6, 129.6, 129.6, 129.8,
129.8, 129.8, 129.8, 132.9, 133.4, 133.5, 137.8, 137.9, 138.2, 165.0,
165.5, 166.1; HRMS (ESI-TOF) m/z calcd for [C54H52O13+Na]+
931.3306, found 931.3328.
(Pent-4-enyl) 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-α-
D-arabinofuranosyl)-α-D-mannopyranoside (19h).12 This com-
pound is prepared using the above-mentioned general procedure using
5a (0.100 g, 0.2 mmol) as the starting material. Yield: (0.148 g, 77%);
[α]2D5 (CHCl3, c 1.3) +3.0; IR (cm−1, CHCl3) 3070, 2926, 1725, 1595,
1440, 1267, 1107, 707; 1H NMR (399.78 MHz, CDCl3) δ 1.58
(quintet, J = 6.9 Hz, 2H), 2.02 (q, J = 13.4, 5.7 Hz, 2H), 3.32 (dt, J =
9.6, 6.3 Hz, 1H), 3.66 (dt, J = 9.6, 6.5 Hz, 1H), 3.75−3.85 (m, 3H),
3.93 (dd, J = 9.4, 3.0 Hz, 1H), 4.11 (t, J = 9.7 Hz, 1H), 4.17 (dd, J =
11.3, 4.5 Hz, 1H), 4.48 (q, J = 7.9, 4.4 Hz, 1H), 4.59 (dd, J = 11.4, 4.6
Hz, 2H), 4.63 (s, 2H), 4.73 (s, 2H), 4.76 (dd, J = 12.1, 3.3 Hz, 1H),
4.83−4.87 (m, 2H), 4.91−5.01 (m, 2H), 5.48 (s, 1H), 5.51 (d, J = 4.4
Hz, 1H), 5.69 (s, 1H), 5.70−5.81 (m, 1H), 7.07−7.71 (m, 24H),
7.93−8.12 (m, 6H); 13C NMR (100.53 MHz, CDCl3) δ 28.5, 30.2,
63.8, 66.5, 66.8, 71.1, 72.0, 72.5, 74.6, 74.8, 75.1, 77.9, 80.2, 81.8, 81.9,
97.9, 106.0, 114.9, 127.5, 127.5, 127.5, 127.5, 127.5, 127.5, 127.6,
127.6, 127.6, 127.7, 127.7, 128.2, 128.3, 128.3, 128.3, 128.3, 128.3,
128.3, 128.5, 128.5, 128.5, 129.0, 129.1, 129.7, 129.7, 129.7, 129.8,
129.8, 130.0, 130.0, 132.9, 133.3, 138.0, 138.3, 138.3, 138.4, 138.5,
Methyl 2,3,4-tri-O-benzoyl-6-O-(2,3,5-tri-O-benzoyl-α-D-lyx-
ofuranosyl)-α-D-glucopyranoside (20a). This compound is
prepared using the above-mentioned general procedure using 6a
(0.10 g, 0.2 mmol) as the starting material. Yield: (0.143 g, 75%);
[α]2D5 (CHCl3, c 1.2) +57.5; IR (cm−1, CHCl3) 3073, 2927, 1729,
1
1594, 1453, 1271, 1104, 709; H NMR (399.78 MHz, CDCl3) δ 3.49
(s, 3H), 3.76 (dd, J = 11.1, 2.5 Hz, 1H), 4.03 (dd, J = 11.1, 4.3 Hz,
1H), 4.27 (ddd, J = 10.2, 4.1, 2.5 Hz, 1H), 4.54 (d, J = 6.1 Hz, 2H),
4.79 (q, J = 6.1 Hz, 1H), 5.27 (d, J = 3.7 Hz, 1H), 5.31 (dd, J = 9.9, 3.7
Hz, 1H), 5.37 (d, J = 0.3 Hz, 1H), 5.71 (dd, J = 5.4, 1.0 Hz, 1H), 5.74
(t, J = 10.0 Hz, 1H), 6.11 (t, J = 5.7 Hz, 1H), 6.16 (t, J = 9.8 Hz, 1H),
7.14−7.63 (m, 18H), 7.81−8.03 (m, 12H); 13C NMR (100.53 MHz,
CDCl3) δ 55.7, 63.2, 65.8, 68.3, 69.0, 70.6, 71.8, 72.1, 75.8, 76.1, 97.1,
104.5, 128.2, 128.2, 128.2, 128.3, 128.3, 128.3, 128.4, 128.4, 128.4,
128.4, 128.4, 128.9, 129.0, 129.0, 129.1, 129.2, 129.6, 129.6, 129.6,
129.7, 129.7, 129.7, 129.7, 129.7, 129.7, 129.7, 129.8, 129.8, 129.9,
129.9, 133.0, 133.0, 133.3, 133.3, 133.3, 133.3, 165.0, 165.2, 165.2,
165.7, 165.8, 166.1; HRMS (ESI-TOF) m/z calcd for
[C54H46O16+Na]+ 973.2684, found 973.2680.
Pent-4-enyl 2,3,5-tri-O-benzoyl α-D-lyxofuranoside (20b).
This compound is prepared using the above-mentioned general
procedure using 6a (0.100 g, 0.2 mmol) as the starting material. Yield:
(0.100 g, 94%); [α]D25 (CHCl3, c 2.4) +11.9; IR (cm−1, CHCl3) 3076,
1
2929, 1729, 1592, 1449, 1269, 1112, 707; H NMR (399.78 MHz,
CDCl3) δ 1.72 (quintet, J = 6.7 Hz, 2H), 2.15 (q, J = 6.9 Hz, 2H), 3.53
(dt, J = 9.5, 6.4 Hz, 1H), 3.80 (dt, J = 9.5, 6.5 Hz, 1H), 4.58−4.69 (m,
2H), 4.82 (q, J = 6.2 Hz, 1H), 4.97 (dq, J = 10.1, 1.4 Hz, 1H), 5.04
G
dx.doi.org/10.1021/jo501052y | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(dq, J = 17.1, 1.6 Hz, 1H), 5.31 (d, J = 1.0 Hz, 1H), 5.62 (dd, J = 5.2,
1.2 Hz, 1H), 5.81 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 6.05 (t, J = 5.8 Hz,
1H), 7.29 (t, J = 7.8 Hz, 2H), 7.36 (t, J = 7.8 Hz, 4H), 7.44−7.57 (m,
3H), 7.86 (dd, J = 8.3, 1.2 Hz, 2H), 7.92−7.97 (m, 4H); 13C NMR
(100.53 MHz, CDCl3) δ 28.6, 30.2, 63.4, 67.6, 71.9, 75.5, 76.1, 104.7,
115.0, 128.3, 128.3, 128.4, 128.4, 128.5, 128.5, 128.8, 129.0, 129.6,
129.7, 129.7, 129.7, 129.7, 129.7, 129.7, 133.1, 133.4, 133.4, 137.9,
165.2, 165.3, 166.2; HRMS (ESI-TOF) m/z calcd for
[C31H30O8+Na]+ 553.1838, found 553.1854.
1.2) +24.0; IR (cm−1, CHCl3) 3065, 2923, 1729, 1595, 1454, 1269,
1104, 706; 1H NMR (399.78 MHz, CDCl3) δ 3.41 (s, 3H), 3.52 (dd, J
= 9.6, 3.5 Hz, 1H), 3.58−3.68 (m, 1H), 3.73 (d, J = 10.8 Hz, 1H), 3.78
(d, J = 5.4 Hz, 2H), 3.79 (s, 1H), 3.94−4.00 (m, 1H), 4.44−4.51 (m,
4H), 4.61 (d, J = 3.5 Hz, 1H), 4.62 (t, J = 12.5 Hz, 1H), 4.70 (d, J =
11.0 Hz, 1H), 4.73 (d, J = 12.1 Hz, 1H), 4.94 (d, J = 10.9 Hz, 1H),
5.60 (dd, J = 5.1, 1.5 Hz, 1H), 5.79 (d, J = 1.4 Hz, 1H), 5.87 (t, J = 5.2
Hz, 1H), 7.03 (dd, J = 5.1, 1.9 Hz, 3H), 7.14−7.39 (m, 18H), 7.41−
7.59 (m, 3H), 7.73−7.84 (m, 4H), 7.87−7.95 (m, 2H); 13C NMR
(100.53 MHz, CDCl3) δ 55.3, 63.3, 68.9, 69.4, 71.7, 73.2, 73.3, 75.1,
75.5, 75.7, 76.1, 79.8, 81.5, 97.8, 105.6, 127.3, 127.5, 127.6, 127.7,
127.7, 127.9, 128.1, 128.1, 128.1, 128.1, 128.1, 128.2, 128.3, 128.3,
128.3, 128.3, 128.3, 128.4, 128.4, 128.4, 128.4, 128.7, 128.8, 129.5,
129.6, 129.6, 129.7, 129.7, 129.7, 129.7, 133.0, 133.3, 133.4, 137.9,
138.0, 138.3, 165.0, 165.1, 166.0; HRMS (ESI-TOF) m/z calcd for
[C54H52O13+Na]+ 931.3306, found 931.3315.
Cholesteryl 2,3,5-tri-O-benzoyl-α-D-lyxofuranoside (20c).
This compound is prepared using the above-mentioned general
procedure using 6a (0.100 g, 0.2 mmol) as the starting material. Yield:
(0.134 g, 81%); [α]D25 (CHCl3, c 1.4) +10.3; IR (cm−1, CHCl3) 3072,
1
2938, 1730, 1599, 1460, 1263, 1103, 710; H NMR (399.78 MHz,
CDCl3) δ 0.67 (s, 3H), 0.84 (d, J = 1.8 Hz, 3H), 0.86 (d, J = 1.8 Hz,
3H), 0.90 (d, J = 6.5 Hz, 3H), 1.01 (s, 3H), 0.97−2.10 (m, 26H),
2.30−2.44 (m, 2H), 3.57 (dt, J = 11.1, 6.2 Hz, 1H), 4.61 (dd, J = 11.3,
5.5 Hz, 1H), 4.65 (dd, J = 11.2, 6.2 Hz, 1H), 4.85 (q, J = 6.2 Hz, 1H),
5.34 (d, J = 5.2 Hz, 1H), 5.46 (d, J = 0.7 Hz, 1H), 5.59 (dd, J = 5.2, 1.1
Hz, 1H), 6.06 (t, J = 6.0 Hz, 1H), 7.25−7.39 (m, 6H), 7.42−7.58 (m,
3H), 7.86 (dd, J = 8.3, 1.1 Hz, 2H), 7.95 (ddd, J = 8.0, 6.4, 1.3 Hz,
4H); 13C NMR (100.53 MHz, CDCl3) δ 11.8, 18.7, 19.4, 21.0, 22.6,
22.8, 23.8, 24.3, 27.9, 28.0, 28.2, 31.8, 31.9, 35.8, 36.1, 36.7, 37.0, 39.5,
39.7, 40.1, 42.3, 50.1, 56.1, 56.7, 63.4, 71.9, 75.3, 76.4, 77.7, 103.0,
121.9, 128.3, 128.3, 128.3, 128.3, 128.5, 128.5, 128.8, 129.1, 129.6,
129.7, 129.7, 129.7, 129.7, 129.7, 129.7, 133.0, 133.4, 133.4, 140.5,
165.3, 165.3, 166.2; HRMS (ESI-TOF) m/z calcd for
[C53H66O8+Na]+ 853.4655, found 853.4664.
Pent-4-enyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-α-D-
lyxofuranosyl)-α-D-mannopyranoside (20g). This compound is
prepared using the above-mentioned general (d) procedure using 6a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.140 g, 73%);
[α]2D5 (CHCl3, c 1.2) +23.6; IR (cm−1, CHCl3) 3079, 2925, 1728,
1
1592, 1456, 1263, 1103, 714; H NMR (399.78 MHz, CDCl3) δ 1.61
(quintet, J = 7.9 Hz, 2H), 2.05 (q, J = 7.6 Hz, 2H), 3.35 (dt, J = 9.7,
6.4 Hz, 1H), 3.66 (dt, J = 9.7, 6.6 Hz, 1H), 3.72−3.79 (m, 2H), 3.85
(dd, J = 11.1, 1.7 Hz, 1H), 3.91 (dd, J = 9.3, 2.9 Hz, 1H), 3.98 (t, J =
9.4 Hz, 1H), 4.09 (dd, J = 11.1, 5.0 Hz, 1H), 4.55 (dd, J = 11.6, 5.4 Hz,
1H), 4.60 (d, J = 6.7 Hz, 1H), 4.63 (s, 2H), 4.67 (d, J = 10.8 Hz, 1H),
4.71 (d, J = 3.8 Hz, 2H), 4.77−4.85 (m, 2H), 4.91−5.01 (m, 3H), 5.48
(s, 1H), 5.69−5.82 (m, 2H), 6.04 (t, J = 6.1 Hz, 1H), 7.20−7.41 (m,
20H), 7.42−7.59 (m, 4H), 7.80−7.87 (m, 2H), 7.93 (dd, J = 8.2, 1.2
Hz, 2H), 7.96 (dd, J = 8.2, 1.2 Hz, 2H); 13C NMR (100.53 MHz,
CDCl3) δ 28.5, 30.2, 63.5, 67.0, 67.0, 71.3, 71.8, 72.0, 72.5, 74.5, 74.8,
75.2, 75.6, 76.0, 80.2, 97.8, 104.7, 114.9, 127.5, 127.6, 127.6, 127.6,
127.7, 127.8, 127.8, 128.0, 128.0, 128.2, 128.2, 128.3, 128.3, 128.3,
128.3, 128.3, 128.3, 128.4, 128.4, 128.5, 128.5, 128.8, 129.1, 129.6,
129.7, 129.7, 129.7, 129.7, 129.7, 129.7, 133.0, 133.3, 133.3, 138.0,
138.3, 138.4, 138.5, 165.1, 165.2, 166.2; HRMS (ESI-TOF) m/z calcd
for [C58H58O13+Na]+ 985.3775, found 985.3776.
Prop-2-ynyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-α-D-
lyxofuranosyl)-α-D-glucopyranoside (20h). This compound is
prepared using the above-mentioned general procedure using 6a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.140 g, 75%);
[α]2D5 (CHCl3, c 1.9) +41.4; IR (cm−1, CHCl3) 3293, 3062, 2925,
1728, 1595, 1453, 1268, 1102, 705; 1H NMR (399.78 MHz, CDCl3) δ
2.42 (t, J = 2.3 Hz, 1H), 3.54−3.69 (m, 2H), 3.74−3.85 (m, 2H), 4.00
(t, J = 9.3 Hz, 1H), 4.05 (dd, J = 11.2, 3.6 Hz, 1H), 4.26 (ddd, J = 18.5,
15.9, 2.3 Hz, 2H), 4.56 (dd, J = 11.5, 5.5 Hz, 1H), 4.61 (dd, J = 11.6,
6.7 Hz, 1H), 4.66 (d, J = 10.7 Hz, 1H), 4.71 (d, J = 10.0 Hz, 2H), 4.77
(dd, J = 12.0, 6.2 Hz, 1H), 4.82 (d, J = 10.9 Hz, 1H), 4.93 (d, J = 10.7
Hz, 1H), 5.00 (d, J = 10.9 Hz, 1H), 5.04 (d, J = 3.6 Hz, 1H), 5.41 (d, J
= 0.9 Hz, 1H), 5.67 (dd, J = 5.3, 1.1 Hz, 1H), 6.02 (t, J = 5.6 Hz, 1H),
7.19−7.42 (m, 21H), 7.43−7.58 (m, 3H), 7.84 (dd, J = 8.3, 1.1 Hz,
2H), 7.90 (dd, J = 8.3, 1.1 Hz, 2H), 7.94 (dd, J = 8.0, 1.0 Hz, 2H); 13C
NMR (100.53 MHz, CDCl3) δ 54.5, 63.4, 70.5, 71.7, 73.1, 74.8, 74.8,
75.2, 75.7, 75.8, 75.9, 78.9, 79.5, 81.8, 95.2, 105.0, 127.6, 127.8, 127.8,
127.9, 127.9, 127.9, 127.9, 128.2, 128.2, 128.2, 128.2, 128.3, 128.4,
128.4, 128.4, 128.4, 128.4, 128.4, 128.4, 128.5, 128.5, 128.5, 128.7,
129.0, 129.5, 129.6, 129.6, 129.7, 129.7, 129.7, 129.7, 133.0, 133.4,
133.4, 137.9, 138.1, 138.7, 165.1, 165.2, 166.1; HRMS (ESI-TOF) m/z
calcd for [C56H52O13+Na]+ 955.3306, found 955.3326.
Benzyl-N-(benzyloxycarbonyl)-O-(2,3,5-tri-O-benzoyl-α-D-
lyxofuranosyl)-L-serinate (20d). This compound is prepared using
the above-mentioned general procedure using 6a (0.100 g, 0.2 mmol)
as the starting material. Yield: (0.121 g, 78%); [α]2D5 (CHCl3, c 1.4)
+1.9; IR (cm−1, CHCl3) 3434, 3368, 3067, 2924, 1727, 1594, 1454,
1
1267, 1111, 707; H NMR (399.78 MHz, CDCl3) δ 3.99 (d, J = 8.9
Hz, 1H), 4.15 (dd, J = 10.5, 2.8 Hz, 1H), 4.52−4.65 (m, 3H), 4.70 (q,
J = 5.7 Hz, 1H), 5.03 (d, J = 12.3 Hz, 1H), 5.10 (d, J = 12.1 Hz, 1H),
5.20 (s, 2H), 5.25 (q, J = 12.1 Hz, 1H), 5.49 (d, J = 5.2 Hz, 1H), 5.87
(t, J = 5.5 Hz, 1H), 5.97 (d, J = 8.7 Hz, 1H), 7.21−7.39 (m, 16H), 7.51
(dt, J = 13.6, 7.4 Hz, 3H), 7.86 (d, J = 8.0 Hz, 2H), 7.90 (d, J = 8.2 Hz,
2H), 7.98 (d, J = 7.9 Hz, 1H); 13C NMR (100.53 MHz, CDCl3) δ
54.5, 63.1, 67.0, 67.5, 69.6, 71.5, 75.9, 76.1, 105.5, 128.0, 128.0, 128.1,
128.3, 128.3, 128.4, 128.4, 128.4, 128.4, 128.5, 128.5, 128.5, 128.6,
128.6, 128.7, 128.8, 129.5, 129.7, 129.7, 129.7, 129.7, 129.7, 129.7,
129.7, 129.7, 133.1, 133.5, 133.5, 135.2, 136.2, 156.0, 165.0, 165.1,
166.1, 169.7; HRMS (ESI-TOF) m/z calcd for [C44H39O12+Na]+
796.2370, found 796.2372.
Methyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-α-D-lyxo-
furanosyl)-α-D-glucopyranoside (20e). This compound is pre-
pared using the above-mentioned general procedure using 6a (0.100 g,
0.2 mmol) as the starting material. Yield: (0.131 g, 72%); [α]D25
(CHCl3, c 1.2) +33.3; IR (cm−1, CHCl3) 3072, 2924, 1729, 1595,
1
1456, 1268, 1100, 709; H NMR (399.78 MHz, CDCl3) δ 3.37 (s,
3H), 3.57 (dd, J = 9.7, 3.5 Hz, 1H), 3.61 (d, J = 9.5 Hz, 1H), 3.72−
3.85 (m, 2H), 4.01 (t, J = 9.3 Hz, 1H), 4.06 (dd, J = 11.3, 3.9 Hz, 1H),
4.53−4.70 (m, 5H), 4.78 (d, J = 12.0 Hz, 1H), 4.79 (q, J = 6.0 Hz,
1H), 4.83 (d, J = 10.9 Hz, 1H), 4.94 (d, J = 10.8 Hz, 1H), 5.00 (d, J =
10.9 Hz, 1H), 5.43 (s, 1H), 5.69 (dd, J = 5.2, 1.3 Hz, 1H), 6.03 (t, J =
5.8 Hz, 1H), 7.19−7.43 (m, 21H), 7.44−7.61 (m, 3H), 7.82−7.88 (m,
2H), 7.89−7.92 (m, 2H), 7.93−7.98 (m, 2H); 13C NMR (100.53
MHz, CDCl3) δ 55.2, 63.4, 66.5, 69.8, 71.7, 73.4, 75.1, 75.7, 75.9, 77.5,
75.7, 80.0, 82.0, 98.0, 105.0, 127.5, 127.7, 127.8. 127.8, 127.9, 127.9,
127.9, 128.1, 128.1, 128.2, 128.2, 128.4, 128.4, 128.4, 128.4, 128.4,
128.4, 128.4, 128.4, 128.5, 128.5, 128.7, 129.0, 129.5, 129.6, 129.6,
129.7, 129.7, 129.7, 129.7, 133.0, 133.4, 133.4, 138.1, 138.1, 138.7,
165.0, 165.2, 166.1; HRMS (ESI-TOF) m/z calcd for
[C54H52O13+Na]+ 931.3306, found 931.3314.
Methyl 2,3,4-tri-O-benzoyl-6-O-(2,3,5-tri-O-benzoyl-β-D-ri-
bofuranosyl)-α-D-glucopyranoside (21a). This compound is
prepared using the above-mentioned general procedure using 7a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.150 g, 79%);
[α]2D5 (CHCl3, c 0.9) +52.8; IR (cm−1, CHCl3) 3062, 2944, 1727,
1
1588, 1449, 1274, 1103, 710; H NMR (399.78 MHz, CDCl3) δ 3.47
(s, 3H), 3.74 (dd, J = 11.6, 6.7 Hz, 1H), 3.96 (dd, J = 11.5, 2.2 Hz,
1H), 4.24 (ddd, J = 9.2, 6.6, 2.0 Hz, 1H), 4.46−4.57 (m, 1H), 4.65−
4.72 (m, 2H), 5.22 (t, J = 3.9 Hz, 1H), 5.25 (dd, J = 9.9, 3.6 Hz, 1H),
5.36 (s, 1H), 5.50 (t, J = 9.9 Hz, 1H), 5.75 (d, J = 4.9 Hz, 1H), 5.86
Methyl 2,3,6-tri-O-benzyl-4-O-(2,3,5-tri-O-benzoyl-α-D-lyxo-
furanosyl)-α-D-glucopyranoside (20f). This compound is prepared
using the above-mentioned general procedure using 6a (0.100 g, 0.2
mmol) as the starting material. Yield: (0.127 g, 70%); [α]2D5 (CHCl3, c
H
dx.doi.org/10.1021/jo501052y | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
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(dd, J = 6.9, 4.9 Hz, 1H), 6.12 (t, J = 9.7 Hz, 1H), 7.22−7.64 (m,
18H), 7.87 (ddd, J = 8.6, 7.4, 1.2 Hz, 6H), 7.96−8.04 (m, 6H); 13C
NMR (100.53 MHz, CDCl3) δ 55.6, 64.7, 66.9, 68.9, 69.5, 70.4, 72.1,
72.2, 75.4, 79.1, 96.7, 106.1, 128.2, 128.2, 128.3, 128.3, 128.3, 128.3,
128.3, 128.4, 128.4, 128.4, 128.4, 128.4, 128.4, 128.8, 128.9, 129.0,
129.2, 129.6, 129.6, 129.6, 129.7, 129.7, 129.7, 129.7, 129.8, 129.8,
129.8, 129.8, 129.9, 129.9, 133.0, 133.1, 133.3, 133.3, 133.3, 133.4,
165.1, 165.3, 165.3, 165.7, 165.7, 166.1; HRMS (ESI-TOF) m/z calcd
for [C54H46O16+Na]+ 973.2684, found 973.2690.
65.5, 67.1, 67.6, 68.4, 72.7, 75.3, 79.3, 106.0, 128.0, 128.0, 128.1, 128.3,
128.3, 128.3, 128.3, 128.4, 128.4, 128.4, 128.4, 128.4, 128.4, 128.4,
128.6, 128.6, 128.8, 129.0, 129.5, 129.7, 129.7, 129.7, 129.7, 129.8,
129.8, 133.1, 133.4, 133.5, 135.1, 136.1, 155.9, 165.1, 165.2, 166.0,
169.6; HRMS (ESI-TOF) m/z calcd for [C44H39O12N+Na]+
796.2370, found 796.2360.
Methyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-β-D-ribo-
furanosyl)-α-D-glucopyranoside (21f). This compound is prepared
using the above-mentioned general procedure using 7a (0.100 g, 0.2
mmol) as the starting material. Yield: (0.162 g, 89%); [α]2D5 (CHCl3, c
0.9) +50.5; IR (cm−1, CHCl3) 3022, 2940, 1728, 1602, 1453, 1270,
1106, 761; 1H NMR (399.78 MHz, CDCl3) δ 3.32 (s, 3H), 3.51 (t, J =
9.3 Hz, 1H), 3.56 (dd, J = 9.7, 3.5 Hz, 1H), 3.61 (dd, J = 10.8, 4.7 Hz,
1H), 3.72 (dd, J = 10.0, 4.2 Hz, 1H), 3.97 (t, J = 11.0 Hz, 2H), 4.54
(dd, J = 11.5, 6.0 Hz, 1H), 4.58 (s, 1H), 4.60 (d, J = 7.3 Hz, 1H),
4.62−4.72 (m, 3H), 4.80 (dd, J = 11.3, 9.3 Hz, 2H), 4.87 (d, J = 11.2
Hz, 1H), 4.99 (d, J = 10.9 Hz, 1H), 5.14 (s, 1H), 5.63 (d, J = 4.9 Hz,
1H), 5.82 (t, J = 5.6 Hz, 1H), 7.15−7.60 (m, 24H), 7.82−7.89 (m,
2H), 7.96−8.05 (m, 4H); 13C NMR (100.53 MHz, CDCl3) δ 55.3,
65.4, 66.7, 69.8, 72.8, 73.5, 75.0, 75.5, 75.8, 77.4, 79.1, 80.2, 82.2, 97.9,
105.9, 127.6, 127.8, 128.0, 128.0, 128.0, 128.0, 128.0, 128.2, 128.2,
128.4, 128.4, 128.4, 128.4, 128.4, 128.5, 128.5, 128.5, 128.6, 128.6,
128.6, 128.6, 129.0, 129.1, 129.3, 129.8, 129.8, 129.8, 129.9, 129.9,
129.9, 133.2, 133.5, 133.6, 138.3, 138.4, 138.9, 165.2, 165.4, 166.3;
HRMS (ESI-TOF) m/z calcd for [C54H52O13+Na]+ 931.3306, found
931.3313.
(Pent-4-enyl) 2,3,5-tri-O-benzoyl-β-D-ribofuranoside (21b).
This compound is prepared using the above-mentioned general
procedure using 7a (0.100 g, 0.2 mmol) as the starting material. Yield:
(0.095 g, 90%); [α]D25 (CHCl3, c 1.1) +41.0; IR (cm−1, CHCl3) 3070,
1
2927, 1728, 1596, 1450, 1269, 1113, 709; H NMR (399.78 MHz,
CDCl3) δ 1.63 (tq, J = 13.8, 6.9, 6.3 Hz, 2H), 2.08 (q, J = 7.1 Hz, 2H),
3.45 (dt, J = 9.4, 6.8 Hz, 1H), 3.78 (dt, J = 9.3, 6.5 Hz, 1H), 4.51 (dd, J
= 12.9, 6.6 Hz, 1H), 4.69−4.74 (m, 2H), 4.91−4.97 (m, 1H), 4.97−
5.04 (m, 1H), 5.24 (s, 1H), 5.68 (d, J = 4.7 Hz, 1H), 5.75 (ddt, J =
16.8, 10.3, 6.6 Hz, 1H), 5.87 (dd, J = 6.4, 5.0 Hz, 1H), 7.29−7.43 (m,
6H), 7.48−7.58 (m, 3H), 7.87−7.89 (m, 2H), 8.00−8.07 (m, 4H); 13C
NMR (100.53 MHz, CDCl3) δ 28.5, 30.1, 64.9, 67.8, 72.5, 75.5, 78.7,
105.5, 115.0, 128.3, 128.3, 128.3, 128.3, 128.3, 128.4, 128.4, 128.9,
129.2, 129.7, 129.7, 129.7, 129.7, 129.7, 129.7, 133.1, 133.3, 133.4,
137.8, 165.2, 165.4, 166.1; HRMS (ESI-TOF) m/z calcd for
[C31H30O8+Na]+ 553.1838, found 553.1836.
Benzyl 2,3,5-tri-O-benzoyl-β-D-ribofuranoside (21c). This
compound is prepared using the above-mentioned general procedure
using 7a (0.100 g, 0.2 mmol) as the starting material. Yield: (0.094 g,
85%); [α]2D5 (CHCl3, c 1.0) +12.1; IR (cm−1, CHCl3)) 3068, 2930,
1727, 1595, 1453, 1268, 1112, 706; 1H NMR (399.78 MHz, CDCl3) δ
4.53−4.59 (m, 1H), 4.59 (d, J = 11.8 Hz, 1H), 4.74 (dd, J = 15.3, 3.5
Hz 1H), 4.75−4.78(m, 1H), 4.82 (d, J = 11.8 Hz, 1H), 5.35 (s, 1H),
5.78 (d, J = 4.8 Hz, 1H), 5.94 (dd, J = 7.0, 4.8 Hz, 1H), 7.26−7.35 (m,
10H), 7.41 (t, J = 7.7 Hz, 2H), 7.49 (t, J = 7.5 Hz, 1H), 7.57 (t, J = 7.4
Hz, 1H), 7.88 (d, J = 7.3 Hz, 2H), 8.03 (dd, J = 12.3, 7.3 Hz, 4H); 13C
NMR (100.53 MHz, CDCl3) δ 64.6, 69.6, 72.3, 75.6, 79.0, 104.4,
127.8, 127.9, 127.9, 128.3, 128.3, 128.3, 128.3, 128.3, 128.4, 128.4,
128.4, 128.8, 129.1, 129.5, 129.6, 129.7, 129.7, 129.7, 129.7, 129.7,
133.0, 133.3, 133.4, 136.7, 165.2, 165.3, 166.2; HRMS (ESI-TOF) m/z
calcd for [C33H28O8+Na]+ 575.1682, found 575.1697.
Methyl 2,3,6-tri-O-benzyl-4-O-(2,3,5-tri-O-benzoyl-β-D-ribo-
furanosyl)-α-D-glucopyranoside (21g). This compound is pre-
pared using the above-mentioned general procedure using 7a (0.100 g,
0.2 mmol) as the starting material. Yield: (0.136 g, 75%); [α]D25
(CHCl3, c 1.1) +34.2; IR (cm−1, CHCl3) 3072, 2923, 1728, 1602,
1
1453, 1268, 1106, 700; H NMR (399.78 MHz, CDCl3) δ 3.35 (s,
3H), 3.52 (dd, J = 9.2, 3.5 Hz, 1H), 3.62−3.71 (m, 2H), 3.79 (dd, J =
10.9, 3.6 Hz, 1H), 3.85−3.99 (m, 2H), 4.43−4.52 (m, 1H), 4.55 (d, J
= 5.9 Hz, 2H), 4.57 (d, J = 5.4 Hz, 1H), 4.60 (d, J = 6.2 Hz, 2H),
4.56−4.64 (m, 1H), 4.75 (d, J = 12.2 Hz, 1H), 4.88 (d, J = 10.5 Hz,
1H), 5.00 (d, J = 10.5 Hz, 1H), 5.59 (dd, J = 4.8, 1.9 Hz, 1H), 5.64 (d,
J = 1.9 Hz, 1H), 5.75 (t, J = 5.4 Hz, 1H), 7.09−7.45 (m, 21H), 7.47−
7.62 (m, 3H), 7.87 (dd, J = 8.3, 1.1 Hz, 2H), 7.93 (dd, J = 8.2, 1.1 Hz,
2H), 8.02 (dd, J = 8.2, 1.2 Hz, 2H); 13C NMR (100.53 MHz, CDCl3)
δ 55.3, 64.6, 68.4, 69.4, 72.0, 73.3, 73.4, 75.3, 75.4, 77.2, 78.6, 79.7,
80.6, 98.1, 106.7, 127.3, 127.4, 127.5, 127.5, 127.9, 127.9, 127.9, 128.1,
128.1, 128.2, 128.2, 128.2, 128.2, 128.3, 128.3, 128.3, 128.3, 128.4,
128.4, 128.4, 128.4, 128.9, 129.1, 129.7, 129.7, 129.7, 129.7, 129.7,
129.7. 129.7. 133.0, 133.4, 133.4, 137.9, 138.0, 138.8, 165.1, 165.3,
166.0; HRMS (ESI-TOF) m/z calcd for [C54H52O13+Na]+ 931.3306,
found 931.3286.
Cholesteryl 2,3,5-tri-O-benzoyl-β-D-ribofuranoside (21d).
This compound is prepared using the above-mentioned general
procedure using 7a (0.100 g, 0.2 mmol) as the starting material. Yield:
(0.136 g, 82%); [α]D25 (CHCl3, c 1.3) −1.5; IR (cm−1, CHCl3) 3071,
1
2942, 1729, 1591, 1455, 1269, 1111, 709; H NMR (399.78 MHz,
CDCl3) δ 0.66 (s, 3H), 0.85 (dd, J = 6.6, 1.5 Hz, 6H), 0.88−1.66 (m,
25H), 1.73−2.03 (m, 6H), 2.21 (t, J = 11.1 Hz, 1H), 2.38 (ddd, J =
13.0, 4.5, 1.9 Hz, 1H), 3.55 (dq, J = 11.1, 5.6, 4.4 Hz, 2H), 4.52 (q, J =
13, 6.8 Hz 1H), 4.64−4.74 (m, 2H), 5.33 (d, J = 5.1 Hz, 1H), 5.41 (s,
1H), 5.63 (d, J = 4.8 Hz, 1H), 5.88 (dd, J = 6.4, 4.9 Hz, 1H), 7.27−
7.45 (m, 6H), 7.45−7.61 (m, 3H), 7.88 (d, J = 7.6 Hz, 2H), 8.03 (dd, J
= 15.8, 7.5 Hz, 4H); 13C NMR (100.53 MHz, CDCl3) δ 12.0, 18.8,
19.4, 21.1, 22.7, 22.9, 23.9, 24.4, 28.1, 28.3, 29.6, 31.9, 32.0, 35.9, 36.3,
36.8, 37.2, 38.6, 39.6, 39.9, 42.4, 50.2, 56.2, 56.8, 65.2, 72.8, 76.2, 78.1,
78.6, 103.9, 122.1, 128.4, 128.4, 128.4, 128.4, 128.6, 128.6, 129.1,
129.4, 129.8, 129.8, 129.8, 129.9, 129.9, 129.9, 129.9, 133.2, 133.4,
133.5, 140.4, 165.4, 165.5, 166.3; HRMS (ESI-TOF) m/z calcd for
[C53H66O8+Na]+ 853.4655, found 853.4664.
Benzyl-N-(benzyloxycarbonyl)-O-(2,3,5-tri-O-benzoyl-β-D-ri-
bofuranosyl)-L-serinate (21e). This compound is prepared using
the above-mentioned general procedure using 7a (0.100 g, 0.2 mmol)
as the starting material. Yield: (0.136 g, 88%); [α]2D5 (CHCl3, c 1.3)
+12.1; IR (cm−1, CHCl3) 3371, 3061, 2947, 1725, 1596, 1504, 1453,
1267, 1114, 703; 1H NMR (399.78 MHz, CDCl3) δ 3.82 (dd, J = 10.1,
3.2 Hz, 1H), 4.30 (dd, J = 10.1, 3.2 Hz, 1H), 4.44 (qd, J = 11.6, 5.7 Hz,
2H), 4.57−4.73 (m, 2H), 5.12 (s, 2H), 5.23 (ABq, J = 12.23 Hz, 2H),
5.25 (s, 1H), 5.59 (t, J = 5.20 Hz, 1H), 5.64 (d, J = 5.0 Hz, 1H), 5.79
(d, J = 8.6 Hz, 1H), 7.23−7.43 (m, 16H), 7.46−7.53 (m, 2H), 7.56 (t,
J = 7.4 Hz, 1H), 7.88 (d, J = 7.3 Hz, 2H), 7.97 (d, J = 7.5 Hz, 2H),
8.01 (d, J = 7.3 Hz, 2H); 13C NMR (100.53 MHz, CDCl3) δ 54.2,
(Pent-4-enyl) 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-β-D-
ribofuranosyl)-α-D-mannopyranoside (21h). This compound is
prepared using the above-mentioned general procedure using 7a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.144 g, 75%);
[α]2D5 (CHCl3, c 1.3) +35.2; IR (cm−1, CHCl3) 3072, 2926, 1728,
1
1599, 1453, 1268, 1109, 705; H NMR (399.78 MHz, CDCl3) δ 1.59
(quintet, J = 6.9 Hz, 2H), 2.04 (q, J = 7.0 Hz, 2H), 3.31 (dt, J = 9.7,
6.4 Hz, 1H), 3.62 (dt, J = 9.7, 6.6 Hz, 1H), 3.68−3.79 (m, 3H), 3.82−
3.93 (m, 2H), 4.03 (d, J = 9.1 Hz, 1H), 4.62 (s, 2H), 4.57−4.72 (m,
5H), 4.74 (s, 1H), 4.81 (d, J = 1.5 Hz, 1H), 4.91 (s, 1H), 4.92−5.01
(m, 2H), 5.32 (s, 1H), 5.70 (d, J = 4.9 Hz, 1H), 5.72−5.84 (m, 2H),
7.09−7.67 (m, 24H), 7.86 (d, J = 7.4 Hz, 2H), 7.97−8.09 (m, 4H);
13C NMR (100.53 MHz, CDCl3) δ 28.5, 30.2, 65.7, 66.9, 67.1, 71.5,
72.0, 72.4, 72.9, 74.5, 74.7, 75.0, 75.4, 79.0, 80.2, 97.6, 105.7, 114.8,
127.5, 127.5, 127.6, 127.6, 127.6, 127.8, 127.8, 128.0, 128.0, 128.3,
128.3, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3,
128.3, 128.4, 128.4, 129.0, 129.3, 129.7, 129.7, 129.8, 129.8, 132.9,
132.9, 133.2, 133.4, 138.1, 138.3, 138.4, 138.5, 165.1, 165.2, 166.2;
HRMS (ESI-TOF) m/z calcd for [C58H58O13+Na]+ 985.3775, found
985.3776.
(Prop-2-ynyl) 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-β-
D-ribofuranosyl)-α-D-glucopyranoside (21i). This compound is
prepared using the above-mentioned general procedure using 7a
I
dx.doi.org/10.1021/jo501052y | J. Org. Chem. XXXX, XXX, XXX−XXX

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(0.100 g, 0.2 mmol) as the starting material. Yield: (0.160 g, 86%);
[α]2D5 (CHCl3, c 1.1) +70.0; IR (cm−1, CHCl3) 3293, 3072, 2927,
1727, 1595, 1453, 1268, 1107, 706; 1H NMR (399.78 MHz, CDCl3) δ
2.42 (t, J = 2.1 Hz, 1H), 3.55 (t, J = 9.5 Hz, 1H), 3.62 (td, J = 10.1, 9.3,
4.1 Hz, 2H), 3.80 (dd, J = 10.2, 3.5 Hz, 1H), 3.95 (d, J = 9.4 Hz, 1H),
4.00 (t, J = 9.3 Hz, 1H), 4.24 (d, J = 2.0 Hz, 2H), 4.55 (dd, J = 11.6,
5.9 Hz, 1H), 4.61 (d, J = 11.3 Hz, 1H), 4.63−4.73 (m, 2H), 4.75 (d, J
= 3.2 Hz, 2H), 4.81 (d, J = 10.9 Hz, 1H), 4.89 (d, J = 11.2 Hz, 1H),
5.01 (d, J = 10.9 Hz, 1H), 5.04 (d, J = 3.6 Hz, 1H), 5.15 (s, 1H), 5.64
(d, J = 4.9 Hz, 1H), 5.82 (t, J = 5.5 Hz, 1H), 7.14−7.46 (m, 20H),
7.44−7.54 (m, 3H), 7.57 (t, J = 7.2 Hz, 1H), 7.88 (d, J = 7.7 Hz, 2H),
8.00 (d, J = 7.8 Hz, 2H), 8.04 (d, J = 7.8 Hz, 2H); 13C NMR (100.53
MHz, CDCl3) δ 54.6, 65.2, 66.3, 70.4, 72.6, 73.0, 74.7, 74.9, 75.34,
75.6, 77.2, 79.0, 79.0, 79.6, 81.9, 95.1, 105.7, 127.5, 127.6, 127.8, 127.9,
127.9, 127.9, 128.2, 128.2, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3,
128.3, 128.3, 128.3, 128.3, 128.4, 128.4, 128.4, 128.4, 128.9, 129.1,
129.7, 129.7, 129.7, 129.7, 129.7, 129.7, 133.0, 133.3, 133.4, 137.9,
138.2, 138.7, 165.1, 165.3, 166.1; HRMS (ESI-TOF) m/z calcd for
[C56H52O13+Na]+ 955.3306, found 955.3303.
133.5, 133.6, 138.0, 165.1, 165.3, 166.1; HRMS (ESI-TOF) m/z calcd
for [C31H30O8+Na]+ 553.1838, found 553.1837.
Benzyl 2,3,5-tri-O-benzoyl-β-D-xylofuranoside (22c). This
compound is prepared using the above-mentioned general procedure
using 8a (0.100 g, 0.2 mmol) as the starting material. Yield: (0.094 g,
84%); [α]2D5 (CHCl3, c 0.7) +6.7; IR (cm−1, CHCl3) 3067, 2923, 1725,
1595, 1450, 1262, 1106, 700; 1H NMR (399.78 MHz, CDCl3) δ 4.57−
4.66 (m, 2H), 4.67−4.74 (m, 1H), 4.93 (d, J = 11.5 Hz, 1H), 5.01 (q, J
= 5.8 Hz, 1H), 5.37 (s, 1H), 5.61 (s, 1H), 5.90 (d, J = 5.6 Hz, 1H),
7.40 (m, 12H), 7.53 (t, J = 7.0 Hz, 1H), 7.60 (t, J = 7.4 Hz, 1H), 7.98
(t, J = 7.6 Hz, 4H), 8.06 (d, J = 7.4 Hz, 2H); 13C NMR (100.53 MHz,
CDCl3) δ 63.6, 69.5, 75.1, 79.1, 81.0, 105.2, 127.8, 128.0, 128.0, 128.3,
128.3, 128.4, 128.4, 128.4, 128.4, 128.4, 128.5, 128.5, 128.9, 129.6,
129.7, 129.7, 129.9, 129.9, 129.9, 129.9, 133.1, 133.5, 133.6, 137.1,
165.0, 165.2, 166.1; HRMS (ESI-TOF) m/z calcd for
[C33H28O8+Na]+ 575.1682, found 575.1693.
Cholesteryl 2,3,5-tri-O-benzoyl-β-D-xylofuranoside (22d).
This compound is prepared using the above-mentioned general
procedure using 8a (0.100 g, 0.2 mmol) as the starting material. Yield:
(0.130 g, 78%); [α]D25 (CHCl3, c 1.6) −25.5; IR (cm−1, CHCl3) 2940,
1728, 1601, 1453, 1263, 1107, 708; 1H NMR (399.78 MHz, CDCl3) δ
0.68 (s, 3H), 0.86 (d, J = 1.7 Hz, 3H), 0.87 (d, J = 1.7 Hz, 3H), 0.92
(d, J = 6.5 Hz, 3H), 1.01 (s, 3H), 1.06−2.09 (m, 26H), 2.28 (ddd, J =
13.3, 4.5, 1.7 Hz, 1H), 2.43 (ddd, J = 13.2, 4.3, 1.7 Hz, 1H), 3.65 (tt, J
= 11.1, 4.5 Hz, 1H), 4.64 (qd, J = 11.4, 6.4 Hz, 2H), 4.95 (q, J = 6.2
Hz, 1H), 5.34 (d, J = 4.9 Hz, 1H), 5.42 (s, 1H), 5.52 (d, J = 1.1 Hz,
1H), 5.88 (dd, J = 5.9, 1.5 Hz, 1H), 7.32−7.64 (m, 9H), 7.96−8.00
(m, 2H), 8.07 (d, J = 8.2 Hz, 4H); 13C NMR (100.53 MHz, CDCl3) δ
11.8, 18.6, 19.3, 21.0, 22.5, 22.8, 23.7, 24.2, 27.9, 28.2, 29.5, 31.8, 31.9,
35.7, 36.1, 36.7, 37.2, 38.3, 39.4, 39.7, 42.2, 50.0, 56.0, 56.7, 63.7, 75.3,
77.0, 78.4, 81.5, 103.9, 121.9, 128.2, 128.2, 128.4, 128.4, 128.4, 128.4,
129.0, 129.0, 129.5, 129.6, 129.6, 129.8, 129.8, 129.9, 129.9, 133.0,
133.4, 133.5, 140.2, 165.1, 165.2, 166.1; HRMS (ESI-TOF) m/z calcd
for [C53H66O8+Na]+ 853.4655, found 853.4667.
Benzyl N-(benzyloxycarbonyl)-O-(2,3,5-tri-O-benzoyl-β-D-xy-
lofuranosyl)-L-serinate (22e). This compound is prepared using the
above-mentioned general procedure using 8a (0.100 g, 0.2 mmol) as
the starting material. Yield: (0.136 g, 88%); [α]2D5 (CHCl3, c 1.0)
+23.7; IR (cm−1, CHCl3) 3431, 3365, 3030, 2933, 1724, 1591, 1447,
1262, 1107, 706; 1H NMR (399.78 MHz, CDCl3) δ 3.85 (dd, J = 10.0,
3.3 Hz, 1H), 4.40 (dd, J = 10.0, 2.8 Hz, 1H), 4.51 (ddd, J = 16.8, 11.4,
6.6 Hz, 2H), 4.66 (dt, J = 8.7, 3.0 Hz, 1H), 4.94 (q, J = 6.1 Hz, 1H),
5.10 (d, J = 4.3 Hz, 2H), 5.13 (d, J = 11.0 Hz, 1H), 5.21 (s, 1H), 5.25
(d, J = 12.2 Hz, 1H), 5.51 (d, J = 1.5 Hz, 1H), 5.70−6.09 (m, 2H),
7.16−7.72 (m, 19H), 7.95 (dd, J = 8.2, 1.2 Hz, 2H), 8.00−8.06 (m,
4H); 13C NMR (100.53 MHz, CDCl3) δ 54.2, 63.3, 67.3, 67.4, 68.0,
74.3, 79.1, 81.1, 106.8, 128.0, 128.0, 128.2, 128.2, 128.3, 128.3, 128.3,
128.4, 128.4, 128.5, 128.5, 128.5, 128.5, 128.6, 128.6, 128.6, 128.7,
129.4, 129.6, 129.6, 129.6, 129.9, 129.9, 129.9, 129.9, 133.1, 133.7,
133.7, 135.1, 136.1, 156.0, 165.1, 165.2, 165.9, 169.7; HRMS (ESI-
TOF) m/z calcd for [C44H39O12N+Na]+ 796.2370, found 796.2371.
Methyl-2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-β-D-xylo-
furanosyl)-α-D-glucopyranoside (22f). This compound is prepared
using the above-mentioned general procedure using 8a (0.100 g, 0.2
mmol) as the starting material. Yield: (0.160 g, 88%); [α]2D5 (CHCl3, c
0.9) +35.7; IR (cm−1, CHCl3) 3068, 2925, 1725, 1594, 1457, 1263,
1103, 706; 1H NMR (399.78 MHz, CDCl3) δ 3.27 (s, 3H), 3.51 (dd, J
= 9.6, 3.6 Hz, 1H), 3.63 (t, J = 9.4 Hz, 1H), 3.71 (dd, J = 10.5, 4.2 Hz,
1H), 3.77 (dd, J = 10.0, 2.9 Hz, 1H), 3.98 (t, J = 9.2 Hz, 1H), 4.03 (dd,
J = 9.7, 0.9 Hz, 1H), 4.56 (dd, J = 11.5, 5.8 Hz, 1H), 4.65 (d, J = 6.3
Hz, 2H), 4.67 (s, 2H), 4.75 (d, J = 12.1 Hz, 1H), 4.85 (dd, J = 11.0 Hz,
2H), 4.91−5.04 (m, 2H), 5.17 (s, 1H), 5.50 (d, J = 1.2 Hz, 1H), 5.85
(dd, J = 6.0, 1.4 Hz, 1H), 7.11−7.74 (m, 24H), 7.95 (dd, J = 8.1, 1.1
Hz, 2H), 8.00−8.06 (m, 4H); 13C NMR (100.53 MHz, CDCl3) δ 55.0,
63.8, 66.4, 69.7, 73.2, 75.0, 75.2, 75.7, 77.4, 78.8, 80.2, 81.2, 82.1, 97.8,
106.0, 127.5, 127.6, 127.8, 127.9, 127.9, 127.9, 127.9, 128.0, 128.0,
128.3, 128.3, 128.3, 128.3, 128.3, 128.3, 128.4, 128.4, 128.4, 128.4,
128.5, 128.5, 128.9, 128.9, 129.6, 129.6, 129.7, 129.9, 129.9, 129.9,
129.9, 133.0, 133.5, 133.6, 138.2, 138.3, 138.7, 165.0, 165.2, 166.1;
(Prop-2-ynyl) 3,5-di-O-benzyl-2-O-(2,3,5-tri-O-benzoyl-β-D-
ribofuranosyl)-α-D-arabinofuranoside (21j). This compound is
prepared using the above-mentioned general procedure using 7a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.107 g, 66%);
[α]2D5 (CHCl3, c 0.8) +31.7; IR (cm−1, CHCl3) H NMR (399.78
1
MHz, CDCl3) δ 2.30 (t, J = 2.3 Hz, 1H), 3.54 (dd, J = 10.7, 5.6 Hz,
1H), 3.57 (dd, J = 10.8, 4.0 Hz, 1H), 4.07 (dd, J = 6.4, 2.7 Hz, 1H),
4.22−4.27 (m, 1H), 4.28 (dd, J = 2.3, 1.4 Hz, 2H), 4.49 (s, 2H), 4.53
(ABq, J = 11.8 Hz, 2H), 4.62 (dd, J = 6.1, 4.1 Hz, 2H), 4.78 (d, J =
11.8 Hz, 1H), 4.96 (q, J = 5.5 Hz, 1H), 5.38 (d, J = 17.6 Hz, 2H), 5.57
(s, 1H), 5.83 (dd, J = 5.4, 1.7 Hz, 1H), 7.16−7.72 (m, 19H), 7.98
(ddd, J = 8.3, 2.8, 1.2 Hz, 4H), 8.06 (dd, J = 8.3, 1.3 Hz, 2H); 13C
NMR (100.53 MHz, CDCl3) δ 54.1, 69.5, 72.4, 72.5, 73.4, 74.7, 75.6,
76.9, 77.1, 79.2, 81.7, 83.8, 86.9, 104.2, 105.4, 127.7, 127.7, 127.7,
127.7, 127.7, 127.8, 127.8, 128.3, 128.3, 128.4, 128.4, 128.4, 128.4,
128.4, 128.5, 128.5, 128.5,, 129.7, 129.7, 129.7, 129.7, 129.7, 129.8,
129.8, 133.2, 133.4, 133.5, 137.6, 137.9, 138.1, 165.1, 165.3, 166.0;
HRMS (ESI-TOF) m/z calcd for [C48H44O12+Na]+ 835.2730, found
835.2735.
Methyl 2,3,4-tri-O-benzoyl-6-O-(2,3,5-tri-O-benzoyl-β-D-xy-
lofuranosyl)-α-D-glucopyranoside (22a). This compound is
prepared using the above-mentioned general procedure using 8a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.152 g, 80%);
[α]2D5 (CHCl3, c 1.3) +33.3; IR (cm−1, CHCl3) 3074, 2929, 1727,
1
1596, 1457, 1268, 1105, 709; H NMR (399.78 MHz, CDCl3) δ 3.39
(s, 3H), 3.79 (dd, J = 11.0, 5.6 Hz, 1H), 4.07 (d, J = 11.3 Hz, 1H),
4.25−4.32 (m, 1H), 4.55−4.71 (m, 2H), 4.95 (q, J = 5.4 Hz, 1H), 5.22
(d, J = 9.5 Hz, 1H), 5.25 (s, 1H), 5.32 (s, 1H), 5.60 (d, J = 10.0 Hz,
1H), 5.63 (s, 1H), 5.87 (d, J = 5.2 Hz, 1H), 6.16 (t, J = 9.4 Hz, 1H),
7.18−7.68 (m, 18H), 7.85 (d, J = 7.5 Hz, 2H), 7.93 (t, J = 7.5 Hz, 4H),
7.99 (d, J = 7.5 Hz, 2H), 8.04 (d, J = 7.5 Hz, 2H), 8.11 (d, J = 7.4 Hz,
2H); 13C NMR (100.53 MHz, CDCl3) δ 55.5, 63.5, 66.6, 68.9, 69.3,
70.5, 72.2, 75.2, 79.0, 81.0, 96.8, 106.5, 128.2, 128.2, 128.3, 128.3,
128.3, 128.3, 128.4, 128.4, 128.5, 128.5, 128.6, 128.6, 128.9, 129.0,
129.1, 129.2, 129.6, 129.6, 129.6, 129.6, 129.6, 129.6, 129.8, 129.8,
129.9, 129.9, 129.9, 129.9, 130.0, 130.0, 133.0, 133.0, 133.3, 133.3,
133.5, 133.6, 164.8, 165.2, 165.3, 165.7, 165.8, 166.0; HRMS (ESI-
TOF) m/z calcd for [C54H46O16+Na]+ 973.2684, found 973.2707.
Pent-4-enyl 2,3,5-tri-O-benzoyl-β-D-xylofuranoside (22b).
This compound is prepared using the above-mentioned general
procedure using 8a (0.100 g, 0.2 mmol) as the starting material. Yield:
(0.100 g, 94%); [α]D25 (CHCl3, c 1.1) +14.2; IR (cm−1, CHCl3) 3074,
1
2927, 1725, 1594, 1453, 1262, 1108, 706; H NMR (399.78 MHz,
CDCl3) δ 1.75 (quintet, J = 6.7 Hz, 2H), 2.18 (q, J = 7.1 Hz, 2H), 3.54
(dt, J = 9.3, 6.4 Hz, 1H), 3.87 (dt, J = 9.3, 6.5 Hz, 1H), 4.64 (dABq, J =
11.4, 6.3 Hz, 2H), 4.93−4.99 (m, 2H), 4.97 (s, 1H), 5.24 (s, 1H), 5.64
(d, J = 0.8 Hz, 1H), 5.81 (ddt, J = 16.8, 10.1, 6.6 Hz, 1H), 5.87 (dd, J =
5.8, 1.4 Hz, 1H), 7.34−7.69 (m, 9H), 7.96−8.02 (m, 2H), 8.03−8.09
(m, 4H); 13C NMR (100.53 MHz, CDCl3) δ 28.7, 30.2, 63.6, 67.6,
75.3, 78.6, 81.1, 106.1, 114.9, 128.3, 128.3, 128.5, 128.5, 128.5, 128.5,
128.5, 129.0, 129.6, 129.7, 129.7, 129.9, 129.9, 129.9, 129.9, 133.0,
J
dx.doi.org/10.1021/jo501052y | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
HRMS (ESI-TOF) m/z calcd for [C54H52O13+Na]+ 931.3306, found
931.3309.
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.109 g, 67%);
[α]2D5 (CHCl3, c 0.9) +38.8; IR (cm−1, CHCl3) 3074, 2929, 1727,
1596, 1457, 1268, 1105, 709;1H NMR (399.78 MHz, CDCl3) δ 2.30
(t, J = 2.3 Hz, 1H), 3.53−3.61 (m, 2H), 4.07 (dd, J = 6.4, 2.7 Hz, 1H),
4.22−4.27 (m, 1H), 4.28 (dd, J = 2.3, 1.4 Hz, 2H), 4.49 (s, 2H), 4.53
(d, J = 11.8 Hz, 1H), 4.62 (dd, J = 6.1, 4.1 Hz, 2H), 4.78 (d, J = 11.8
Hz, 1H), 4.96 (q, J = 5.5 Hz, 1H), 5.36 (s, 1H), 5.40 (s, 1H), 5.57 (d, J
= 1.5 Hz, 2H), 5.83 (dd, J = 5.4, 1.7 Hz, 1H), 7.03−7.77 (m, 19H),
7.79−8.32 (m, 6H); 13C NMR (100.53 MHz, CDCl3) δ 54.1, 63.3,
69.7, 72.3, 73.3, 74.6, 74.9, 79.0, 79.1, 80.9, 81.6, 83.9, 86.5, 104.3,
105.9, 127.6, 127.7, 127.7, 127.7, 127.7, 128.3, 128.3, 128.3, 128.3,
128.3, 128.3, 128.4, 128.4, 128.5, 128.5, 128.5, 128.5, 128.8, 129.4,
129.7, 129.7, 129.8, 129.9, 129.9, 129.9, 133.2, 133.6, 133.7, 137.6,
137.9, 164.9, 165.2, 166.0, HRMS (ESI-TOF) m/z calcd for
[C48H44O12+Na]+ 812.2833, found 812.2830.
Methyl 2,3,6-tri-O-benzyl-4-O-(2,3,5-tri-O-benzoyl-β-D-xylo-
furanosyl)-α-D-glucopyranoside (22g). This compound is pre-
pared using the above-mentioned general procedure using 8a (0.100 g,
0.2 mmol) as the starting material. Yield: (0.140 g, 77%); [α]D25
(CHCl3, c 0.6) +29.0; IR (cm−1, CHCl3) 3071, 2924, 1725, 1595,
1
1443, 1262, 1105, 706; H NMR (399.78 MHz, CDCl3) δ 3.36 (s,
3H), 3.53 (dd, J = 9.4, 3.6 Hz, 1H), 3.59 (d, J = 9.2 Hz, 1H), 3.65−
3.77 (m, 2H), 3.91 (t, J = 9.2 Hz, 1H), 3.99 (t, J = 9.1 Hz, 1H), 4.38
(s, 2H), 4.52 (dd, J = 11.6, 6.4 Hz, 1H), 4.56 (s, 1H), 4.58 (d, J = 7.4
Hz, 1H), 4.63 (dd, J = 11.5, 5.3 Hz, 1H), 4.73 (d, J = 12.1 Hz, 1H),
4.81 (q, J = 5.6 Hz, 1H), 4.91 (d, J = 10.5 Hz, 1H), 5.10 (d, J = 10.5
Hz, 1H), 5.51 (s, 1H), 5.57 (s, 1H), 5.76 (dd, J = 5.1, 1.8 Hz, 1H),
7.06−7.68 (m, 24H), 7.95 (d, J = 7.4 Hz, 2H), 7.98 (d, J = 7.4 Hz,
2H), 8.02 (d, J = 7.4 Hz, 2H); 13C NMR (100.53 MHz, CDCl3) δ
55.3, 63.0, 68.4, 69.5, 73.2, 73.5, 74.91, 75.2, 77.7, 78.4, 79.7, 80.7,
80.8, 98.1, 107.9, 127.3, 127.3, 127.4, 127.4, 127.7, 127.7, 127.8, 128.1,
128.1, 128.1, 128.1, 128.2, 128.2, 128.3, 128.3, 128.4, 128.4, 128.5,
128.5, 128.5, 128.5, 128.8, 128.9, 129.5, 129.7, 129.7, 129.9, 129.9,
129.9, 129.9, 133.0, 133.6, 133.6, 137.8, 138.1, 138.9, 164.9, 165.2,
166.0; HRMS (ESI-TOF) m/z calcd for [C54H52O13+Na]+ 931.3306,
found 931.3311.
Methyl 2,3,4-tri-O-benzyl-6-O-(3,5-di-O-benzyl β-D-ribofura-
nosyl) α-D-glucopyranoside (23a).12 This compound is prepared
using the above-mentioned general procedure using 7b (0.200 g, 0.42
mmol) as the starting material. Yield: (0.263 g, 80% over two steps);
[α]2D5 (CHCl3, c 1.1) δ 1.5; IR (cm−1, CHCl3) 3456, 3073, 3031, 2923,
1
2862, 1594, 1455, 1059, 740; H NMR (399.78 MHz, CDCl3) δ 2.71
(d, J = 2.7 Hz, 1H), 3.33 (s, 3H), 3.46 (t, J = 9.2 Hz, 1H), 3.51 (dd, J =
9.7, 3.5 Hz, 1H), 3.55 (d, J = 5.6 Hz, 2H), 3.55 (dd, J = 10.9, 5.0 Hz,
1H), 3.70 (ddd, J = 10.0, 4.8, 1.5 Hz, 1H), 3.89 (dd, J = 10.9, 1.7 Hz,
1H), 3.98 (t, J = 9.2 Hz, 1H), 4.00−4.12 (m, 2H), 4.22 (q, J = 5.5 Hz,
1H), 4.50 (ABq, J = 12.0 Hz, 2H), 4.56 (s, 3H), 4.57 (d, J = 9.8 Hz,
1H), 4.67 (d, J = 12.2 Hz, 1H), 4.80 (t, J = 10.8 Hz, 2H), 4.88 (d, J =
11.0 Hz, 1H), 4.95 (s, 1H), 4.99 (d, J = 10.8 Hz, 1H), 7.19−7.43 (m,
25H); 13C NMR (100.53 MHz, CDCl3) δ 55.0, 66.3, 69.9, 71.6, 72.7,
73.2, 73.3, 73.3, 74.9, 75.7, 77.6, 79.6, 79.9, 80.7, 82.1, 97.9, 107.8,
127.5, 127.6, 127.6, 127.6, 127.7, 127.8, 127.8, 127.8, 127.8, 127.8,
127.9, 127.9, 128.1, 128.1, 128.1, 128.3, 128.3, 128.4, 128.4, 128.4,
128.4, 128.4, 128.4, 128.5, 128.5, 137.1, 138.1, 138.1, 138.1, 138.6;
HRMS (ESI-TOF) m/z calcd for [C47H52O10+Na]+ 799.3458, found
799.3470.
Pent-4-enyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-β-D-
xylofuranosyl)-α-D-mannopyranoside (22h). This compound is
prepared using the above-mentioned general procedure using 8a
(0.100 g, 0.2 mmol) as the starting material. Yield: (0.150 g, 78%);
[α]2D5 (CHCl3, c 1.0) +26.3; IR (cm−1, CHCl3) 3074, 2926, 1726,
1
1595, 1450, 1264, 1108, 710; H NMR (399.78 MHz, CDCl3) δ 1.49
(quintet, J = 6.9 Hz, 2H), 1.89−1.99 (m, 2H), 3.22 (dt, J = 9.8, 6.4 Hz,
1H), 3.54 (dt, J = 9.7, 6.5 Hz, 1H), 3.73−3.79 (m, 2H), 3.84 (dd, J =
10.8, 5.8 Hz, 1H), 3.90 (dd, J = 9.3, 3.0 Hz, 1H), 3.97 (t, J = 9.4 Hz,
1H), 4.08 (dd, J = 10.8, 1.2 Hz, 1H), 4.58−4.62 (m, 1H), 4.62 (s, 2H),
4.64 (d, J = 2.6 Hz, 1H), 4.67 (d, J = 2.3 Hz, 2H), 4.73 (dd, J = 11.5,
7.1 Hz, 1H), 4.79 (d, J = 1.6 Hz, 1H), 4.88 (s, 1H), 4.91 (s, 1H),
4.89−4.99 (m, 2H), 5.32 (s, 1H), 5.57 (d, J = 1.2 Hz, 1H), 5.69 (ddt, J
= 16.9, 10.2, 6.7 Hz, 1H), 5.85 (dd, J = 6.2, 1.5 Hz, 1H), 7.10−7.69
(m, 24H), 7.97 (dd, J = 8.0, 1.0 Hz, 2H), 8.02−8.15 (m, 4H); 13C
NMR (100.53 MHz, CDCl3) δ 28.5, 30.1, 63.8, 66.8, 67.5, 71.5, 72.1,
72.3, 74.5, 74.8, 75.1, 75.5, 78.7, 80.2, 81.3, 97.6, 106.4, 114.7, 127.5,
127.5, 127.6, 127.6, 127.6, 127.8, 127.8, 128.0, 128.0, 128.2, 128.2,
128.2, 128.2, 128.3, 128.3, 128.3, 128.3, 128.5, 128.5, 128.5, 128.5,
128.9, 129.1, 129.7, 129.7, 129.8, 129.9, 129.9, 130.0, 130.0, 132.9,
133.4, 133.5, 138.0, 138.2, 138.4, 138.5, 164.9, 165.4, 166.1.; HRMS
(ESI-TOF) m/z calcd for [C58H58O13+Na]+ 985.3775, found
985.3779.
Menthyl 3,5-di-O-benzyl β-D-ribofuranoside (23b).12 This
compound is prepared using the above-mentioned general procedure
using 7b (0.200 g, 0.42 mmol) as the starting material. Yield: (0.155 g,
78% over two steps); [α]D25 (CHCl3, c 1.0) −73.8; IR (cm−1, CHCl3)
1
3414, 3043, 2924, 2861, 1591, 1457, 1111, 691; H NMR (399.78
MHz, CDCl3) δ 0.70 (d, J = 6.9 Hz, 3H), 0.83 (d, J = 7.2 Hz, 3H),
0.70−1.05 (m, 2H), 0.89 (d, J = 6.5 Hz, 3H), 1.08−1.21 (m, 1H),
1.21−1.44 (m, 2H), 1.60 (d, J = 14.7 Hz, 2H), 1.96−2.26 (m, 2H),
2.64 (d, J = 2.7 Hz, 1H), 3.42 (td, J = 10.6, 4.2 Hz, 1H), 3.55 (d, J =
5.7 Hz, 2H), 3.90−4.05 (m, 2H), 4.22 (q, J = 5.6 Hz, 1H), 4.51 (d, J =
12.0 Hz, 1H), 4.54−4.64 (m, 3H), 5.16 (s, 1H), 6.90−7.67 (m, 10H);
13C NMR (100.53 MHz, CDCl3) δ 16.0, 21.1, 22.3, 23.0, 25.1, 31.3,
(Prop-2-ynyl) 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzoyl-β-
D-xylofuranosyl)-α-D-glucopyranoside (22i). This compound is
prepared using the above-mentioned general procedure using 8a
(0.100 g, 1 mmol) as the starting material. Yield: (0.160 g, 86%); [α]D25
(CHCl3, c 1.1) +38.0; IR (cm−1, CHCl3) 3293, 3065, 3034, 2926,
1726, 1596, 1453, 1264, 1105, 706; 1H NMR (399.78 MHz, CDCl3) δ
2.38 (t, J = 2.3 Hz, 1H), 3.56 (dd, J = 9.6, 3.7 Hz, 1H), 3.66 (t, J = 9.2
Hz, 1H), 3.74 (dd, J = 10.7, 4.0 Hz, 1H), 3.83 (dd, J = 10.0, 2.6 Hz,
1H), 4.01 (t, J = 9.4 Hz, 2H), 4.19 (dABq, J = 16.0, 2.4 Hz, 2H), 4.58
(dd, J = 11.5, 5.7 Hz, 1H), 4.63−4.69 (m, 2H), 4.72 (s, 2H), 4.86
(ABq, J = 11.0 Hz, 2H), 4.93−5.03 (m, 2H), 5.12 (d, J = 3.6 Hz, 1H),
5.18 (s, 1H), 5.51 (d, J = 1.1 Hz, 1H), 5.86 (dd, J = 6.0, 1.4 Hz, 1H),
7.06−7.71 (m, 24H), 7.98 (dd, J = 8.2, 1.0 Hz, 2H), 8.01−8.08 (m,
4H); 13C NMR (100.53 MHz, CDCl3) δ 54.3, 63.8, 66.2, 70.3, 72.8,
74.7, 75.0, 75.2, 75.7, 78.8, 79.0, 79.7, 81.1, 81.1, 81.9, 95.0, 105.9,
127.5, 127.6, 127.8, 127.9, 127.9, 128.0, 128.0, 128.0, 128.0, 128.0,
128.0, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3, 128.4, 128.4, 128.4,
128.4, 128.5, 128.5, 128.9, 129.6, 129.6, 129.9, 129.9, 129.9, 129.9,
133.0, 133.5, 133.6, 138.0, 138.2, 138.7, 165.0, 165.2, 166.0; HRMS
(ESI-TOF) m/z calcd for [C56H52O13+Na]+ 955.3306, found
955.3308.
34.4, 39.9, 47.9, 72.0, 72.7, 73.0, 74.1, 75.4, 79.7, 80.2, 103.8, 127.6,
127.7, 127.7, 127.9, 127.9, 128.2, 128.4, 128.4, 128.6, 128.6, 137.2,
138.1; HRMS (ESI-TOF) m/z calcd for [C29H40O5+Na]+ 491.2773,
found 491.2775.
Methyl 2,3,4-tri-O-benzyl 6-O-(3,5-di-O-benzyl β-D-arabino-
furanosyl)-α-D-glucopyranoside (24a).12 This compound is
prepared using the above-mentioned general procedure using 23a
(0.100 g, 0.13 mmol) as the starting material. Yield: (0.093 g, 93%
over two steps); [α]D25 (CHCl3, c 1.0) +2.0; IR (cm−1, CHCl3) 3421,
1
3063, 3033, 2926, 2866, 1588, 1454, 1106, 1063, 735, 692; H NMR
(399.78 MHz, CDCl3) δ 2.59 (s, 1H), 3.31 (s, 3H), 3.33−3.40 (m,
2H), 3.49 (dd, J = 9.7, 3.5 Hz, 1H), 3.50 (d, J = 5.9 Hz, 2H), 3.54 (dd,
J = 11.1, 5.8 Hz, 1H), 3.74 (ddd, J = 10.1, 5.8, 1.9 Hz, 1H), 3.80 (t, J =
5.8 Hz, 1H), 3.94 (d, J = 2.1 Hz, 1H), 3.97 (t, J = 9.3 Hz, 1H), 4.09 (q,
J = 5.7 Hz, 1H), 4.15−4.24 (m, 1H), 4.48 (ABq, J = 12.0 Hz, 2H),
4.53 (dd, J = 7.3, 3.8 Hz, 1H), 4.58 (d, J = 11.9 Hz, 1H), 4.65 (d, J =
12.2 Hz, 1H), 4.72 (d, J = 11.9 Hz, 1H), 4.77 (d, J = 7.3 Hz, 1H), 4.80
(d, J = 6.0 Hz, 1H), 4.87 (dd, J = 7.9, 3.2 Hz, 2H), 4.98 (d, J = 10.7
Hz, 1H), 7.02−7.65 (m, 25H); 13C NMR (100.53 MHz, CDCl3) δ
55.2, 67.3, 69.9, 71.8, 72.0, 73.2, 73.4, 75.0, 75.8, 77.9, 78.2, 79.9, 80.8,
82.0, 84.6, 97.9, 102.2, 127.6, 127.6, 127.6, 127.6, 127.7, 127.7, 127.7,
127.8, 127.8, 127.8, 128.0, 128.0, 128.0, 128.1, 128.1, 128.3, 128.3,
128.3, 128.3, 128.4, 128.4, 128.4, 128.4, 128.5, 128.5, 137.9, 138.0,
(Prop-2-ynyl) 3,5-di-O-benzyl-2-O-(2,3,5-tri-O-benzoyl-β-D-
xylofuranosyl)-α-D-arabinofuranoside (22j). This compound is
prepared using the above-mentioned general procedure using 8a
K
dx.doi.org/10.1021/jo501052y | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
138.0, 138.0, 138.5; HRMS (ESI-TOF) m/z calcd for
[C47H52O10+Na]+ 799.3458, found 799.3438.
128.4, 128.4, 128.4, 128.4, 128.4, 128.5, 137.8, 137.8, 138.2, 138.4,
138.8; HRMS (ESI-TOF) m/z calcd for [C47H52O10+Na]+ 799.3458,
found 799.3454.
Menthyl 3,5-di-O-benzyl β-D-arabinofuranoside (24b).12 This
compound is prepared using the above-mentioned general procedure
using 23b (0.100 g, 0.21 mmol) as the starting material. Yield: (0.092
g, 92% over two steps); [α]2D5 (CHCl3, c 1.0) −89.3; IR (cm−1, CHCl3)
Menthyl 3,5-di-O-benzyl-α-D-ribofuranoside (26b). This
compound is prepared using the above-mentioned general procedure
using 25b (0.100 g, 0.21 mmol) as the starting material. Yield: (0.090
g, 90% over two steps); [α]2D5 (CHCl3, c 0.9) +48.2; IR (cm−1, CHCl3)
1
3529, 3083, 3036, 2926, 2864, 1591, 1456, 1117, 1029, 732, 685; H
1
NMR (399.78 MHz, CDCl3) δ 0.74 (d, J = 6.9 Hz, 3H), 0.86 (d, J =
7.0 Hz, 3H), 0.69−1.11 (m, 2H), 0.90 (d, J = 6.5 Hz, 3H), 1.15−1.28
(m, 1H), 1.28−1.42 (m, 2H), 1.58−1.73 (m, 2H), 2.01−2.25 (m, 2H),
2.70 (d, J = 8.8 Hz, 1H), 3.48−3.61 (m, 3H), 3.80 (t, J = 5.9 Hz, 1H),
4.09 (q, J = 5.9 Hz, 1H), 4.21 (dt, J = 8.8, 5.4 Hz, 1H), 4.53 (ABq, J =
12.0 Hz, 2H), 4.62 (d, J = 11.9 Hz, 1H), 4.78 (d, J = 11.9 Hz, 1H),
5.20 (d, J = 5.0 Hz, 1H), 7.06−7.55 (m, 10H); 13C NMR (100.53
MHz, CDCl3) δ 15.8, 21.0, 22.2, 22.9, 25.2, 31.4, 34.3, 40.4, 47.8, 71.9,
72.2, 73.3, 76.8, 77.1, 79.9, 84.9, 98.2, 127.6, 127.6, 127.7, 127.7, 127.7,
127.7, 128.3, 128.3, 128.3, 128.3, 138.0, 138.0; HRMS (ESI-TOF) m/z
calcd for [C29H40O5+Na]+ 491.2773, found 491.2773.
3554, 3030, 2930, 1643, 1454, 1264, 1097, 764; H NMR (399.78
MHz, CDCl3) δ 0.77 (d, J = 7.0 Hz, 3H), 0.89 (d, J = 4.3 Hz, 2H),
0.79−1.03 (m, 3H), 0.91 (d, J = 3.8 Hz, 2H), 1.03−1.20 (m, 1H),
1.27−1.50 (m, 2H), 1.55−1.70 (m, 3H), 2.10−2.28 (m, 2H), 2.94 (d, J
= 10.2 Hz, 1H), 3.37 (dd, J = 10.6, 4.4 Hz, 1H), 3.48 (dABq, J = 10.4,
4.0 Hz, 2H), 3.78 (dd, J = 7.0, 3.5 Hz, 1H), 4.10 (bs, 1H), 4.19 (q, J =
4.0 Hz, 1H), 4.52 (ABq, J = 12.1 Hz, 2H), 4.56 (d, J = 12.3 Hz, 1H),
4.73 (d, J = 12.3 Hz, 1H), 5.09 (d, J = 4.7 Hz, 1H), 7.12−7.42 (m,
10H); 13C NMR (100.53 MHz, CDCl3) δ 15.9, 21.2, 22.3, 23.0, 25.3,
31.6, 34.3, 43.2, 48.5, 70.1, 72.0, 72.5, 73.4, 76.5, 80.0, 81.3, 102.7,
127.6, 127.6, 127.6, 127.6, 127.6, 127.6, 128.3, 128.3, 128.3, 128.3,
137.9, 138.2; HRMS (ESI-TOF) m/z calcd for [C29H40O5+Na]+
491.2773, found 491.2759.
Methyl 2,3,4-tri-O-benzyl-6-O-(3,5-di-O-benzyl-α-D-arabino-
furanosyl)-α-D-glucopyranoside (25a). This compound is pre-
pared using the above-mentioned general procedure using 5b (0.200 g,
0.42 mmol) as the starting material. Yield: (0.270 g, 82% over two
steps); [α]2D5 (CHCl3, c 1.0) +47.1; IR (cm−1, CHCl3) 3425, 30683,
Methyl 2,3,4-tri-O-benzyl-6-O-(3,5-di-O-benzyl-β-D-xylofura-
nosyl)-α-D-glucopyranoside (27a). This compound is prepared
using the above-mentioned general procedure using 8b (0.200 g, 0.42
mmol) as the starting material. Yield: (0.266 g, 81% over two steps);
[α]2D5 (CHCl3, c 1.0) −6.1; IR (cm−1, CHCl3) 3420, 3029, 2925, 1600,
1
3039, 2929, 1591, 1450, 1106, 1065, 735; H NMR (399.78 MHz,
CDCl3) δ 3.35 (s, 3H), 3.45 (dd, J = 10.4, 2.1 Hz, 1H), 3.51 (dd, J =
9.8, 3.7 Hz, 2H), 3.58 (ddd, J = 10.9, 4.9, 2.0 Hz, 2H), 3.60−3.71 (m,
1H), 3.74 (dd, J = 9.9, 2.3 Hz, 2H), 3.86 (d, J = 2.4 Hz, 1H), 3.95 (t, J
= 9.3 Hz, 1H), 4.16 (dd, J = 7.8, 2.6 Hz, 2H), 4.18 (d, J = 2.6 Hz, 1H),
4.26 (d, J = 10.7 Hz, 1H), 4.42 (d, J = 11.7 Hz, 1H), 4.46 (d, J = 11.8
Hz, 1H), 4.60 (t, J = 12.0 Hz, 1H), 4.64 (d, J = 3.7 Hz, 1H), 4.68 (s,
2H), 4.79 (d, J = 11.4 Hz, 2H), 4.95 (d, J = 10.9 Hz, 1H), 5.10 (s, 1H),
7.10−7.44 (m, 25H); 13C NMR (100.53 MHz, CDCl3) δ 55.1, 65.5,
69.7, 69.7, 72.0, 73.3, 73.7, 74.8, 75.6, 77.2, 77.4, 79.7, 82.0, 84.0, 85.4,
98.2, 109.5, 127.4, 127.4, 127.6, 127.6, 127.7, 127.7, 127.8, 127.8,
127.8, 127.9, 127.9, 128.0, 128.1, 128.1, 128.2, 128.2, 128.3, 128.3,
128.3, 128.4, 128.4, 128.4, 128.4, 128.5, 128.5, 136.8, 137.6, 138.1,
138.6, 138.9; HRMS (ESI-TOF) m/z calcd for [C47H52O10+Na]+
799.3458, found 799.3450.
1
1454, 1361, 1065, 741; H NMR (399.78 MHz, CDCl3) δ 2.15 (bs,
1H), 3.28 (s, 3H), 3.43−3.54 (m, 2H), 3.58 (dd, J = 10.8, 5.5 Hz, 1H),
3.68 (dd, J = 10.3, 7.1 Hz, 1H), 3.76 (dd, J = 10.4, 4.6 Hz, 2H), 3.94
(dd, J = 6.1, 3.1 Hz, 1H), 3.96−4.02 (m, 2H), 4.14−4.26 (m, 1H),
4.41−4.49 (m, 2H), 4.49 (d, J = 15.4 Hz, 1H), 4.53−4.61 (m, 4H),
4.63 (d, J = 12.1 Hz, 1H), 4.76 (d, J = 12.1 Hz, 1H), 4.81 (d, J = 10.9
Hz, 1H), 4.85 (dd, J = 6.4, 4.6 Hz, 2H), 4.97 (d, J = 10.9 Hz, 1H),
6.80−7.70 (m, 25H); 13C NMR (100.53 MHz, CDCl3) δ 55.0, 66.9,
69.7, 69.9, 72.1, 73.3, 73.3, 74.8, 75.7, 77.8, 79.3, 79.8, 79.9, 82.0, 83.5,
97.8, 108.5, 127.4, 127.4, 127.5, 127.6, 127.6, 127.6, 127.7, 127.8,
127.8, 127.8, 127.9, 127.9, 128.0, 128.0, 128.2, 128.2, 128.3, 128.3,
128.3, 128.3, 128.3, 128.3, 128.4, 128.4, 131.5, 137.8, 138.1, 138.2,
138.3, 138.7; HRMS (ESI-TOF) m/z calcd for [C47H52O10+Na]+
799.3458, found 799.3442.
Menthyl 3,5-di-O-benzyl-α-D-arabinofuranoside (25b). This
compound is prepared using the above-mentioned general procedure
using 5b (0.200 g, 0.42 mmol) as the starting material. Yield: (0.165 g,
83% over two steps); [α]D25 (CHCl3, c 1.1) +62.3; IR (cm−1, CHCl3)
Menthyl 3,5-di-O-benzyl-β-D-xylofuranside (27b). This com-
pound is prepared using the above-mentioned general procedure using
8b (0.200 g, 1 mmol) as the starting material. Yield: (0.165 g, 83%
over two steps); [α]D25 (CHCl3, c 0.5) −15.1; IR (cm−1, CHCl3) 3554,
1
3357, 3071, 2970, 1591, 1453, 1368, 1105, 741; H NMR (399.78
1
MHz, CDCl3) δ 0.76 (d, J = 7.0 Hz, 3H), 0.87 (d, J = 4.3 Hz, 3H),
0.89 (d, J = 3.7 Hz, 3H), 0.96 (dd, J = 12.7, 3.1 Hz, 1H), 1.00−1.08
(m, 1H), 1.08−1.16 (m, 1H), 1.22−1.32 (m, 1H), 1.38 (ddq, J = 11.9,
6.4, 3.3 Hz, 1H), 1.55−1.67 (m, 2H), 2.08−2.20 (m, 2H), 3.22−3.40
(m, 2H), 3.49 (dd, J = 10.4, 2.3 Hz, 1H), 3.66 (dd, J = 10.4, 2.3 Hz,
1H), 3.85 (d, J = 3.1 Hz, 1H), 4.12 (d, J = 10.4 Hz, 1H), 4.30 (q, J =
2.4 Hz, 1H), 4.49 (t, J = 12.4 Hz, 2H), 4.61 (d, J = 11.8 Hz, 1H), 4.67
(d, J = 12.2 Hz, 1H), 5.08 (s, 1H), 7.04−7.53 (m, 10H); 13C NMR
(100.53 MHz, CDCl3) δ 16.2, 21.1, 22.3, 23.2, 25.3, 31.6, 34.3, 42.9,
48.3, 69.8, 71.8, 73.7, 77.9, 79.1, 83.0, 85.3, 110.2, 127.6, 127.6, 127.8,
127.8, 128.0, 128.0, 128.3, 128.3, 128.5, 128.5, 137.0, 138.0; HRMS
(ESI-TOF) m/z calcd for [C29H40O5+Na]+ 491.2773, found 491.2776.
Methyl 2,3,4-tri-O-benzyl-6-O-(3,5-di-O-benzyl-α-D-ribofura-
nosyl)-α-D-glucopyranoside (26a). This compound is prepared
using the above-mentioned general procedure using 25a (0.100 g, 0.13
mmol) as the starting material. Yield: (0.087 g, 87% over two steps);
[α]2D5 (CHCl3, c 1.6) +23.7; IR (cm−1, CHCl3) 3457, 3069, 2927,
3030, 2930, 1643, 1454, 1264, 1097, 764; H NMR (399.78 MHz,
CDCl3) δ 0.70 (d, J = 6.9 Hz, 3H), 0.80 (d, J = 7.2 Hz, 3H), 0.90 (d, J
= 6.6 Hz, 3H), 0.62−1.07 (m, 3H), 1.09−1.48 (m, 2H), 1.55−1.72 (m,
2H), 2.08−2.17 (m, 2H), 2.21−2.34 (m, 1H), 3.48 (td, J = 10.6, 4.1
Hz, 1H), 3.68 (dd, J = 10.0, 6.6 Hz, 1H), 3.79 (dd, J = 10.1, 4.9 Hz,
1H), 3.95 (dd, J = 5.5, 3.1 Hz, 1H), 4.24 (s, 1H), 4.40−4.50 (m, 1H),
4.50 (dd, J = 11.9, 1.8 Hz, 2H), 4.59 (d, J = 12.1 Hz, 1H), 4.63 (d, J =
11.8 Hz, 1H), 5.12 (d, J = 1.7 Hz, 1H), 6.74−7.79 (m, 10H); 13C
NMR (100.53 MHz, CDCl3) δ 15.9, 21.0, 22.3, 23.0, 24.8, 31.3, 34.5,
39.6, 48.0, 69.5, 72.1, 73.4, 74.7, 79.1, 79.9, 83.1, 104.0, 127.4, 127.4,
127.5, 127.5, 127.7, 127.7, 128.2, 128.3, 128.3, 128.3, 138.0, 138.3;
HRMS (ESI-TOF) m/z calcd for [C29H40O5+Na]+ 491.2773, found
491.2770.
Methyl 2,3,4-tri-O-benzyl-6-O-(3,5-di-O-benzyl-β-D-lyxofura-
nosyl)-α-D-glucopyranoside (28a). This compound is prepared
using the above-mentioned general procedure using 27a (0.100 g, 0.13
mmol) as the starting material. Yield: (0.082 g, 82% over two steps);
[α]2D5 (CHCl3, c 1.0) −16.7; IR (cm−1, CHCl3) 3450, 3070, 2929,
1
1455, 1269, 1109, 744; H NMR (399.78 MHz, CDCl3) δ 3.32 (s,
1
3H), 3.33−3.44 (m, 3H), 3.48−3.53 (m, 1H), 3.61 (t, J = 9.3 Hz, 1H),
3.66 (dd, J = 11.0, 1.7 Hz, 1H), 3.71−3.77 (m, 1H), 3.79 (dd, J = 6.9,
2.8 Hz, 1H), 3.96 (t, J = 9.3 Hz, 1H), 4.12 (d, J = 3.7 Hz, 1H), 4.10−
4.21 (m, 2H), 4.38−4.52 (m, 3H), 4.58−4.70 (m, 4H), 4.75−4.84 (m,
3H), 4.96 (d, J = 10.9 Hz, 1H), 5.06 (d, J = 4.7 Hz, 1H), 7.00−7.63
(m, 25H); 13C NMR (100.53 MHz, CDCl3) δ 55.1, 66.2, 69.8, 70.0,
72.0, 72.9, 73.4, 75.0, 75.8, 76.9, 77.2, 77.7, 80.0, 82.0, 82.2, 98.0,
101.8, 127.6, 127.6, 127.7, 127.7, 127.7, 127.7, 127.9, 127.9, 127.9,
128.0, 128.0, 128.0, 128.0, 128.3, 128.4, 128.4, 128.4, 128.4, 128.4,
1455, 1270, 1109, 740; H NMR (399.78 MHz, CDCl3) δ 3.24 (s,
3H), 3.40−3.47 (m, 1H), 3.49 (dd, J = 9.6, 3.5 Hz, 1H), 3.58 (dd, J =
10.9, 6.1 Hz, 1H), 3.64 (dd, J = 9.8, 6.3 Hz, 1H), 3.73−3.82 (m, 2H),
3.94−4.04 (m, 3H), 4.13 (t, J = 5.3 Hz, 1H), 4.19−4.30 (m, 1H), 4.48
(ABq, J = 11.8 Hz, 2H), 4.56 (dd, J = 10.6, 4.1 Hz, 2H), 4.64 (d, J =
12.1 Hz, 1H), 4.68 (d, J = 11.8 Hz, 2H), 4.75 (s, 1H), 4.79 (d, J = 5.3
Hz, 1H), 4.83 (d, J = 3.1 Hz, 1H), 4.82−4.91 (m, 1H), 4.97 (ABq, J =
10.8 Hz, 1H), 6.72−7.72 (m, 25H); 13C NMR (100.53 MHz, CDCl3)
δ 54.9, 67.6, 69.8, 70.1, 73.0, 73.3, 73.5, 74.4, 75.0, 75.7, 78.2, 79.3,
L
dx.doi.org/10.1021/jo501052y | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
80.0, 82.1, 97.7, 101.4, 127.3, 127.3, 127.6, 127.6, 127.6, 127.6, 127.7,
127.7, 127.8, 127.8, 127.8, 128.0, 128.0, 128.0, 128.0, 128.3, 128.3,
128.3, 128.3, 128.4, 128.4, 128.4, 128.4, 128.4, 128.4, 128.4, 138.0,
138.1, 138.1, 138.2, 138.7; HRMS (ESI-TOF) m/z calcd for
[C47H52O10+Na]+ 799.3458, found 799.3457.
ACKNOWLEDGMENTS
■
S.A.T. thanks the CSIR New Delhi, B.M. thanks UGC New
Delhi for the financial assistance, and S.H. thanks the DST New
Delhi for the financial assistance in the form of SwarnaJayanthi
Fellowship.
Menthyl 3,5-di-O-benzyl-β-D-lyxofuranoside (28b). This com-
pound is prepared using the above-mentioned general procedure using
27b (0.100 g, 0.21 mmol) as the starting material. Yield: (0.090 g,
90%); [α]2D5 (CHCl3, c 0.5) −138.1; IR (cm−1, CHCl3) 3427, 2939,
REFERENCES
■
1
(1) (a) Rudd, P. M.; Elliott, T.; Cresswell, P.; Wilson, I. A.; Dwek, R.
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1584, 1454, 1148, 1027, 740; H NMR (399.78 MHz, CDCl3) δ 0.70
(d, J = 6.9 Hz, 3H), 0.80 (d, J = 7.2 Hz, 3H), 0.75−0.96 (m, 2H), 0.90
(d, J = 6.5 Hz, 3H), 1.07−1.44 (m, 2H), 1.54−1.73 (m, 3H), 2.07 (dd,
J = 12.1, 4.0 Hz, 1H), 2.22−2.43 (m, 1H), 3.02 (d, J = 11.4 Hz, 1H),
3.47 (td, J = 10.6, 4.2 Hz, 1H), 3.63 (dd, J = 9.4, 6.2 Hz, 1H), 3.79 (dd,
J = 9.4, 6.5 Hz, 1H), 3.94−4.05 (m, 1H), 4.08−4.27 (m, 2H), 4.47 (d,
J = 11.8 Hz, 1H), 4.56 (d, J = 11.8 Hz, 1H), 4.63 (d, J = 11.6 Hz, 1H),
4.75 (d, J = 11.7 Hz, 1H), 5.13 (d, J = 5.2 Hz, 1H), 7.10−7.73 (m,
10H); 13C NMR (100.53 MHz, CDCl3) δ 15.9, 21.1, 22.3, 22.8, 24.7,
31.3, 34.4, 39.9, 48.0, 69.4, 73.0, 73.5, 74.4, 75.1, 77.7, 78.8, 96.5,
127.0, 127.0, 127.3, 127.6, 127.9, 127.9, 128.2, 128.2, 128.3, 128.3,
138.0, 138.5; HRMS (ESI-TOF) m/z calcd for [C29H40O5+Na]+
491.2773, found 491.2774.
(4) Koeller, K. M.; Wong, C.-H. Chem. Rev. 2000, 100, 4465−4494.
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Methyl 2,3,4-tri-O-benzyl-6-O-(3,5-di-O-benzyl-α-D-lyxofura-
nosyl)-α-D-glucopyranoside (29a). This compound is prepared
using the above-mentioned general procedure using 6b (0.200 g, 0.42
mmol) as the starting material. Yield: (0.266 g, 85% over two steps);
[α]2D5 (CHCl3, c 0.7) +48.1; IR (cm−1, CHCl3) 3386, 3032, 2923,
1
1597, 1454, 1271, 1057, 703; H NMR (399.78 MHz, CDCl3) δ 3.34
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(s, 3H), 3.64−3.45 (m, 5H), 3.75−3.68 (m, 1H), 3.96 (t, J = 9.2 Hz,
1H), 4.01 (dd, J = 11.1, 3.3 Hz, 1H), 4.13 (dd, J = 10.2, 4.9 Hz, 1H),
4.22−4.17 (m, 1H), 4.64−4.36 (m, 7H), 4.69 (t, J = 12.4 Hz, 2H),
4.86−4.77 (m, 3H), 4.98 (d, J = 10.8 Hz, 1H), 5.04 (s, 1H), 7.49−7.02
(m, 25H); 13C NMR (100.53 MHz, CDCl3) δ 55.2, 65.8, 67.7, 69.7,
71.9, 72.4, 73.3, 73.8, 75.0, 75.8, 77.2, 77.5, 77.6, 79.8, 82.0, 98.1,
107.5, 127.7, 127.7, 127.7, 127.8, 127.8, 127.8, 127.8, 127.8, 127.9,
127.9, 127.9, 128.0, 128.0, 128.1, 128.1, 128.4, 128.4, 128.4, 128.4,
128.4, 128.4, 128.4, 128.4, 128.4, 128. 4, 137.0, 137.7, 138.1, 138.2,
138.7; HRMS (ESI-TOF) m/z calcd for [C47H52O10+Na]+ 799.3458,
found 799.3453.
Menthyl 3,5-di-O-benzyl-α-D-lyxofuranoside (29b). This
compound is prepared using the above-mentioned general procedure
using 6b (0.200 g, 0.42 mmol) as the starting material. Yield: (0.163 g,
82%); [α]2D5 (CHCl3, c 1.0) +58.1; IR (cm−1, CHCl3) 3429, 2927,
1
1594, 1455, 1150, 1028, 741; H NMR (399.78 MHz, CDCl3) δ 0.77
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(d, J = 6.9 Hz, 3H), 0.82 (dd, J = 12.3, 3.2 Hz, 1H), 0.87 (d, J = 5.3
Hz, 3H), 0.89 (d, J = 5.7 Hz, 3H), 0.89−1.00 (m, 1H), 1.08−1.21 (m,
1H), 1.30−1.46 (m, 1H), 1.52−1.72 (m, 3H), 1.96−2.15 (m, 2H),
3.29 (td, J = 10.6, 4.4 Hz, 1H), 3.61 (dd, J = 10.5, 2.1 Hz, 1H), 3.66
(dd, J = 10.5, 3.2 Hz, 1H), 4.08 (dd, J = 9.9, 4.7 Hz, 1H), 4.29−4.42
(m, 2H), 4.45 (d, J = 4.8 Hz, 1H), 4.48 (d, J = 11.4 Hz, 1H), 4.54 (d, J
= 11.8 Hz, 1H), 4.64 (d, J = 11.8 Hz, 1H), 4.72 (d, J = 11.3 Hz, 1H),
5.04 (s, 1H), 7.03−7.67 (m, 10H); 13C NMR (100.53 MHz, CDCl3) δ
16.2, 21.1, 22.2, 23.2, 25.5, 31.6, 34.3, 43.2, 48.7, 67.9, 72.0, 72.4, 73.9,
77.0, 78.0, 79.1, 108.5, 127.7, 127.7, 127.7, 127.8, 127.9, 127.9, 128.4,
128.4, 128.4, 128.4, 137.2, 137.9; HRMS (ESI-TOF) m/z calcd for
[C29H40O5+Na]+ 491.2773, found 491.2767.
ASSOCIATED CONTENT
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(10) (a) Holimann, A.; Stocker, B. L.; Seeberger, P. H. J. Org. Chem.
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* Supporting Information
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Copies of 1H, 13C and DEPT NMR spectra for all compounds.
This material is available free of charge via the Internet at
http://pubs.acs.org
AUTHOR INFORMATION
Corresponding Author
*E-mail: s.hotha@iiserpune.ac.in.
■
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G. Curr. Med. Chem. 2010, 17, 3099−3108. (b) Trefzer, C.;
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́ ́
Skovierova, H.; Buroni, S.; Bobovska, A.; Nenci, S.; Molteni, E.;
Notes
Pojer, F.; Pasca, M. R.; Makarov, V.; Cole, S. T.; Riccardi, G.;
The authors declare no competing financial interest.
Mikuso
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K.; Johnsson, K. J. Am. Chem. Soc. 2012, 134, 912−915.
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