Methanesulfonic-acid-catalysed ring opening and glycosylation of 1,2-(Acetylcyclopropane)-annulated d -lyxofuranose

Article abstract of DOI:10.1002/ejoc.201402037

A mild and effective method for the synthesis of 2-C-branched disaccharides, glycoconjugates, and nucleoside analogues is described. 1,2-(acetylcyclopropane)-annulated D-lyxofuranose underwent ring opening catalysed by CH₃SO₃H to act as an efficient glycosyl donor and give the glycosylation products in good yields and with high diastereoselectivities. Copyright

Full text of DOI:10.1002/ejoc.201402037

Job/Unit: O42037
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Date: 17-06-14 12:33:16
Pages: 9
FULL PAPER
DOI: 10.1002/ejoc.201402037
Methanesulfonic-Acid-Catalysed Ring Opening and Glycosylation of
1,2-(Acetylcyclopropane)-Annulated -Lyxofuranose
D
Cong Wang,[a,b] Xiaofeng Ma,[a,b] Jichao Zhang,[a,b] Qin Tang,[a,b] Wei Jiao,[a] and
Huawu Shao*[a]
Keywords: Carbohydrates / Disaccharides / Glycosylation / Glycoconjugates / Small-ring systems
A mild and effective method for the synthesis of 2-C-
branched disaccharides, glycoconjugates, and nucleoside
analogues is described. 1,2-(acetylcyclopropane)-annulated
CH3SO3H to act as an efficient glycosyl donor and give the
glycosylation products in good yields and with high dia-
stereoselectivities.
D-lyxofuranose underwent ring opening catalysed by
of our knowledge, the only two examples were reported by
Madsen and co-workers in 1998, when cyclopropanated
xylofuranose reacted with MeOH and BnOH catalysed by
Zeise’s dimer ([Pt(C2H4)Cl2]2) at 70 °C to give the 2-C-
branched furanosides as mixtures of anomers.[16c,16d]
Introduction
C-Branched sugars have received much attention from
the glycochemistry and organic chemistry communities as
an important class of carbohydrate mimetics, as well as po-
tential antibiotics.[1,2] 2-C-Branched sugar analogues in par-
ticular have recently been the subject of intense study. For
example, 2-C-branched pyranosides have been used to
mimic the role of 2-N-acetyl sugars, and to inhibit the bio-
synthesis of lipid A.[3] 2-C-Branched nucleosides, one of the
most important classes of nucleoside analogues, have shown
promising biological activities, including antiviral ac-
tivity,[4,5] antitumor activity,[6] and ribonucleotide reductase
inhibition.[7] They can also be used as probes to study the
structure–activity relationship of nucleic acids and help in
the search for new antitumor agents.[8,9] A number of ele-
gant synthetic routes to 2-C-branched carbohydrates,[10,11]
nucleosides,[12,13] and sugar amino acids have been devel-
oped,[14] but new strategies for the highly stereoselective
synthesis of these compounds are still highly desirable to
facilitate biological and medical studies.
Donor–acceptor cyclopropanes, due to their remarkable
reactivity, are useful building blocks in organic chemis-
try.[15] Also, 1,2-cyclopropanated sugars, especially 1,2-cy-
clopropanated pyranoses, have been extensively used in the
synthesis of branched glycosides,[10a,10b,16] oxepanes,[17,18]
and some other functionalized chemical structures.[19] How-
ever, 1,2-cyclopropanated furanoses have only rarely been
used to prepare carbohydrate-based derivatives. To the best
In recent years, we have developed strategies for ring-
opening 1,2-cyclopropanated pyranoses to achieve the
highly stereoselective synthesis of 2-C-branched carbo-
hydrates and their derivatives.[16a,16b,20] For example, in the
presence of Et3N or K2CO3, 2-C-branched O- and S-
glycosides, as well as glycosyl azides, could be obtained as
single anomers from nucleophilic substitution reactions of
1,2-cyclopropanated glucose in good to excellent
yields.[20a,20b] We also found that 1,2-cyclopropanated ga-
lactose derivatives could be used as efficient glycosyl donors
to synthesize 2-C-branched pyranosyl conjugates.[16a,16b]
Furthermore, 1,2-cyclopropanated carbohydrates have been
used to construct 2,2-disubstituted, 2,3-disubstituted, and
2,2,3-trisubstituted perhydrofuro[2,3-b]pyrans (and furans)
by ring-opening–recyclization–addition and [3+2] cycload-
dition, respectively.[20c–20f] In this paper, we report an ef-
ficient method for the highly stereoselective synthesis of 2-
C-branched (acetylmethyl) furanosyl conjugates by
CH3SO3H-catalysed ring-opening of 1,2-cyclopropanated
lyxose. A variety of O-, N-, and S-nucleophiles, including
monosaccharides, amino acids, alcohols and TMS-pyrimid-
ines (TMS = trimethylsilyl) reacted with 1,2-(acetylcyclo-
propane)-annulated d-lyxofuranose to give a wide range of
furanosyl conjugates highly stereoselectively.
[a] Natural Product Research Center, Chengdu Institute of
Biology, Chinese Academy of Sciences,
Chengdu 610041, P. R. China
Results and Discussion
E-mail: shaohw@cib.ac.cn
The glycosyl donor, 1,2-(acetylcyclopropane)-annulated
lyxose 1, was prepared from d-xlyose according to our pre-
viously reported procedure.[20d] We began our investigation
by examining the glycosylation reaction of 1,2-(acetylcyclo-
http://english.cib.cas.cn/
[b] University of Chinese Academy of Sciences,
Beijing, P. R. China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201402037.
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C. Wang, X. Ma, J. Zhang, Q. Tang, W. Jiao, H. Shao
FULL PAPER
propane)-annulated lyxose 1 and glycosyl acceptor 2 in the
We found that the temperature did not influence the
presence of different Lewis and Brønsted acids. As shown yield, but a significant loss in stereoselectivity was observed
in Table 1, TMSOTf and BF3·OEt2 were tested first due to when the reaction was run at higher temperatures. For ex-
their excellent performance in the ring-opening reactions of ample, when we carried out the glycosylation at 0 °C to
1,2-cyclopropanated galactose.[16a,16b] The coupling reac- room temperature, disaccharide 18 was isolated in 80%
tion between 1 and 2, in the presence of TMSOTf (20 mol- yield with α/β = 6:1 (Table 1, entry 13). However, when the
%) or BF3·OEt2 (20 mol-%) in dichloromethane at –20 °C, same reaction was carried out at –20 °C to room tempera-
followed by gradual warming to 0 °C, smoothly gave the ture, only α product was obtained (Table 1, entry 10). Based
desired disaccharide (i.e., 18) in 77 or 79% yield, respec- on the above results, this transformation is best carried out
tively (Table 1, entries 1 and 2). Interestingly, and in con- using CH3SO3H (20 mol-%) as catalyst, CH2Cl2 as solvent,
trast to the ring-opening reactions of 1,2-cyclopropanated at –20 °C to room temperature for 5 h.
galactose, where the formation of different anomeric prod-
Having established the optimal reaction conditions, the
ucts could be controlled by the Lewis acid,[16a,16b] BF3·OEt2 scope of the glycosylation was investigated by testing the
and TMSOTf both led only to the formation of the α-prod- reaction of 1,2-cyclopropanated lyxose with a number of
uct in this study. Next, some further Lewis acids were scre- acceptors including simple alcohols, sugar alcohols, thiols,
ened to find the optimal catalyst for this transformation. phenol, amino acids, and TMS-pyrimidines. As shown in
Among them, TFA (trifluoroacetic acid), NH2SO3H, and Table 2, when monosaccharide 3 was used as the nucleo-
H2SO4–silica gave no conversion, or led to only trace phile, the desired 2-keto-lyxosyl disaccharide (i.e., 19) was
amounts of the product (Table 1, entries 5, 9, and 11). With obtained in 78% yield with α/β = 11:1 (Table 2, entry 1).
ZnCl2, BiCl3, CuBr2, FeCl3, and AlCl3, the products were Furanosyl alcohols 4 and 5 were used as acceptors, and the
formed in moderate to good yields (Table 1, entries 3, 4, corresponding α-2-C-furanosyl disaccharides were formed
and 6–8). It is worth mentioning that, in all of these cases, in 63 and 81% yields, respectively (Table 2, entries 2 and 3).
only a single α isomer was formed. After a series of trials, The glycosylation of 1,2-cyclopropanated lyxose was fur-
CH3SO3H was found to be the most efficient catalyst for ther applied to construct glycoconjugates 24, 25, and 27.
this reaction, and in the presence of CH3SO3H (20 mol-%), Again, glycoconjugates 24, 25, and 27 were exclusively ob-
the α disaccharide was isolated in 83% yield (Table 1, en- tained as α anomers (Table 2, entries 6, 7, and 9). Small
try 10).
alcohols, thiols, phenol, and a thiophenol were also suitable
glycosyl acceptors, and the 2-C-branched glycosylation
products were formed in 72–86% yield (Table 2, entries 2–4
and 10–13). In all these cases, only α products were ob-
tained. Encouragingly, TMS-pyrimidines could also be used
as acceptors, and the α nucleoside derivatives were obtained
in 55 and 58% yields in the presence of CH3SO3H (Table 2,
entries 14 and 15).
Table 1. Glycosylation of glycosyl donor 1 and acceptor 2 catalysed
by different acids.
The stereochemistry of the products was unambiguously
determined by extensive NMR spectroscopic studies, and
was further confirmed by 2D-NOESY experiments. There
are significant correlations between 1Ј-H and 1ЈЈa-H (18
Entry[a,b] Catalyst[c]
Temp.
Time [h] Yield[d] [%] α/β[e]
1
2
3
4
5
6
7
8
TMSOTf
BF3·Et2O
ZnCl2
BiCl3
TFA
CuBr2
FeCl3
AlCl3
NH2SO3H
CH3SO3H
–20 °C to r.t.
–20 °C to r.t.
–20 °C to r.t.
–20 °C to r.t.
–20 °C to r.t.
–20 °C to r.t.
–20 °C to r.t.
–20 °C to r.t.
–20 °C to r.t.
–20 °C to r.t.
2.5
2.5
12
5
4
6
6
8
12
5
3
77
79
47
63
trace
63
76
74
0
83
α
α
α
α
–
α
α
α
–
α
–
α
6:1
9
10
11
12
13
H2SO4–silica –20 °C to r.t.
CH3SO3H
CH3SO3H
trace
76
80
–40 °C
0 °C to r.t.
6
5
[a] Reactions were carried out with donor (1.0 equiv.) and acceptor
(1.1 equiv.) in CH2Cl2 (1.25 mL). [b] Molecular sieves (4 Å; 120
wt.-%) were used. [c] 20 mol-% of the donor was used. [d] Isolated
1
yield. [e] Values were determined by H NMR spectroscopy.
Figure 1. Key NOE correlations for compounds 18, 26, and 32.
2
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1,2-(Acetylcyclopropane)-Annulated d-Lyxofuranose
Table 2. The reaction of 1 with glycosyl acceptors catalysed by CH3SO3H.
[a] Unless otherwise noted, reactions were carried out with donor (1.0 equiv.) and acceptor (1.1 equiv.) in CH2Cl2 (1.25 mL) at –20 °C –
room temp. for 5 h. [b] Molecular sieves (4 Å; 120 wt.-%) were used. [c] Isolated yield. [d] Values were determined by 1H NMR spec-
troscopy. [e] Reaction was carried out with 1.0 equiv. of donor, 2.0 equiv. of acceptor, and 1.0 equiv. of CH3SO3H in CH2Cl2 at –20 °C.
and 32) as well as between 1-H and 1Јa-H (26) of 2-C- carbenium ion intermediate 35.[21] Nucleophiles could ap-
branched-lyxofuranosyl derivatives, which suggests that proach the oxocarbenium ion from either the upper (path a)
these protons are positioned on the same side of the fur- or the lower (path b) face of the molecule to give isomers 36
anose ring. Also, correlations between the pyrimidine pro- or 39. In the presence of the neighbouring carbonyl group,
tons and 2Ј-H and 4Ј-H further confirmed the α configura- however, bicyclic oxocarbonium ion 37 is formed.[16b,20d]
tion of product 32 (Figure 1).
Nucleophiles react with 37 predominantly from the bottom
Based on the experimental results described above, a face of the ring (path c) to produce 1,2-trans-configured α
plausible mechanism for the CH3SO3H-catalysed ring- glycoside 39. In our previous research,[16b] we assumed that
opening of 1,2-cyclopropanated lyxose is proposed, as path d was logical because a product containing a bicyclic
shown in Scheme 1. Firstly, protonation promotes cleavage ketal was obtained. However, with the substrate used in this
of the C-1–C-1Ј bond of the cyclopropane to produce oxo- study, we did not observe the formation of product 38.
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C. Wang, X. Ma, J. Zhang, Q. Tang, W. Jiao, H. Shao
FULL PAPER
Scheme 1. Plausible mechanism for the CH3SO3H-catalysed ring-opening of 1,2-cyclopropanated lyxose.
tion mixture was warmed slowly to room temperature, stirred for
Conclusions
5 h, and then quenched by the addition of Et3N. The suspension
was concentrated in vacuo, and the residue was purified by silica
gel flash column chromatography (petroleum ether/ethyl acetate) to
give the corresponding products.
We have developed a method of CH3SO3H-catalysed
ring-opening glycosylation of 1,2-(acetylcyclopropane)-
annulated d-lyxofuranose for the stereoselective synthesis of
2-C-branched d-lyxofuranosyl derivatives. The glycosyl-
ation was efficient, and gave access to a series of 2-C-
branched lyxofuranosyl conjugates, including disaccharides
and nucleoside analogues, in good yields and with high dia-
stereoselectivities. Further investigations of the scope of this
reaction and the biological activities of the products are in
progress.
6-O-(2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-
D-lyxofuranos-
yl)-1,2:3,4-di-O-isopropylidene-α- -galactopyranose (18): The cou-
D
pling between donor 1 (50.0 mg, 0.142 mmol, 1.0 equiv.) and ac-
ceptor 2 (40.6 mg, 0.156 mmol, 1.1 equiv.) was carried out accord-
ing to the general procedure. The resulting crude product was puri-
fied by flash chromatography (petroleum ether/ethyl acetate, 6:1)
to give 18 (72 mg, 83%) as a colourless syrup. [α]2D0 = +2.8 (c =
0.83, CHCl3). 1H NMR (600 MHz, CDCl3): δ = 7.36–7.25 (m, 8
H, Ar-H), 7.21 (d, J = 7.1 Hz, 2 H, Ar-H), 5.50 (d, J = 5.0 Hz, 1
H, 1-H), 4.89 (d, J = 4.4 Hz, 1 H, 1Ј-H), 4.63–4.47 (m, 4 H), 4.37
(dd, J = 10.0, 6.1 Hz, 1 H, 2-H), 4.32–4.27 (m, 3 H), 4.24 (d, J =
7.9 Hz, 1 H, 4-H), 4.00 (t, J = 6.8 Hz, 1 H), 3.77 (dd, J = 10.5,
6.4 Hz, 1 H, 6-H), 3.73 (dd, J = 9.6, 6.9 Hz, 1 H, 5Ј-H), 3.69 (dd,
J = 10.4, 7.7 Hz, 1 H, 6-H), 3.65 (dd, J = 9.6, 5.7 Hz, 1 H, 5Ј-H),
2.84–2.69 (m, 2 H, 1ЈЈ-H, 2Ј-H), 2.53 (dd, J = 17.1, 3.7 Hz, 1 H,
1ЈЈ-H), 2.00 (s, 3 H, COCH3), 1.51 (s, 3 H), 1.43 (s, 3 H), 1.33 (s,
3 H), 1.32 (s, 3 H, 4 CH3) ppm. 13C NMR (150 MHz, CDCl3): δ
= 207.1 (CO), 138.2, 138.0, 128.3, 127.8, 127.6, 127.6 (overlap, 2
Ph), 109.1, 108.5 [2 C(CH3)2], 107.9 (C-1Ј), 96.3 (C-1), 79.8 (C-4Ј),
79.7 (C-3Ј), 74.2 (CH2Ph), 73.4 (CH2Ph), 70.8, 70.7, 70.6, 68.3 (C-
5Ј), 66.9 (C-5), 65.8 (C-6), 45.5 (C-2Ј), 39.7 (CH2CO), 29.9
Experimental Section
General Remarks: All reactions sensitive to air or moisture were
carried out under argon in anhydrous solvents. All reagents were
purchased from commercial suppliers, and used without further pu-
rification unless otherwise noted. Reactions were monitored by
thin-layer chromatography (TLC) using silica gel HSGF254 plates
(0.20–0.25 mm thickness) with a fluorescent indicator. Visualiza-
tion of TLC plates was achieved by exposure to UV light (254 nm)
and to a typical TLC indicator solution (5% sulfuric acid/ethanol
solution). Column chromatography was carried out on silica gel
90, 300–400 mesh. Optical rotations were measured with a Perkin–
Elmer-341 Digital Polarimeter. H (600 or 400 MHz) and 13C (150
1
(COCH ), 26.0, 26.0, 24.9, 24.5 (4 CH ) ppm. IR (KBr): ν = 3435,
˜
3
3
2987, 2933, 1717, 1382, 1372, 1256, 1211, 1173, 1111, 1004, 739,
699 cm–1. HRMS (ESI): calcd. for C34H44O10Na [M + Na]+
635.2827; found 635.2816.
or 100 MHz) NMR spectra were recorded with Bruker Avance 600
and 400 spectrometers. 1H NMR chemical shifts are reported in
ppm (δ) relative to tetramethylsilane, and the solvent resonance was
used as the internal standard (CDCl3, δ = 7.26 ppm). Data are
reported as follows: chemical shift, multiplicity (s = singlet, d =
doublet, t = triplet, m = multiplet), coupling constants [Hz], and
integration. 13C NMR chemical shifts are reported in ppm from
tetramethylsilane, and the solvent resonance was used as the in-
ternal standard (CDCl3, δ = 77.0 ppm). HRMS electrospray (ESI)
spectra were recorded with a BioTOF Q instrument.
Methyl 6-O-(2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-
D-lyxo-
furanosyl)-2,3,4-tri-O-benzyl-α- -glucopyranoside (19): The cou-
D
pling between donor 1 (50.0 mg, 0.142 mmol, 1.0 equiv.) and ac-
ceptor 3 (72.4 mg, 0.156 mmol, 1.1 equiv.) was carried out accord-
ing to the general procedure. The resulting crude product was puri-
fied by flash chromatography (petroleum ether/ethyl acetate, 5:1)
to give 19 (90 mg, 78%) as a colourless syrup. [α]2D0 = +37.4 (c =
1
General Procedure for the Glycosylation Reaction: A suspension of
acceptor alcohol (0.156 mmol, 1.1 equiv.) containing freshly acti-
vated molecular sieves (4 Å; 120 wt.-%) in dry CH2Cl2 (0.5 mL)
was stirred at room temperature for 10 min under an argon atmo-
sphere. The mixture was then cooled to –20 °C, and stirred for an-
other 10 min. A solution of glycosyl donor 1 (50.0 mg, 0.142 mmol,
1.0 equiv.) in dry CH2Cl2 (0.5 mL) was then added dropwise, and
0.47, CHCl3). H NMR (400 MHz, CDCl3): δ = 7.44–7.15 (m, 25
H, Ar-H), 5.00 (d, J = 10.9 Hz, 1 H, CH2Ph), 4.92 (d, J = 4.2 Hz,
1 H, 1Ј-H), 4.89–4.79 (m, 3 H, CH2Ph), 4.69 (d, J = 11.3 Hz, 2 H,
CH2Ph), 4.62 (d, J = 3.5 Hz, 1 H, 1-H), 4.55–4.40 (m, 3 H), 4.38–
4.25 (m, 3 H), 4.09 (dd, J = 11.1, 3.4 Hz, 1 H), 4.00 (t, J = 9.3 Hz,
1 H, 3-H), 3.76–3.66 (m, 2 H), 3.66–3.50 (m, 4 H), 3.37 (s, 3 H,
OCH3), 2.90–2.69 (m, 2 H, 1ЈЈ-H, 2Ј-H), 2.54 (dd, J = 17.0, 3.3 Hz,
1 H, 1ЈЈ-H), 1.99 (s, 3 H, COCH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 207.1 (CO), 138.8, 138.3, 138.2, 138.1, 137.9, 128.4,
then
a solution of CH3SO3H (2.7 mg, 1.8 μL, 0.028 mmol,
0.2 equiv.) in dry CH2Cl2 (0.25 mL) was added dropwise. The reac-
4
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1,2-(Acetylcyclopropane)-Annulated d-Lyxofuranose
128.4, 128.3, 128.3, 128.1, 127.9, 127.9, 127.8, 127.8, 127.7, 127.7,
127.6, 127.6, 127.5 (overlap, 5 Ph), 107.5 (C-1Ј), 98.1 (C-1), 82.0,
was carried out according to the general procedure. The resulting
crude product was purified by flash chromatography (petroleum
79.8, 79.8, 79.7, 77.6, 75.7 (CH2Ph), 75.0 (CH2Ph), 74.2 (CH2Ph), ether/ethyl acetate, 8:1) to give 22 (41 mg, 75%) as a colourless
73.4 (CH2Ph), 73.3 (CH2Ph), 70.0, 68.1 (C-5Ј), 66.6 (C-6), 55.1 syrup. [α]2D0 = +56.1 (c = 0.15, CHCl3). 1H NMR (600 MHz,
(OCH3), 45.6 (C-2Ј), 39.8 (CH2CO), 29.9 (COCH3) ppm. IR (KBr):
CDCl3): δ = 7.36–7.26 (m, 8 H, Ar-H), 7.21 (d, J = 7.1 Hz, 2 H,
Ar-H), 4.73 (d, J = 4.2 Hz, 1 H, 1-H), 4.60 (d, J = 11.9 Hz, 1 H,
CH2Ph), 4.52 (dd, J = 11.7, 6.0 Hz, 2 H, CH2Ph, 4-H), 4.37–4.28
(m, 3 H, CH2Ph, 3-H), 3.74 (dd, J = 9.8, 6.4 Hz, 1 H, 5-H), 3.67
(dd, J = 9.8, 6.0 Hz, 1 H, 5-H), 3.36 (s, 3 H, OCH3), 2.80 (dd, J =
17.8, 9.6 Hz, 1 H, 1Ј-H), 2.68 (td, J = 9.7, 4.8 Hz, 1 H, 2-H), 2.50
(dd, J = 17.8, 4.9 Hz, 1 H, 1Ј-H), 2.01 (s, 3 H, COCH3) ppm. 13C
NMR (150 MHz, CDCl3): δ = 207.2 (CO), 138.1, 138.0, 128.3,
127.8, 127.7, 127.6 (overlap, 2 Ph), 108.4 (C-1), 79.7 (C-4), 79.6 (C-
3), 74.2, 73.5 (2 CH2Ph), 68.4 (C-5), 55.8 (OCH3), 45.3 (C-2), 39.8
ν = 3427, 2923, 2854, 1717, 1624, 1454, 1360, 1090, 1074, 741,
˜
699 cm–1. HRMS (ESI): calcd. for C50H56O10Na [M + Na]+
839.3766; found 839.3775.
3-O-(2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-
D-lyxofuranos-
yl)-1,2:5,6-Di-O-isopropylidene-α- -glucofuranose (20): The cou-
D
pling between donor 1 (50.0 mg, 0.142 mmol, 1.0 equiv.) and ac-
ceptor 4 (40.6 mg, 0.156 mmol, 1.1 equiv.) was carried out accord-
ing to the general procedure. The resulting crude product was puri-
fied by flash chromatography (petroleum ether/ethyl acetate, 6:1)
to give 20 (55 mg, 63%) as a colourless syrup. [α]2D0 = +33.3 (c =
0.12, CHCl3). 1H NMR (600 MHz, CDCl3): δ = 7.37–7.24 (m, 8
H, Ar-H), 7.21 (d, J = 7.1 Hz, 2 H, Ar-H), 5.84 (d, J = 3.4 Hz, 1
H, 1-H), 5.01 (d, J = 4.6 Hz, 1 H, 1Ј-H), 4.66 (d, J = 3.5 Hz, 1 H,
2-H), 4.59 (d, J = 11.8 Hz, 1 H, CH2Ph), 4.53 (d, J = 12.3 Hz, 2
H, CH2Ph), 4.36 (dd, J = 9.8, 6.1 Hz, 1 H), 4.31–4.24 (m, 2 H),
4.17 (dt, J = 8.2, 5.7 Hz, 1 H), 4.15–4.07 (m, 2 H), 4.04 (dd, J =
8.5, 2.9 Hz, 1 H, 6-H), 3.96 (dd, J = 8.5, 5.3 Hz, 1 H, 6-H), 3.76
(dd, J = 9.6, 6.7 Hz, 1 H, 5Ј-H), 3.69 (dd, J = 9.7, 5.8 Hz, 1 H, 5Ј-
H), 2.81 (dd, J = 18.0, 10.2 Hz, 1 H, 1ЈЈ-H), 2.70 (td, J = 9.8,
4.7 Hz, 1 H, 2Ј-H), 2.54 (dd, J = 18.0, 4.1 Hz, 1 H, 1ЈЈ-H), 1.99 (s,
3 H, COCH3), 1.48 (s, 3 H), 1.39 (s, 3 H), 1.32 (s, 3 H), 1.29 (s, 3
H, 4 CH3) ppm. 13C NMR (150 MHz, CDCl3): δ = 206.9 (CO),
138.0, 137.9, 128.4, 127.8, 127.8, 127.7, 127.7 (overlap, 2 Ph), 111.8,
109.0 [2 C(CH3)2], 109.0 (C-1Ј), 105.4 (C-1), 84.1, 81.5, 81.3, 80.3,
79.5, 74.3 (CH2Ph), 73.5 (CH2Ph), 72.5, 68.3 (C-5Ј), 67.7 (C-6),
45.8 (C-2Ј), 39.5 (CH2CO), 29.9 (COCH3), 26.9, 26.8, 26.3, 25.4 (4
(CH CO), 29.9 (COCH ) ppm. IR (KBr): ν = 3427, 2918, 1717,
˜
2
3
1454, 1359, 1166, 1064, 1037, 1027, 739, 699 cm–1. HRMS (ESI):
calcd. for C23H28O5Na [M + Na]+ 407.1829; found 407.1840.
Benzyl 2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-D-lyxofuran-
oside (23): The coupling between donor 1 (50.0 mg, 0.142 mmol,
1.0 equiv.) and acceptor 7 (16.9 mg, 16.2 μL, 0.156 mmol,
1.1 equiv.) was carried out according to the general procedure. The
resulting crude product was purified by flash chromatography (pe-
troleum ether/ethyl acetate, 9:1) to give 23 (56 mg, 86 %) as a
colourless syrup. [α]2D0 = +73.1 (c = 0.31, CHCl3). 1H NMR
(400 MHz, CDCl3): δ = 7.49–7.17 (m, 15 H, Ar-H), 4.96 (d, J =
3.8 Hz, 1 H, 1-H), 4.80 (d, J = 11.9 Hz, 1 H, CH2Ph), 4.64–4.47
(m, 4 H, CH2Ph), 4.44 (td, J = 6.1, 4.2 Hz, 1 H, 4-H), 4.40–4.35
(m, 1 H, 3-H), 4.32 (d, J = 11.4 Hz, 1 H, CH2Ph), 3.83–3.75 (m, 1
H, 5-H), 3.72 (dd, J = 9.8, 6.1 Hz, 1 H, 5-H), 2.89–2.76 (m, 2 H,
1Ј-H, 2-H), 2.50 (q, J = 9.2 Hz, 1 H, 1Ј-H), 2.02 (s, 3 H, COCH3)
ppm. 13C NMR (150 MHz, CDCl3): δ = 207.1 (CO), 138.1, 138.0,
137.9, 128.5, 128.3, 127.8, 127.7, 127.6, 127.6, 126.9 (overlap, 3 Ph),
106.6 (C-1), 79.8 (C-4), 79.7 (C-3), 74.2, 73.5, 69.9 (3 CH2Ph), 68.5
ϫCH ) ppm. IR (KBr): ν = 3436, 2926, 1718, 1627, 1455, 1373,
˜
3
1256, 1216, 1167, 1071, 1023, 849, 740, 700 cm–1. HRMS (ESI):
calcd. for C34H44O10Na [M + Na]+ 635.2827; found 635.2843.
(C-5), 45.4 (C-2), 39.8 (CH CO), 29.9 (COCH ) ppm. IR (KBr): ν
˜
2
3
= 3434, 2918, 2885, 1713, 1455, 1361, 1103, 1054, 1039, 1019, 746,
698 cm–1. HRMS (ESI): calcd. for C29H32O5Na [M + Na]+
483.2142; found 483.2156.
Methyl 5-O-(2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-
D-lyxo-
furanosyl)-2,3-O-isopropylidene-β- -riboside (21): The coupling be-
D
tween donor 1 (50.0 mg, 0.142 mmol, 1.0 equiv.) and acceptor 5
(31.8 mg, 0.156 mmol, 1.1 equiv.) was carried out according to the
general procedure. The resulting crude product was purified by
flash chromatography (petroleum ether/ethyl acetate, 6:1) to give
21 (64 mg, 81%) as a colourless syrup. [α]2D0 = +12.0 (c = 0.26,
O-(2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-
D-lyxofuranosyl)-
N-benzyloxycarbonyl- -threonine Methyl Ester (24): The coupling
L
between donor 1 (50.0 mg, 0.142 mmol, 1.0 equiv.) and acceptor 8
(41.7 mg, 0.156 mmol, 1.1 equiv.) was carried out according to the
general procedure. The resulting crude product was purified by
flash chromatography (petroleum ether/ethyl acetate = 4:1) to give
24 (63 mg, 72%) as a colourless syrup. [α]2D0 = +34.0 (c = 0.60,
CHCl3). 1H NMR (600 MHz, CDCl3): δ = 7.39–7.27 (m, 13 H, Ar-
H), 7.20 (d, J = 7.0 Hz, 2 H, Ar-H), 5.51 (d, J = 9.6 Hz, 1 H, NH),
5.16–5.10 (m, 2 H, CH2Ph), 4.78 (d, J = 4.2 Hz, 1 H, 1-H), 4.58
(d, J = 11.9 Hz, 1 H, CH2Ph), 4.51 (dd, J = 11.8, 3.1 Hz, 2 H,
CH2Ph, 4-H), 4.37–4.30 (m, 2 H, OCH, NCH), 4.28 (d, J =
11.6 Hz, 2 H, CH2Ph), 4.26–4.22 (m, 1 H, 3-H), 3.74 (s, 3 H,
OCH3), 3.71 (dd, J = 14.3, 7.6 Hz, 1 H, 5-H), 3.64 (dd, J = 9.7,
5.9 Hz, 1 H, 5-H), 2.72 (dd, J = 17.9, 9.6 Hz, 1 H, 1Ј-H), 2.58 (dt,
J = 9.5, 4.8 Hz, 1 H, 2-H), 2.38 (dd, J = 17.9, 4.9 Hz, 1 H, 1Ј-H),
1
CHCl3). H NMR (600 MHz, CDCl3): δ = 7.36–7.26 (m, 8 H, Ar-
H), 7.21 (d, J = 7.1 Hz, 2 H, Ar-H), 4.94 (s, 1 H, 1-H), 4.83 (d, J
= 3.7 Hz, 1 H, 1Ј-H), 4.65 (d, J = 5.9 Hz, 1 H), 4.59 (d, J = 11.9 Hz,
1 H, CH2Ph), 4.55 (d, J = 5.9 Hz, 1 H), 4.52 (d, J = 4.8 Hz, 1 H),
4.50 (d, J = 4.3 Hz, 1 H), 4.36 (dd, J = 10.3, 6.0 Hz, 1 H, CH2Ph),
4.33–4.27 (m, 3 H), 3.76 (dd, J = 9.9, 5.9 Hz, 1 H, 5Ј-H), 3.73 (dd,
J = 9.8, 6.3 Hz, 1 H, 5Ј-H), 3.66 (dd, J = 9.8, 6.0 Hz, 1 H, 5-H),
3.36 (t, J = 9.3 Hz, 1 H, 5-H), 3.28 (s, 3 H, OCH3), 2.85–2.68 (m,
2 H, 1ЈЈ-H, 2Ј-H), 2.50 (dd, J = 16.6, 3.9 Hz, 1 H, 1ЈЈ-H), 2.01 (s,
3 H, COCH3), 1.47 (s, 3 H), 1.32 (s, 3 H), (2 CH3) ppm. 13C NMR
(150 MHz, CDCl3): δ = 207.1 (CO), 138.0, 138.0, 128.3, 127.8,
127.7, 127.7, 127.6 (overlap, 2 Ph), 112.3 [C(CH3)2], 109.2 (C-1Ј),
107.5 (C-1), 85.2, 85.1, 82.1, 79.6, 74.2 (CH2Ph), 73.5 (CH2Ph),
69.1 (C-5), 68.4 (C-5Ј), 54.7 (OCH3), 45.3 (C-2Ј), 39.8 (CH2CO),
1.99 (s, 3 H, COCH3), 1.28 (d, J = 6.3 Hz, 3 H, CHCH3) ppm. 13
C
NMR (150 MHz, CDCl3): δ = 206.9 (CO), 171.2 (COO), 156.6
(CONH), 138.0, 136.3, 128.5, 128.3, 128.1, 128.0, 127.8, 127.7,
127.6 (overlap, 3 Ph), 107.9 (C-1), 79.9 (C-4), 79.5 (C-3), 75.0, 74.2,
73.4 (3 CH2Ph), 68.2 (C-5), 67.1 (OCH2), 58.6 (OCH3), 52.3
(NHCH), 45.7 (C-2), 39.5 (CH2CO), 29.9 (COCH3), 18.7 (CHCH3)
29.9 (COCH ), 26.4, 25.0 (2 CH ) ppm. IR (KBr): ν = 3436, 2929,
˜
3
3
1711, 1376, 1354, 1210, 1108, 1093, 1052, 1023, 964, 871, 740,
696 cm–1. HRMS (ESI): calcd. for C31H40O9Na [M + Na]+
579.2565; found 579.2552.
ppm. IR (KBr): ν = 3436, 3292, 2929, 1731, 1710, 1698, 1547, 1454,
˜
Methyl 2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-D
-lyxofuranos- 1361, 1342, 1254, 1207, 1100, 1054, 1027, 738, 698 cm–1. HRMS
ide (22): The coupling between donor 1 (50.0 mg, 0.142 mmol,
1.0 equiv.) and acceptor 6 (5.0 mg, 6.3 μL, 0.156 mmol, 1.1 equiv.)
(ESI): calcd. for C35H41NO9Na [M + Na]+ 642.2674; found
642.2693.
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5

Job/Unit: O42037
/KAP1
Date: 17-06-14 12:33:16
Pages: 9
C. Wang, X. Ma, J. Zhang, Q. Tang, W. Jiao, H. Shao
FULL PAPER
O-(2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-
D
-lyxofuranosyl)-
206.8 (CO), 171.2 (COO), 155.6 (CONH), 138.0, 137.8, 128.4,
128.4, 127.9, 127.8, 127.7 (overlap, 2 Ph), 89.1 (C-1), 80.5
[C(CH3)3Boc], 79.6 (C-4), 79.1 (C-3), 74.4, 73.5 (2 CH2Ph), 67.2 (C-
5), 53.6 (OCH3), 52.3 (CHNH), 45.9 (C-2), 40.0 (CH2CO), 35.4
N-(tert-butoxycarbonyl)- -serine Methyl Ester (25): The coupling
L
between donor 1 (50.0 mg, 0.142 mmol, 1.0 equiv.) and acceptor 9
(34.2 mg, 0.156 mmol, 1.1 equiv.) was carried out according to the
general procedure. The resulting crude product was purified by
flash chromatography (petroleum ether/ethyl acetate = 4:1) to give
25 (65 mg, 80%) as a colourless syrup. [α]2D0 = +45.2 (c = 0.27,
(SCH2), 29.9 (COCH3), 28.3 (CH3Boc) ppm. IR (KBr): ν = 3424,
˜
2925, 1743, 1711, 1520, 1498, 1455, 1367, 1248, 1207, 1167, 1098,
1054, 1027, 740, 700 cm–1. HRMS (ESI): calcd. for C31H41NO8SNa
[M + Na]+ 610.2445; found 610.2463.
1
CHCl3). H NMR (600 MHz, CDCl3): δ = 7.36–7.26 (m, 8 H, Ar-
H), 7.19 (d, J = 6.9 Hz, 2 H, Ar-H), 5.60 (d, J = 8.6 Hz, 1 H, NH),
4.76 (d, J = 4.4 Hz, 1 H, 1-H), 4.59 (d, J = 11.9 Hz, 1 H, CH2Ph),
4.52 (dd, J = 11.7, 2.9 Hz, 2 H, CH2Ph, 4-H), 4.40 (d, J = 5.4 Hz,
1 H), 4.35 (dd, J = 10.1, 6.2 Hz, 1 H, CH2Ph), 4.31–4.24 (m, 2 H),
3.95 (d, J = 8.4 Hz, 1 H, OCH2), 3.85 (d, J = 9.8 Hz, 1 H, OCH2),
3.75–3.70 (m, overlap, 4 H, OCH3, 5-H), 3.66 (dd, J = 9.7, 5.8 Hz,
1 H, 5-H), 2.76 (dd, J = 17.7, 9.7 Hz, 1 H, 1Ј-H), 2.65 (td, J = 9.8,
4.9 Hz, 1 H, 2-H), 2.43 (dd, J = 17.7, 4.9 Hz, 1 H, 1Ј-H), 1.99 (s,
3 H, COCH3), 1.44 (s, 9 H, 3 CH3Boc) ppm. 13C NMR (150 MHz,
CDCl3): δ = 206.9 (CO), 171.0 (COO), 155.5 (CONH), 138.0,
137.9, 128.3, 127.8, 127.7, 127.7 (overlap, 2 Ph), 108.0 (C-1), 80.0
[C(CH3)3Boc], 79.8 (C-4), 79.5 (C-3), 74.2, 73.5 (2 CH2Ph), 69.3
(OCH2), 68.1 (C-5), 54.0 (OCH3), 52.3 (NHCH), 45.5 (C-2), 39.7
Ethyl 2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-1-thio-α-D-lyxo-
furanoside (28): The coupling between donor 1 (50.0 mg,
0.142 mmol, 1.0 equiv.) and acceptor 12 (9.7 mg, 11.5 μL,
0.156 mmol, 1.1 equiv.) was carried out according to the general
procedure. The resulting crude product was purified by flash
chromatography (petroleum ether/ethyl acetate, 10:1) to give 28
(45 mg, 77%) as a colourless syrup. [α]2D0 = +93.2 (c = 0.22, CHCl3).
1H NMR (600 MHz, CDCl3): δ = 7.37–7.27 (m, 8 H, Ar-H), 7.22
(d, J = 7.1 Hz, 2 H, Ar-H), 4.94 (d, J = 8.5 Hz, 1 H, 1-H), 4.60–
4.55 (m, 2 H, CH2Ph), 4.52 (d, J = 11.9 Hz, 1 H, CH2Ph), 4.38–
4.34 (m, 1 H, 4-H), 4.30 (d, J = 11.4 Hz, 1 H, CH2Ph), 4.29–4.25
(m, 1 H, 3-H), 3.80–3.71 (m, 1 H, 5-H), 3.67 (dd, J = 9.5, 5.5 Hz,
1 H, 5-H), 2.83 (dd, J = 18.9, 11.1 Hz, 1 H, 1Ј-H), 2.72–2.61 (m, 2
H, 1Ј-H, -SCH2CH3), 2.61–2.54 (m, 2 H, 2-H, -SCH2CH3), 2.00 (s,
3 H, COCH3), 1.27 (t, J = 7.4 Hz, 3 H, -SCH2CH3) ppm. 13C NMR
(150 MHz, CDCl3): δ = 207.1 (CO), 138.1, 138.0, 128.4, 128.3,
127.9, 127.7, 127.6 (overlap, 2 Ph), 87.6 (C-1), 80.4 (C-4), 79.3 (C-
3), 74.3, 73.4 (2 CH2Ph), 67.8 (C-5), 45.7 (C-2), 40.1 (CH2CO),
29.9 (COCH3), 25.3 (SCH2CH3), 15.2 (SCH2CH3) ppm. IR (KBr):
(CH2CO), 29.9 (COCH3), 28.3 (CH3Boc) ppm. IR (KBr): ν = 3436,
˜
2926, 1748, 1715, 1498, 1366, 1210, 1167, 1112, 1027, 740,
700 cm–1. HRMS (ESI): calcd. for C31H41NO9Na [M + Na]+
594.2674; found 594.2677.
Ethyl S-(2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-D-lyxofur-
anosyl)-2-mercaptoacetate (26): The coupling between donor 1
(50.0 mg, 0.142 mmol) and acceptor 10 (18.7 mg, 17.2 μL,
0.156 mmol, 1.1 equiv.) was carried out according to the general
procedure. The resulting crude product was purified by flash
chromatography (petroleum ether/ethyl acetate, 8:1) to give 26
(49 mg, 73%) as a colourless syrup. [α]2D0 = +129.1 (c = 0.24,
ν = 3425, 2926, 2870, 1715, 1406, 1374, 1354, 1264, 1208, 1163,
˜
1129, 1098, 1053, 1028, 739, 698 cm–1. HRMS (ESI): calcd. for
C24H30O4SNa [M + Na]+ 437.1757; found 437.1743.
p-Tolyl 2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-1-thio-α-D-lyxo-
1
furanoside (29): The coupling between donor 1 (50.0 mg,
0.142 mmol, 1.0 equiv.) and acceptor 13 (19.4 mg, 0.156 mmol,
1.1 equiv.) was carried out according to the general procedure. The
resulting crude product was purified by flash chromatography (pe-
troleum ether/ethyl acetate, 10:1) to give 29 (58 mg, 86%) as a
colourless syrup. [α]2D0 = +104.5 (c = 0.27, CHCl3). 1H NMR
(600 MHz, CDCl3): δ = 7.40–7.26 (m, 10 H, Ar-H), 7.21 (d, J =
7.3 Hz, 2 H, Ar-H), 7.09 (d, J = 7.7 Hz, 2 H, Ar-H), 5.10 (d, J =
8.9 Hz, 1 H, 1-H), 4.58 (dd, J = 11.6, 6.3 Hz, 2 H, CH2Ph), 4.52
(d, J = 11.8 Hz, 1 H, CH2Ph), 4.37–4.32 (m, 1 H, 4-H), 4.30 (d, J
= 11.5 Hz, 1 H, CH2Ph), 4.28–4.24 (m, 1 H, 3-H), 3.76 (t, J =
8.5 Hz, 1 H, 5-H), 3.73–3.66 (m, 1 H, 5-H), 2.85 (dd, J = 18.3,
10.8 Hz, 1 H, 1Ј-H), 2.63 (d, J = 17.6 Hz, 2 H, 1Ј-H, 2-H), 2.32 (s,
3 H, PhCH3), 2.01 (s, 3 H, COCH3) ppm. 13C NMR (150 MHz,
CDCl3): δ = 207.0 (CO), 138.1, 138.0, 137.4, 132.1, 130.6, 129.6,
128.4, 127.8, 127.7, 127.6 (overlap, 3 Ph), 90.4 (C-1), 80.9 (C-4),
79.1 (C-3), 74.3, 73.4 (2 CH2Ph), 67.7 (C-5), 45.4 (C-2), 39.9
CHCl3). H NMR (400 MHz, CDCl3): δ = 7.39–7.29 (m, 8 H, Ar-
H), 7.27–7.20 (m, 2 H, Ar-H), 5.11 (d, J = 7.8 Hz, 1 H, 1-H), 4.57
(dt, J = 18.8, 9.1 Hz, 3 H, CH2Ph), 4.42–4.35 (m, 1 H, 4-H), 4.31
(dd, J = 7.3, 3.9 Hz, 2 H, CH2Ph, 3-H), 4.18 (q, J = 7.1 Hz, 2 H, -
OCH2CH3), 3.76 (dd, J = 9.5, 7.1 Hz, 1 H, 5-H), 3.69 (dd, J = 9.6,
5.7 Hz, 1 H, 5-H), 3.49 (d, J = 15.4 Hz, 1 H, -SCH2COOEt), 3.30
(d, J = 15.4 Hz, 1 H, -SCH2COOEt), 2.88 (dd, J = 19.0, 11.2 Hz,
1 H, 1Ј-H), 2.68–2.55 (m, 2 H, 1Ј-H, 2-H), 2.03 (s, 3 H, COCH3),
1.28 (t, J = 7.1 Hz, 3 H, OCH2CH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 207.0 (CO), 170.4 (COOEt), 138.0, 137.9, 128.4, 128.4,
127.9, 127.8, 127.7 (overlap, 2 Ph), 87.3 (C-1), 80.6 (C-4), 79.40 (C-
3), 74.4, 73.5 (2 CH2Ph), 67.7 (C-5), 61.4 (OCH2CH3), 45.6 (C-2),
40.1 (CH2CO), 32.5 (SCH2CO), 29.9 (COCH3), 14.1 (CH2CH3)
ppm. IR (KBr): ν = 3438, 2920, 2871, 1733, 1717, 1711, 1455, 1408,
˜
1356, 1287, 1130, 1098, 1028, 700, 699 cm–1. HRMS (ESI): calcd.
for C26H32O6SNa [M + Na]+ 495.1812; found 495.1823.
S-(2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-
D-lyxofuranosyl)-
(CH CO), 29.9 (COCH ), 21.0 (PhCH ) ppm. IR (KBr): ν = 3431,
˜
2
3
3
N-(tert-butoxycarbonyl)- -cysteine Methyl Ester (27): The coupling
L
2923, 2866, 1717, 1494, 1454, 1354, 1063, 1015, 810, 738, 698 cm–1.
HRMS (ESI): calcd. for C29H32O4SNa [M + Na]+ 499.1914; found
499.1936.
between donor 1 (50.0 mg, 0.142 mmol, 1.0 equiv.) and acceptor 11
(36.7 mg, 0.156 mmol, 1.1 equiv.) was carried out according to the
general procedure. The resulting crude product was purified by
flash chromatography (petroleum ether/ethyl acetate, 6:1) to give
27 (70 mg, 84%) as a colourless syrup. [α]2D0 = +31.8 (c = 0.22,
CHCl3). 1H NMR (400 MHz, CDCl3): δ = 7.52–7.18 (m, 10 H, Ar-
Isopropyl 2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-D-lyxofur-
anoside (30): The coupling between donor 1 (50.0 mg, 0.142 mmol,
1.0 equiv.) and acceptor 14 (9.4 mg, 12.0 μL, 0.156 mmol,
H), 6.31 (d, J = 8.8 Hz, 1 H, NH), 4.86 (d, J = 8.7 Hz, 1 H, 1-H), 1.1 equiv.) was carried out according to the general procedure. The
4.69–4.52 (m, 4 H), 4.42 (dd, J = 6.9, 4.0 Hz, 1 H, 4-H), 4.35–4.23
(m, 2 H), 3.81 (t, J = 7.1 Hz, 1 H, 5-H), 3.79–3.70 (m, overlap, 4
resulting crude product was purified by flash chromatography (pe-
troleum ether/ethyl acetate, 8:1) to give 30 (42 mg, 72 %) as a
H, 5-H, OCH3), 3.30 (d, J = 4.5 Hz, 1 H, -SCH2), 2.89 (dd, J = colourless syrup. [α]2D0 = +62.0 (c = 0.16, CHCl3). 1H NMR
10.7, 3.7 Hz, 1 H, -SCH2), 2.84 (dd, J = 14.9, 7.1 Hz, 1 H, 1Ј-H), (400 MHz, CDCl3): δ = 7.41–7.29 (m, 8 H, Ar-H), 7.27–7.20 (m, 2
2.56 (dt, J = 7.4, 3.0 Hz, 2 H, 1Ј-H, 2-H), 2.02 (s, 3 H, COCH3), H, Ar-H), 4.95 (d, J = 4.7 Hz, 1 H, 1-H), 4.65–4.59 (m, 1 H,
1.44 (s, 9 H, 3 CH3Boc) ppm. 13C NMR (100 MHz, CDCl3): δ =
CH2Ph), 4.55 (t, J = 7.8 Hz, 2 H, CH2Ph, 4-H), 4.40 (td, J = 6.3,
6
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O42037
/KAP1
Date: 17-06-14 12:33:16
Pages: 9
1,2-(Acetylcyclopropane)-Annulated d-Lyxofuranose
4.0 Hz, 1 H, 3-H), 4.36–4.30 (m, 2 H, CH2Ph), 3.88 [dt, J = 12.4,
ethyl acetate, 3:1) to give 33 (38 mg, 58%) as a colourless syrup.
1
6.2 Hz, 1 H, CH(CH3)2], 3.76 (dd, J = 9.7, 6.6 Hz, 1 H, 5-H), 3.68 [α]2D0 = +6.1 (c = 0.36, CHCl3). H NMR (400 MHz, CDCl3): δ =
(dd, J = 9.7, 5.9 Hz, 1 H, 5-H), 2.80 (dd, J = 17.6, 9.6 Hz, 1 H, 1Ј-
H), 2.66 (td, J = 9.9, 4.9 Hz, 1 H, 2-H), 2.50 (dd, J = 17.6, 4.8 Hz,
8.92 (br. s, 1 H, NH), 7.43–7.29 (m, 9 H, Ar-H, 6-H), 7.27–7.22
(m, 2 H, Ar-H), 6.01 (d, J = 8.7 Hz, 1 H, 5-H), 5.79 (d, J = 8.2 Hz,
1 H, 1Ј-H), 2.04 (s, 3 H, COCH3), 1.21 (d, J = 6.2 Hz, 3 H), 1.13 1 H, 1Ј-H), 4.61 (dd, J = 11.7, 5.5 Hz, 2 H, CH2Ph), 4.57–4.50 (m,
(d, J = 6.1 Hz, 3 H, 2 CH3) ppm. 13C NMR (100 MHz, CDCl3): δ
= 207.3 (CO), 138.1, 138.0, 128.3, 127.8, 127.8, 127.7, 127.6 (over-
lap, 2 Ph), 105.4 (C-1), 79.7 (C-4), 79.4 (C-3), 74.2, 73.4 (2 CH2Ph),
2 H, CH2Ph, 4Ј-H), 4.36 (dd, J = 7.4, 3.9 Hz, 2 H, CH2Ph, 3Ј-H),
3.81–3.63 (m, 2 H, 5Ј-H), 2.88 (dd, J = 19.2, 9.4 Hz, 1 H, 1ЈЈ-H),
2.79–2.62 (m, 2 H, 1ЈЈ-H, 2Ј-H), 2.02 (s, 3 H) ppm. 13C NMR
70.0 [OCH(CH3)2], 68.5 (C-5), 45.6 (C-2), 39.7 (CH2CO), 29.9 (100 MHz, CDCl3): δ = 206.8 (CO), 162.9 (C-4), 150.6 (C-2), 139.2
(COCH ), 23.5, 21.7 (2 CH ) ppm. IR (KBr): ν = 3436, 2969, 2924,
(C-5), 137.5, 137.5, 128.5, 128.5, 128.1, 128.0, 127.9, 127.9 (overlap,
2 Ph), 103.1 (C-6), 88.7 (C-1Ј), 82.8 (C-4Ј), 79.7 (C-3Ј), 74.6, 73.7
(2 CH2Ph), 68.0 (C-5Ј), 45.7 (C-2Ј), 38.7 (CH2CO), 29.8 (COCH3)
˜
3
3
2872, 1718, 1626, 1455, 1358, 1208, 1169, 1113, 1056, 1028, 737
699 cm–1. HRMS (ESI): calcd. for C25H32O5Na [M + Na]+:
435.2142; found 435.2149.
ppm. IR (KBr): ν = 3435, 2925, 1693, 1631, 1455, 1383, 1275, 1172,
˜
1078, 1048, 810, 738, 700 cm–1. HRMS (ESI): calcd. for
C26H28N2O6Na [M + Na]+ 487.1840; found 487.1833.
Phenyl 2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-O-α-D-lyxofur-
anoside (31): The coupling between donor 1 (50.0 mg, 0.142 mmol,
1.0 equiv.) and acceptor 15 (14.7 mg, 0.156 mmol, 1.1 equiv.) was
carried out according to the general procedure. The resulting crude
product was purified by flash chromatography (petroleum ether/
ethyl acetate, 9:1) to give 31 (53 mg, 84%) as a colourless syrup.
[α]2D0 = +88.4 (c = 0.35, CHCl3). 1H NMR (400 MHz, CDCl3): δ =
7.46–7.27 (m, 12 H, Ar-H), 7.09–6.96 (m, 3 H, Ar-H), 5.49 (d, J =
4.9 Hz, 1 H, 1-H), 4.66–4.50 (m, 4 H, CH2Ph, 4-H), 4.45 (dd, J =
5.1, 3.7 Hz, 1 H, 3-H), 4.37 (d, J = 11.4 Hz, 1 H, CH2Ph), 3.82
(dd, J = 9.6, 7.2 Hz, 1 H, 5-H), 3.74 (dd, J = 9.6, 5.5 Hz, 1 H, 5-
H), 3.02 (dt, J = 9.7, 5.0 Hz, 1 H, 2-H), 2.92 (dd, J = 17.8, 10.2 Hz,
1 H, 1Ј-H), 2.63 (dd, J = 17.8, 4.2 Hz, 1 H, 1Ј-H), 2.05 (s, 3 H,
COCH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 207.0 (CO),
157.3, 138.0, 137.9, 129.4, 128.4, 128.4, 127.9, 127.8, 127.7, 121.9,
116.5 (overlap, 3 Ph), 105.5 (C-1), 80.8 (C-4), 79.3 (C-3), 74.4, 73.5
(2 CH2Ph), 67.8 (C-5), 45.9 (C-2), 39.6 (CH2CO), 30.0 (COCH3)
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures and NMR spectra for all new com-
pounds.
Acknowledgments
The authors are grateful for the financial support from the
National Natural Science Foundation of China (NSFC) (grant
number 21372215).
[1] a) W. D. Celmer, Pure Appl. Chem. 1971, 28, 413–453; b) H.
Grisebach, R. Schmid, Angew. Chem. Int. Ed. Engl. 1972, 11,
159–173; Angew. Chem. 1972, 84, 192–206; c) H.-W. Liu, J. S.
Thorson, Annu. Rev. Microbiol. 1994, 48, 223–256; d) S.
Knapp, Chem. Rev. 1995, 95, 1859–1876; e) X. M. He, H.-W.
Liu, Annu. Rev. Biochem. 2002, 71, 701–754.
[2] a) D. Rouzaud, P. Sinaÿ, J. Chem. Soc., Chem. Commun. 1983,
1353–1354; b) M. H. D. Postema, J. L. Piper, V. Komanduri, L.
Lei, Angew. Chem. Int. Ed. 2004, 43, 2915–2918; Angew. Chem.
2004, 116, 2975–2978; c) C. Wiebe, C. Schlemmer, S. Weck, T.
Opatz, Chem. Commun. 2011, 47, 9212–9214; d) D. C. Koester,
E. Kriemen, D. B. Werz, Angew. Chem. Int. Ed. 2013, 52, 2985–
2989; e) S. Dharuman, Y. D. Vankar, Org. Lett. 2014, 16, 1172–
1175.
[3] a) H. C. Hang, C. R. Bertozzi, J. Am. Chem. Soc. 2001, 123,
1242–1243; b) J. E. Jackman, C. A. Fierke, L. N. Tumey, M.
Pirrung, T. Uchiyama, S. H. Tahir, O. Hindsgaul, C. R. H. Ra-
etz, J. Biol. Chem. 2000, 275, 11002–11009; c) X. Li, T. Uchi-
yama, C. R. H. Raetz, O. Hindsgaul, Org. Lett. 2003, 5, 539–
541.
ppm. IR (KBr): ν = 3431, 2919, 2872, 1717, 1599, 1495, 1360, 1228,
˜
1102, 1070, 1009, 755, 697 cm–1. HRMS (ESI): calcd. for
C28H30O5Na [M + Na]+ 469.1985; found 469.1992.
1-(2-C-Acetylmethyl-3,5-di-O-benzyl-2-deoxy-α-D-lyxofuranosyl)-5-
fluorouracil (32): The coupling between donor 1 (50.0 mg,
0.142 mmol, 1.0 equiv.) and acceptor 16 (77.9 mg, 0.284 mmol,
2.0 equiv.) was carried out with CH3SO3H (13.7 mg, 9.2 μL,
0.142 mmol, 1.0 equiv.) according to the general procedure. The
resulting crude product was purified by flash chromatography (pe-
troleum ether/ethyl acetate, 3:1) to give 32 (38 mg, 55 %) as a
colourless syrup. [α]2D0 = +7.4 (c = 0.15, CHCl3). 1H NMR
(400 MHz, CDCl3): δ = 8.65 (d, J = 4.6 Hz, 1 H, NH), 7.39–7.30
(m, 9 H, Ar-H, 6-H), 7.26 (dd, J = 5.1, 2.9 Hz, 2 H, Ar-H), 5.99
(dd, J = 8.6, 1.5 Hz, 1 H, 1Ј-H), 4.62 (dd, J = 11.7, 3.7 Hz, 2 H,
CH2Ph), 4.58–4.51 (m, 2 H, CH2Ph, 4Ј-H), 4.37 (d, J = 11.5 Hz, 1
H, CH2Ph), 4.35–4.31 (m, 1 H, 3Ј-H), 3.73 (d, J = 6.3 Hz, 2 H, 5Ј-
H), 2.81 (ddd, J = 15.7, 14.0, 6.6 Hz, 2 H, 1ЈЈ-H, 2Ј-H), 2.68 (dq,
J = 8.7, 4.9 Hz, 1 H, 1ЈЈ-H), 2.03 (s, 3 H, COCH3) ppm. 13C NMR
(100 MHz, CDCl3): δ = 206.6 (CO), 156.5, 156.2 (d, C-4), 149.0
(C-2), 142.0, 139.6 (d, C-5), 137.5, 137.4, 128.6, 128.5, 128.1, 128.0,
127.9, 127.9 (overlap, 2 Ph), 123.5, 123.2 (d, C-6), 89.0 (C-1Ј), 82.9
(C-4Ј), 79.7 (C-3Ј), 74.6, 73.7 (2 CH2Ph), 67.9 (C-5Ј), 45.6 (C-2Ј),
[4] B. R. Babu, L. Keinicke, M. Petersen, C. Nielsen, J. Wengel,
Org. Biomol. Chem. 2003, 1, 3514–3526.
[5] a) P. G. Reddy, D. Bao, W. Chang, B.-K. Chun, J. Du, D. Naga-
rathnam, S. Rachakonda, B. S. Ross, H.-R. Zhang, S. Bansal,
C. L. Espiritu, M. Keilman, A. M. Lam, C. Niu, H. M. Steuer,
P. A. Furman, M. J. Otto, M. J. Sofia, Bioorg. Med. Chem.
Lett. 2010, 20, 7376–7380; b) M. M. Bio, F. Xu, M. Waters,
J. M. Williams, K. A. Savary, C. J. Cowden, C. Yang, E. Buck,
Z. J. Song, D. M. Tschaen, R. P. Volante, R. A. Reamer, E. J. J.
Grabowski, J. Org. Chem. 2004, 69, 6257–6266; c) J. L. Clark,
L. Hollecker, J. C. Mason, L. J. Stuyver, P. M. Tharnish, S. Los-
tia, T. R. McBrayer, R. F. Schinazi, K. A. Watanabe, M. J.
Otto, P. A. Furman, W. J. Stec, S. E. Patterson, K. W. Pankiew-
icz, J. Med. Chem. 2005, 48, 5504–5508.
38.8 (CH CO), 29.8 (COCH ) ppm. IR (KBr): ν = 3439, 2919,
˜
2
3
2850, 1715, 1664, 1466, 1455, 1361, 1275, 1272, 1075, 1048, 743,
700 cm–1. HRMS (ESI): calcd. for C26H27FN2O6Na [M + Na]+
505.1745; found 505.1755.
[6] a) A. Matsuda, K. Takenuki, T. Sasaki, T. Ueda, J. Med. Chem.
1991, 34, 234–239; b) K. Hanaoka, M. Suzuki, T. Kobayashi,
F. Tanzawa, K. Tanaka, T. Shibayama, S. Miura, T. Ikeda, H.
Iwabuchi, A. Nakagawa, Y. Mitsuhashi, M. Hisaoka, M.
Kaneko, A. Tomida, Y. Wataya, T. Nomura, T. Sasaki, A. Mat-
suda, T. Tsuruo, S. Kurakata, Int. J. Cancer 1999, 82, 226–236;
c) K. Yamagami, A. Fujii, M. Arita, T. Okumoto, S. Sakata,
1-(2-C-Acetylmethyl-3,5-Di-O-benzyl-2-deoxy-α-D-lyxofuranosyl)-
uracil (33): The coupling between donor 1 (50.0 mg, 0.142 mmol,
1.0 equiv.) and acceptor 17 (72.7 mg, 0.284 mmol 2.0 equiv.) was
carried out with CH3SO3H (13.7 mg, 9.2 μL, 0.142 mmol,
1.0 equiv.) according to the general procedure. The resulting crude
product was purified by flash chromatography (petroleum ether/
Eur. J. Org. Chem. 0000, 0–0
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C. Wang, X. Ma, J. Zhang, Q. Tang, W. Jiao, H. Shao
FULL PAPER
A. Matsuda, T. Ueda, T. Sasaki, Cancer Res. 1991, 51, 2319–
2323; d) H. Eda, M. Ura, K. F.-Ouchi, Y. Tanaka, M. Miwa,
H. Ishitsuka, Cancer Res. 1998, 58, 1165–1169; e) X. Liu, Y.
Guo, Y. Li, Y. Jiang, S. Chubb, A. Azuma, P. Huang, A. Mat-
suda, W. Hittelman, W. Plunkett, Cancer Res. 2005, 65, 6874–
6881; f) A. Matsuda, T. Sasaki, Cancer Sci. 2004, 95, 105–111;
g) A. Azuma, K. Hanaoka, A. Kurihara, T. Kobayashi, S. Mi-
yauchi, N. Kamo, M. Tanaka, T. Sasaki, A. Matsuda, J. Med.
Chem. 1995, 38, 3391–3397; h) A. Azuma, Y. Nakajima, N.
Nishizono, N. Minakawa, M. Suzuki, K. Hanaoka, T. Kobaya-
shi, M. Tanaka, T. Sasaki, A. Matauda, J. Med. Chem. 1993,
36, 4183–4189.
[15]
For reviews on donor–acceptor cyclopropanes, see: a) E. Wenk-
ert, Acc. Chem. Res. 1980, 13, 27–31; b) H.-U. Reissig, Top.
Curr. Chem. 1988, 144, 73–135; c) H.-U. Reissig, R. Zimmer,
Chem. Rev. 2003, 103, 1151–1196; d) D. Agrawal, V. K. Yadav,
Chem. Commun. 2008, 6471–6488; e) C. A. Carson, M. A.
Kerr, Chem. Soc. Rev. 2009, 38, 3051–3060; f) F. De Simone, J.
Waser, Synthesis 2009, 3353–3374; For recent examples, see: g)
T. F. Schneider, J. Kaschel, B. Dittrich, D. B. Werz, Org. Lett.
2009, 11, 2317–2320; h) J. Kaschel, T. F. Schneider, D. Kratzert,
D. Stalke, D. B. Werz, Angew. Chem. Int. Ed. 2012, 51, 11153–
11156; i) T. F. Schneider, J. Kaschel, S. I. Awan, B. Dittrich,
D. B. Werz, Chem. Eur. J. 2010, 16, 11276–11288; j) J. Kaschel,
C. D. Schmidt, M. Mumby, D. Kratzert, D. Stalke, D. B. Werz,
Chem. Commun. 2013, 49, 4403–4405; k) J. Kaschel, T. F.
Schneider, P. Schirmer, C. Maaß, D. Stalke, D. B. Werz, Eur. J.
Org. Chem. 2013, 4539–4551.
a) Q. Tian, L. Y. Xu, X. F. Ma, W. Zou, H. W. Shao, Org. Lett.
2010, 12, 540–543; b) Q. Tian, L. Dong, X. F. Ma, L. Y. Xu,
C. W. Hu, W. Zou, H. W. Shao, J. Org. Chem. 2011, 76, 1045–
1053; c) J. Beyer, P. R. Skaanderup, R. Madsen, J. Am. Chem.
Soc. 2000, 122, 9575–9583; d) J. Beyer, R. Madsen, J. Am.
Chem. Soc. 1998, 120, 12137–12138.
a) R. J. Hewitt, J. E. Harvey, J. Org. Chem. 2010, 75, 955–958;
b) N. V. Ganesh, S. Raghothama, R. Sonti, N. Jayaraman, J.
Org. Chem. 2010, 75, 215–218; c) N. V. Ganesh, N. Jayaraman,
J. Org. Chem. 2009, 74, 739–746; d) R. Batchelor, J. E. Harvey,
P. T. Northcote, P. Teesdale-Spittle, J. O. Hoberg, J. Org. Chem.
2009, 74, 7627–7632; e) N. V. Ganesh, N. Jayaraman, J. Org.
Chem. 2007, 72, 5500–5504.
[7] a) R. Pontikis, J. Wolf, C. Monneret, J.-C. Florent, Tetrahedron
Lett. 1995, 36, 3523–3526; b) S. P. Ong, S. C. McFarlan,
H. P. C. Hogenkamp, Biochemistry 1993, 32, 11397–11404; c)
C. H. Baker, J. Banzon, J. M. Bollinger, J. Stubbe, V. Samano,
M. J. Robins, B. Lippert, E. Jarvi, R. Resvick, J. Med. Chem.
1991, 34, 1879–1884.
[8] a) P. M. Gordon, R. Fong, S. K. Deb, N.-S. Li, J. P. Schwans,
J.-D. Ye, J. A. Piccirilli, Chem. Biol. 2004, 11, 237–246; b) J. P.
Schwans, N.-S. Li, J. A. Piccirilli, Angew. Chem. Int. Ed. 2004,
43, 3033–3037; Angew. Chem. 2004, 116, 3095–3099; c) J. B. J.
Pavey, A. J. Lawrence, I. A. O’Neil, S. Vortler, R. Cosstick, Org.
Biomol. Chem. 2004, 2, 869–875.
[9] K. Takenuki, A. Matsuda, T. Ueda, T. Sasaki, A. Fujii, K.
Yamagami, J. Med. Chem. 1988, 31, 1063–1064.
[10] For selected reviews, see: a) G. S. Cousins, J. O. Hoberg, Chem.
Soc. Rev. 2000, 29, 165–174; b) M. Yu, B. L. Pagenkopf, Tetra-
hedron 2005, 61, 321–347; c) J. Yin, T. Linker, Org. Biomol.
Chem. 2012, 10, 2351–2362.
[11] For some examples, see: a) T. Linker, T. Sommermann, F. Kah-
lenberg, J. Am. Chem. Soc. 1997, 119, 9377–9384; b) J. Yin, T.
Sommermann, T. Linker, Chem. Eur. J. 2007, 13, 10152–10167;
c) T. Linker, D. Schanzenbach, E. Elamparuthi, T. Som-
mermann, W. Fudickar, V. Gyóllai, L. Somsák, W. Demuth,
M. Schmittel, J. Am. Chem. Soc. 2008, 130, 16003–16010; d)
E. Elamparuthi, T. Linker, Angew. Chem. Int. Ed. 2009, 48,
1853–1855; Angew. Chem. 2009, 121, 1885–1887; e) J. Yin, T.
Linker, Org. Biomol. Chem. 2009, 7, 4829–4831; f) S. R. Vidad-
ala, T. M. Pimpalpalle, T. Linker, S. Hotha, Eur. J. Org. Chem.
2011, 2426–2430.
[12] For a review, see: N.-S. Li, J. Lu, J. A. Piccirilli, Org. Prep.
Proced. Int. 2010, 42, 191–283.
[13] For some examples, see: a) A. J. Lawrence, J. B. J. Pavey, R.
Cosstick, I. A. O’Neil, J. Org. Chem. 1996, 61, 9213–9222; b)
J. Lim, Y. H. Kim, J. Chem. Soc. Perkin Trans. 1 1999, 3239–
3241; c) N.-S. Li, J. Lu, J. A. Piccirilli, Org. Lett. 2007, 9, 3009–
3012.
[16]
[17]
[18]
a) J. O. Hoberg, J. J. Bozell, Tetrahedron Lett. 1995, 36, 6831–
6834; b) J. O. Hoberg, J. Org. Chem. 1997, 62, 6615–6618; c)
R. Batchelor, J. O. Hoberg, Tetrahedron Lett. 2003, 44, 9043–
9045; d) P. R. Sridhar, P. Venukumar, Org. Lett. 2012, 14, 5558–
5561.
[19] M. Yu, B. L. Pagenkopf, J. Am. Chem. Soc. 2003, 125, 8122–
8123.
[20] a) H. W. Shao, S. Ekthawatchai, S.-H. Wu, W. Zou, Org. Lett.
2004, 6, 3497–3499; b) H. W. Shao, S. Ekthawatchai, C.-S.
Chen, S.-H. Wu, W. Zou, J. Org. Chem. 2005, 70, 4726–4734;
c) X. F. Ma, Q. Tian, Q. Tang, J. Z. Zhao, H. W. Shao, Org.
Lett. 2011, 13, 4276–4279; d) X. F. Ma, Q. Tang, J. Ke, J. C.
Zhang, C. Wang, H. B. Wang, Y. X. Li, H. W. Shao, Chem.
Commun. 2013, 49, 7085–7087; e) X. F. Ma, Q. Tang, J. Ke,
X. L. Yang, J. C. Zhang, H. W. Shao, Org. Lett. 2013, 15, 5170–
5173; f) X. F. Ma, J. C. Zhang, Q. Tang, J. Ke, W. Zou, H. W.
Shao, Chem. Commun. 2014, 50, 3505–3508.
[21] C. U. Pittman, S. P. McManus, J. Am. Chem. Soc. 1969, 91,
5915–5918.
[14] For some examples, see: a) K. Bischofberger, A. J. Brink,
O. G. D. Villiers, R. H. Hall, A. Jordaan, J. Chem. Soc. Perkin
Trans. 1 1977, 1472–1476; b) P. R. Sridhar, P. V. Kumar, K.
Seshadri, R. Satyavathi, Chem. Eur. J. 2009, 15, 7526–7529.
Received: April 19, 2014
Published Online: ᭿
8
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Eur. J. Org. Chem. 0000, 0–0

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Date: 17-06-14 12:33:16
Pages: 9
1,2-(Acetylcyclopropane)-Annulated d-Lyxofuranose
Branched-Chain Sugars
The acid-catalysed ring-opening coupling
reaction of 1,2-(acetylcyclopropane)-annu-
lated d-lyxofuranose is reported. Various
nucleophiles (alcohols, thiols, nucleobases,
monosaccharides, and amino acids) reacted
with this donor to give a wide variety of 2-
C-branched d-lyxofuranosyl derivatives in
high yields and with excellent α stereoselec-
tivities.
C. Wang, X. Ma, J. Zhang, Q. Tang,
W. Jiao, H. Shao* ............................ 1–9
Methanesulfonic-Acid-Catalysed
Opening and Glycosylation of 1,2-(Acetyl-
cyclopropane)-Annulated d-Lyxofuranose
Ring
Keywords: Carbohydrates / Disaccharides /
Glycosylation / Glycoconjugates / Small-
ring systems
Eur. J. Org. Chem. 0000, 0–0
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