Intramolecular and Ferrier Rearrangement Strategy for the Construction of C1-β-d-xylopyranosides: Synthesis, Mechanism and Biological Activity Study

Article abstract of DOI:10.1002/adsc.201801423

A stereoselective synthesis of C1-β-d-xylopyranoside derivatives had been developed via intramolecular 1,3-acyloxy migration/Ferrier rearrangement stategy from readily available propargylic carboxylates and d-xylal. A combined catalytic system of chloro(t

Full text of DOI:10.1002/adsc.201801423

Title: Intramolecular and Ferrier Rearrangement Strategy for the
Construction of C1-β-D-xylopyranosides: Synthesis, Mechanism
and Biological Activity Study
Authors: Yuan Yao, Cai-Ping Xiong, Ya-Ling Zhong, Guo-Wei Bian,
Nianyu Huang, Long Wang, and Kun Zou
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201801423
Link to VoR: http://dx.doi.org/10.1002/adsc.201801423

10.1002/adsc.201801423
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Intramolecular and Ferrier Rearrangement Strategy for the
Construction of C1-β-D-xylopyranosides: Synthesis, Mechanism
and Biological Activity Study
Yuan Yaoa, Cai-Ping Xionga, Ya-Ling Zhonga, Guo-Wei Biana, Nian-Yu Huanga,*,
Long Wangb, and Kun Zoua
a
Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences,
China Three Gorges University, Yichang, Hubei 443002, P. R. China
Fax: (+86)-717-639-5580; phone: (+86)-717-639-7478; e-mail: huangny@ctgu.edu.cn (N. Huang)
College of Materials and Chemical Engineering, China Three Gorges University, Yichang, Hubei 443002, P. R. China
b
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Lactoquinomycin A[6] and (+)-Ambruticin S[7] (Figure
Abstract.
A
stereoselective synthesis of C1-β-D-
xylopyranoside derivatives had been developed via 1). Because of the potential bioactivity as well as the
intramolecular
1,3-acyloxy
migration/Ferrier
synthetic challenges, these carbohydrate moieties
have attracted considerable interest in the total
synthesis and glycosylation methodologies[8].
rearrangement stategy from readily available propargylic
carboxylates and D-xylal. A combined catalytic system of
chloro(triphenylphosphine)gold(I) (Ph3PAuCl) and silver
hexafluoroantimonate (AgSbF6) was found to possess the
most effective of the reaction, and 20 examples tested the
wide functional compatibility for these transformation.
Nuclear magnetic resonance (NMR), infrared spectrum
(IR), high resolution electrospray ionization mass
spectroscopy (HRESIMS) and isotopic labelling
experiments were utilized to investigate the C1-
glycosylation process. The relative configuration for the
products was determined by two-dimensional (2D) NMR
NMR and electronic circular dichroism spectroscopy. 3-
(4,5)-Dimethylthiahiazo(-z-y1)-3,5-diphenytetrazoliumro-
mide (MTT) cell viability assays indicated that three of
them showed strong anti-proliferative activities against
human gastric cancer HGC-27 cells with IC50 values of
17.09-38.88 μM. This method opened up new horizons for
the synthesis of bioactive C-glycosylated molecules.
Figure 1. Some natural products and drugs containing C-
glycosides.
Generally, C-glycosylation reactions can involve
glycosyl electrophilic/cationic species, anionic
species, radical species, or transition-metal complexes.
Therefore, the synthesis of C-glycosylation usually
involves the metal reagents as glycosyl donors or
catalysts, and the process is much more sluggish due
to the air and moisture sensitivities[9]. Although lots of
transitional metal-catalyzed cross coupling including
Heck, Suzuki, Stille and Negishi-type reactions have
been developed for the synthesis of C-glycosides
using glycals, the functional regioselectivity and α/β
stereoselectivity at the anomeric carbon constitute are
still one of the most challenging issues in
carbohydrate chemistry[10]. For example, Ernest’s
group utilized Pd0-mediated cyclo-etherification of 1-
acetoxy-2,3-dideoxy-oct-2-enitols to produce C-vinyl
α- and β-glycopyranosides with high stereoselectivity
Keywords: C1-glycosylation; 1,3-acyloxy migration;
Ferrier rearrangement; gold (I) catalysis; cytotoxicity
Compared to O- and N-glycoside, the C-glycoside
comprises a carbohydrate unit attached to an aglycone
or another carbohydrate unit through a C-C bond
linkage. Due to the stability toward hydrolysis of C-
glycosides, the mimics of O-glycosides have been
widely reported with potent biologically activities in
natural products and synthetic drugs in recent years,
such as (-)-Dysiherbaine[1], (-)-Neodysiherbaine A[2],
Deoxyfrenolicin[3], Pro-XylaneTM[4],(-)-Kendomycin[5],
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801423
Advanced Synthesis & Catalysis
using (S,S) or (R,R)-DACH ligands in 2014[11], and rearrangement of 2a to give the C1-alkylation
then Martin’s group produced epimeric mixture of C- products, however, gold (III) chloride was found to be
vinyl deoxyriboside by the Lindlar hydrogenation of the effective catalyst to transform the propargylic
the epimeric mixture of C-ethynyl deoxyriboside[12]
.
ester to the nucleophillic allene intermediate and give
Liu’s group reported a palladium-catalyzed one-pot the final Ferrier rearrangement C1-glycosylation
Tsuji-Trost type decarboxylative allylation/Wittig product 3a in 24% isolated yields (Table 1, entries 1-
reaction to synthesize β,(E)-selective C-vinyl 7). This positive result promoted us to further search
glycosides with pyridyl group containing aldehydes more appropriate catalyst to improve the efficiency of
and β,(Z)-selective C-vinyl glycosides with the reaction, and then the gold (I) complex and silver
nonpyridyl aldehydes in 2017, which had potential to (I) salts could catalyze the reaction in comparative
be applied in synthesizing C-vinyl glycosides in high yields (entries 8-10). To our surprise, we found that
efficiency with controlled diastereoselectivity[13]
.
the combined catalytic system exhibited superior to
the single catalyst (entries 11-14). Therefore,
Ph3PAuCl and AgSbF6 system was selected as the
best catalyst for the high yield of 58% yields, and
further optimization of solvent contributed to improve
the yield of 3a in 75% yields (Table 1, entries 14-20).
Finally, the C1-glycoside could be smoothly prepared
from propargylic acetate and diacetyl-D-xylal under
the catalytic Ph3PAuCl/AgSbF6 in nitromethane at
ambient temperature.
Table 1. Optimization of C1-glycosylationa
Entry
1
2
3
4
5
6
7
8
Catalyst
AgNO3
Pd(OAc)2
Cr(OAc)3
Cu(OAc)2
PdCl2
SrCl2
AuCl3
Ph3PAuCl
Solvent
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH3NO2
CHCl3
Yieldb
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
24%
45%
35%
20%
50%
42%
38%
58%
75%
37%
43%
N.D.
N.D.
N.D.
Scheme 1. The synthesis of C-vinyl glycosides
For facial construction of synthetically valuable
complex C-glycosides, the intramolecular
rearrangements including Claisen rearrangement,
Ramberg-Bäcklund rearrangement, and 1,2-Wittig
rearrangement have become powerful tools for the C-
glycosylations[14]. The homogeneous gold catalysis,
an exciting new synthetic tool to build synthetically
valuable complex molecules, has become a hot spot in
organometallic chemistry since 2005[15], which could
activate alkenyl, allenyl and alkynyl p-bonds based on
the strong p-acidic character of complexes of Au(I)
and Au(III)[16]. Among them, cationic phosphine-gold
(I) complexes are especially versatile and selective
9
AgSbF6
AgOTf
10
11
12
13
14
15
16
17
18
19
20
Ph3PAuCl+ AgOTf
AuCl3+ AgOTf
AuCl3+ AgSbF6
Ph3PAuCl + AgSbF6
Ph3PAuCl + AgSbF6
Ph3PAuCl + AgSbF6
Ph3PAuCl + AgSbF6
Ph3PAuCl + AgSbF6
Ph3PAuCl + AgSbF6
Ph3PAuCl + AgSbF6
Toluene
EtOAc
CH3CN
HCON(CH3)2
catalysts for
a growing number of synthetic
transformations[17]. Recently, β-xylopyranosides have
a)
attracted renewed interest due to the development of
General conditions: propargylic carboxylate (1a, 1.0
interesting biological activities and material usage[18]
.
equiv.), diacetyl-D-xylal (2a, 1.0 equiv.), Ph3PAuCl and
AgSbF6 (5 mol %). Solvent: 2 mL. b) Isolated yield. N.D. =
not detected.
As continuation of previous studies on the C-
glycosylation reaction using homogeneous gold
catalysis by Ferrier rearrangement[19], the one-pot
intramolecular cross coupling reactions of propargylic
acetates and diacetyl-D-xylal via 1,3-acyloxy
migration and Ferrier rearrangement was investigated
in this work.
In order to screen the proper conditions for C1-
glycosylation from propargylic acetate (1a) and
diacetyl-D-xylal (2a), seven transitional metals were
evaluated the abilities of inducing the Ferrier
Under the optimized reaction condition, the
substrate scope of the C1-glycosylation reaction was
examined (Scheme 2). The electron-donating groups
connected on the phenyl group (R1) of propargylic
acetate resulted in poor β-stereoselectivity at the
anomeric carbon and lower yields (62%-70%) for the
C1-β-D-xylopyranoside derivatives (compounds 3k-
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801423
Advanced Synthesis & Catalysis
3q), while the electron-withdrawing groups usually
Based on the experimental results and related
resulted in better stereoselectivity and yields (79%- literatures[22], the following mechanistic pathways
85%, compounds 3f-3k). Further exploration of the were proposed. At first, the formation of allylic
substrate scope was focused on the aliphatic oxocarbenium ion (B) from diacetyl-D-xylal (2a) via a
substituted group or heterocyclic group (R1) on the Ferrier rearrangement was promoted by gold catalyst,
triple bond of propargylic acetate, which also gave then transformation of the propargylic carboxylate (1)
moderate yields (68%~80%) for compounds 3r-3t. It into the nucleophilic allenic intermediate (A) through
was worth noticing that the Boc-protecting-D-xylal a 1,3-acyloxymigration which subsequently attacked
failed to give the C1-β-D-xylopyranosides (3) under intermediate (B) to give the oxocar benium ion (3').
the same reaction condition.
Finally, the hydrolysis of oxocarbenium ion (3')
The relative β-configuration for 3d was confirmed delivered the target C1-β-D-xylopyranosides (3).
by NMR and electronic circular dichroism Owing to the stability of the equatorial conformation
spectroscopy. In NOESY, the correlation between H- for large substituents, the stereo-structure for the C1-
1 (5.32 ppm) and H-7 (6.38 ppm) could be observed, β-D-xylopyranosides was finally obtained (Scheme 3).
and its relative β-configuration could be defined as
trans-isomer for the anomeric carbon with the
observed coupling constants of 5-Ha (4.27 ppm, dd, J
= 10.8, 5.2 Hz, 1H) and 5-Hb (3.59 ppm, dd, J = 10.8,
7.6 Hz, 1H), which were consistent with previuos
reported[20]. Furthermore, the absolute configuration
of the C1-glycoside was also tested by experimental
electronic circular dichroism spectroscopy, and its
possible configurations were calculated by DFT
B3LYP method of gaussian software[21]. The result
was found to be consistent with the β-anomer’s
calculations and the product configuration was
inferred to be the β-configuration.
Scheme 3. Proposed mechanism for C1-β-D-xylopyranosyl
ation reaction
In order to confirm this reaction mechanism, 31P
1
NMR experiment, infrared detection experiment, H
NMR detection experiments and isotopic labeling
experiments were carried out to monitor the catalyst
combination way and reaction process more clearly.
Considering the proposed mechanism for the
synthesis of the C1-β-D-xylopyranosides (Scheme 3)
and the prerequisite for the generation of
nucleophillic allene intermediate (A) from
propargylic acetate (1), the monitored infrared
spectrum experiment was also carried out to observe
the spectrum properties of intermediate and the
synchronous monitoring results were shown in Figure
2. Notably, a peak signal at the wavelength of 2435
cm-1 could be observed when the catalyst was added,
which disappeared after quenching. This signal might
be attributed to the allene intermediate (A) from
propargylic carboxylate (1) (Figure 2a). Furthermore,
allene experiment in the same condition further
confirmed this result (Figure 2b).
To assess the product more clearly, 1H NMR
detection experiment was carried out in CDCl3
solution[23]. As shown in Figure 3, before adding the
1
catalyst, the multiplet H NMR peaks appeared 6.52
ppm which be longed to 1-H signal of the diacetyl-D-
xylal. With the catalyst added in, this proton signal
Scheme 2. Substrate scope for C1-β-D-xylopyranoside
derivatives
3
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801423
Advanced Synthesis & Catalysis
compounds were also evaluated for in vitro anti-
proliferative activities against two human cancer cell
lines (HGC-27 and Caski) for 48 h at 37゜C by MTT
assays[26]. Unfortunately, just three of them (3c, 3f, 3l)
were found to possess the better anti-cytotoxic
activities against HGC-27 cells with IC50 values of
17.09~38.88 μM (Table 2). Compound 3l also
showed cytotoxic activities against Caski cells with
IC50 63.63 μM. These results indicated the
introduction of phenyl resulted in increasing
cytostatic effect while unsubstituted phenyl group
shows better inhibition rate than substituted. Notably,
these C1-β-D-xylopyranosides exhibited low toxicity
against to the normal human hepatic LO2 cells (IC50 >
500 μM). The further structural exploration and anti-
tumor mechanism study for these C1-β-D-
xylopyranosides are under way in our research group.
Figure 2. IR monitoring of the reaction progress.
propargylic carboxylates (1a, 0.05 mol), diacetyl-D-xylal
(2a, 0.05 mol) and (Ph3P)AuSbF6 (5% mol).
intermediate (0.05 mol), D-xylal (0.05 mol) and
(Ph3P)AuSbF6 (5% mol).
a
b
allenic
disappeared because of Ferrier rearrangement. Two
minutes later, a new doublet appeared at 6.38 ppm
when the catalyst was added, which might attribute as
the olefinic proton of H-7 in the enone skeleton.
Table 2. Calculated antiproliferative IC50 values for some
cytotoxic compounds
IC50 values (μM)
Compounds
HGC-27
17.09
30.12
Caski
>100
>100
63.63
LO2
>500
>500
>500
3c
3f
3l
38.88
Inhibition against HGC-27 for 48 hrs
100
50
0
3,125 6,25
12,5
Concentration (μM)
3c 3f
25
50
100
Figure 3. 1H NMR monitoring of the reaction progress.
3l
Figure 4. Inhibition against HGC-27 cells for 48 hours
The mechanism was further confirmed through
isotopic labeling experiments by performing the
reaction with 18O-labeled propargylic carboxylate 1m-
18O according to related literatures[24]. The 18O-labeled
ketone’s carbon signal at 197.2 ppm could be clearly
In conclusion, a highly stereoselective synthesis of
bioactive C1-β-D-xylopyranosides was developed
based on strategy of intramolecular 1,3-acyloxy
migration/Ferrier rearrangement process. The
versatility and flexibility of this method was evident
from its extensive substrate scope. Remarkably, high
13
found in the C NMR of 3w-18O, where ESI-HR-MS
analysis also showed the presence of 18O in the
product, which indicated the success of the 1,3-
acyloxy rearrangement and nucleophilic C1-
glycosylation process (Scheme 4).
yields
and
exclusive
regioselectivity
and
diasteroselectivity were obtained, demonstrating that
the reaction tolerates a wide range of substituents. In
addition, the potential of employing this method to
construct synthetically valuable complex molecules
will be their increasing applications in synthesizing of
structurally diverse and functional natural products.
As our continuous interest in search of the
biological antitumor agents[25], all the target
Experimental Section
Scheme 4. Isotopic labeling experiment
Typical procedure for the synthesis of 1-phenylhept-1-
yn-3-yl acetate (1a)
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801423
Advanced Synthesis & Catalysis
Phenylacetylene (0.91 g, 7.0 mmol) was added to the
Carrino, A. I. Caplan, L. Breton, Eur. J. Dermatol.
2011, 21, 359-370.
reaction flask and then nitrogen protection, after that, added
in re-steamed THF (6 mL) to stir for 5 minutes. n-BuLi
(2.4 mol/L, 2.9 mL, 7mmol) was injected at a low
temperature (-78℃), after the mixture was stirred for 5 min
under the dewar, added the 1-butyraldehyde (0.435 g) and
stirred at room temperature until the starting material was
completely consumed. The mixture was concentrated in
vacuo. Purification of the residue by flash chromatography
on silica gel (petroleum ether / ethyl acetate = 100:1, V/V)
and afforded the propargylic carboxylate (1a) as colorless
oil.
[5] a) Y. Yuan, H. Men, C. Lee, J. Am. Chem. Soc. 2004,
126, 14720-14721. b) K. C. Nicolaou, S. P. Ellery, J. S.
Chen, Angew.Chem. Int. Ed. 2009, 48, 7140-7165. c) T.
Sengoku, S. Xu, K. Ogura, Y. Emori, K. Kitada, D.
Uemura, H. Arimoto, Angew. Chem. Int. Ed. 2014, 53,
4213-4216.
[6] a) P. M. Léo, C. Morin, C. Philouze, Org. Lett. 2002, 4,
2711-2714. b) R. T. Williamson, L. A. McDonald, L. R.
Barbieri, G. T. Carter, Org. Lett. 2002, 4, 4659-4662. c)
H. Sun, Z. Liu, H. Zhao, E. L. Ang, Drug Des. Devel.
Ther. 2015, 9, 823-833.
Typical procedure for the synthesis of (3R,6S)-6-((Z)-1-
oxo-1-phenylhex-2-en-2-yl)-3,6-dihydro-2H-pyran-3-yl
acetate (3a)
[7] a) T. A. Kirkland, J. Colucci, L. S. Geraci, M. A. Marx,
M. Schneider, D. E. Kaelin, S. F. Martin, J. Am. Chem.
Soc. 2001, 123, 12432-12433. b) E. Lee, S. J. Choi, H.
Kim, H. O. Han, Y. K. Kim, S. J. Min, S. H. Son, S. M.
Lim, W. S. Jang, Angew. Chem. Int. Ed. 2002, 41, 176-
178. c) S. F. Martin, J. Org. Chem. 2017, 82, 10757-
10794.
A solution of diacetyl-D-xylal (2a, 0.2 mmol) and 1-
phenylhex-1-yn-3-yl acetate (1a, 0.2 mmol) in anhydrous
CH3NO2 (2.0 mL) was stirred at room temperature for 10
min. Ph3PAuCl (4.9 mg, 5.0 mol %) and AgSbF6 (2.6 mg,
5 mol %) was added sequentially. The reaction was stirred
at room temperature until the starting material was
completely consumed. The mixture was filtered through a
plug of silica and concentrated in vacuo. Purification of the
residue by flash chromatography on silica gel (petroleum
ether / ethyl acetate = 100:1, V/V) and afforded the C-
xylopyranoside (3a).
[8] a) C. Taillefumier, Y. Chapleur, Chem. Rev. 2004, 104,
263-292. b) K. Lalitha, K. Muthusamy, Y. S. Prasad, P.
K. Vemula, S. Nagarajan, Carbohydr. Res. 2015, 402,
158-171. c) M. M. Wei, Y. S. Wang, X. S. Ye, Med.
Res. Rev. 2018, 38, 1003-1026. d) S. Tang, Q. Zheng,
D. C. Xiong, S. Jiang, Q. Li, X. S. Ye, Org. Lett. 2018,
20, 3079-3082.
[9] For selected reviews on chemical synthesis of C-
glycosides, see: a) Y. Yang, B. Yu, Chem. Rev. 2017,
117, 12281-12356. b) H. Liao, J. Ma, H. Yao, X. W.
Liu, Org. Biomol. Chem. 2018, 16, 1791-1806. c) W. L.
Leng, H. Yao, J. X. He, X. W. Liu, Acc. Chem. Res.
2018, 51, 628-639.
Acknowledgements
We gratefully acknowledge financial support of this work by
the National Natural Science Foundation of China (21602123,
21272136) and Youth Talent Development Foundation of China
Three Gorges University. Special thanks to Dr. Xuewei Liu of
Nanyang Technological University for his guidance in organic
chemistry and biochemistry.
[10] M. J. Mckay, H. M. Nguyen, ACS. Catal. 2012, 2,
1563-1595.
[11] E. G. Nolen, V. C. Ezeh, M. J. Feeney, Carbohydr.
Res. 2014, 396, 43-47.
References
[1] a) R. Sakai, H. Kamiya, M. Murata, K. Shimamoto, J. [12] I. Snajdr, K. Parkan, F. Hessler, M. Kotora, Beilstein.
Am. Chem. Soc. 1997, 119, 4112-4116. b) H. Masak, J.
J. Maeyama, Kazuko Kamada, T. Esumi, Y. Iwabuchi,
S. Hatakeyama, J. Am. Chem. Soc. 2000, 122, 5216-
5217. c) L. V. Flórez, P. H. W. Biedermann, T. Engla,
M. Kaltenpoth, Nat. Prod. Rep. 2015, 32, 904-936.
J. Org. Chem. 2015, 11, 1392-1397.
[13] W. L. Leng, H. Liao, H. Yao, Z. E. Ang, S. Xiang, X.
W. Liu, Org. Lett. 2017, 19, 416-419.
[14] Y. Yang, B. Yu, Chem. Rev. 2017, 117, 12281-12356.
b) B. Yu, Acc. Chem. Res. 2018, 51, 507-516.
[2] a) R. Sakai, T. Koike, M. Sasaki, K. Shimamoto, C.
Oiwa, A. Yano, K. Suzuki, K. Tachibana, H. Kamiya,
Org. Lett. 2001, 3, 1479-1482. b) P. Escavabaja, J.
Viala, Y. Coquerel, J. Rodriguez, Adv. Synth. Catal.
2012, 354, 3200-3204. c) R. Sakai, G. T. Swansonb,
Nat. Prod. Rep. 2014, 31, 273-309.
[15] For reviews on gold-catalyzed reactions, see: a) A.
Stephen K. Hashmi, Chem. Rev. 2007, 107, 3180-
3211 b) D. Qian, J. Zhang, Chem. Soc. Rev. 2015, 44,
677-698. c) D. Pflästerer, A. S. K. Hashmi, Chem. Soc.
Rev. 2016, 45, 1331-1367. d) G. J. Hutchings. ACS
Cent Sci. 2018, 4, 1095-1101.
[3] a) L. D. Foland, O. H. W. Decker, H. W. Moore, J. Am.
Chem. Soc. 1989, 111, 989-995. b) Briar J. Naysmith,
Paul A. Hume, Jonathan Sperry and Margaret A.
Brimble, Nat. Prod. Rep. 2017, 34, 25-61.
[16] a) D. P. Day, P. W. H. Chan, Adv. Synth. Catal. 2016,
358, 1368-1384. b) Y. Yu, W. B. Yang, F. Rominger,
A. Stephen, K. Hashmi, Angew. Chem. Int. Ed. 2013,
52, 7586-7589. c) C. Obradors, A. M. Echavarren, Acc.
Chem. Res. 2013, 47, 902-912. d) D. H. Zhang, X.Y.
Tang, M. Shi, Acc. Chem. Res. 2013, 47, 913-924.
[4] A. Cavezza, C. Boulle, A. Gueguiniat, P. Pichaud, S.
Trouille, L. Ricard and M. Dalko-Csiba, Bioorg. Med.
Chem. Lett. 2009, 19, 845-849. N. Pineau, D. A.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801423
Advanced Synthesis & Catalysis
[17] D. J. Gorin, F. D. Toste, Nature 2007, 446, 395-403.
[18] a) C. H. Yao, J. S. Song, C. T. Chen, T. K. Yeh, M. S.
Hung, J. Med. Chem. 2011, 54, 166-178. b) A.
Siegbahn, K. Thorsheim, J. Stahle, S. Manner, C.
Hamark, Org. Biomol. Chem. 2015, 13, 3351-3362. c)
C. Brusa, M. Muzard, C. Rémond, R. Plantier-Royon,
RSC Adv. 2015, 5, 91026-91055.
[19] a) N. Y. Huang, H. Liao, H. Yao, T. P. Xie, S. Zhang,
K. Zou, X. W. Liu, Org. Lett. 2018, 20, 16-19. b) H.
Liao, W. L. Leng, K. L. M. Hoang, H. Yao, J. He, A.
Y. H. Voo, X. W. Liu, Chem. Sci. 2017, 8, 6656-6661.
[20] a) R. F.N. Pradilla, M. Tortosa, Org. Lett. 2004, 6,
2157-2160. b) R. F. N. Pradilla, N. Lwoff, M. N.Guila,
M. Tortosa, A.Viso, J. Org. Chem. 2008, 73, 8929-
8941.
[21] a) M. B.Arapinis, V. Gandon, E. Prost, L. Micouin, T.
Lecourt, Adv. Synth. Catal. 2014, 356, 2493-2505. b)
M. Khajehzadeh, M. Moghadam, S. Acta A. Mol.
Biomol. Spectrosc. 2017, 180, 51-66.
[22] a) Meng Yu, G. T. Li, S. Z. Wang, L. M. Zhang, Adv.
Synth. Catal. 2007, 349, 871-875. b) P. Nun, S.
Gaillard, A. M. Slawin, S. P. Nolan, Chem. Commun.
2010, 46, 9113-9115. c) L. M. Zhang, S. Z. Wang, J.
Am. Chem. Soc. 2006, 128, 1442-1443.
[23] a) N. Conde, R. Sanmartin, M. T. Herrero, E.
Domínguez, Adv. Synth. Catal. 2016, 358, 3283-3292.
b) S. P. Swain, Y. L. Chou, D. R. Hou, Adv. Synth.
Catal. 2015, 357, 2644-2650.
[24] a) H. Aruri, U. Singh, S. Kumar, M. Kushwaha, A. P.
Gupta, R. A. Vishwakarma, P. P. Singh, Org. Lett.
2016, 18, 3638-3641. b) C. Veryser, G. Steurs, L. V.
Meervelt, W. M. Borggraeve, Adv. Synth. Catal. 2017,
359, 1271-1276.
[25] a) X. Y. Li, B. F. He, H. J. Luo, N. Y. Huang, W. Q.
Deng, Bioorg. Med. Chem. Lett. 2013, 23, 4617-4621.
b) X. F. Lu, Z. Yang, N. Y. Huang, H. B. He, W. Q.
Deng, K. Zou, Bioorg. Med. Chem. Lett. 2015, 25,
3726-3729. c) L. Wang, Y. B. Xie, N. Y. Huang, J. Y.
Yan, W. M. Hu, M. G. Liu, M. W. Ding, ACS Catal.
2016, 6, 4010-4016. d) N. Y. Huang, W. B. Wang, L.
Chen, H. J. Luo, J. Z. Wang, W. Q. Deng, K. Zou,
Bioorg. Med. Chem. Lett. 2016, 26, 2268-2272
[26] Q. Xiao, F. Zheng, Q. Tang, J. J. Wu, J. Xie, H. D.
Huang, X. B. Yang, S. S. Hann, Cell Physiol. Biochem.
2018, 49, 1615-1632.
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801423
Advanced Synthesis & Catalysis
COMMUNICATION
Intramolecular and Ferrier Rearrangement
Strategy for the Construction of C1-β-D-
xylopyranosides: Synthesis, Mechanism and
Biological Activity Study
Adv. Synth. Catal. Year, Volume, Page – Page
Yuan Yao, Cai-Ping Xiong, Ya-Ling Zhong, Guo-
Wei Bian, Nian-Yu Huang*, Long Wang, Kun Zou
7
This article is protected by copyright. All rights reserved.