Stereoselective Phenylselenoglycosylation of Glycals Bearing a Fused Carbonate Moiety toward the Synthesis of 2-Deoxy-β-galactosides and β-Mannosides

Article abstract of DOI:10.1021/acs.orglett.0c00732

A phenylselenoglycosylation reaction of glycal derivatives mediated by diphenyl diselenide and phenyliodine(III) bis(trifluoroacetate) under mild conditions is described. Stereoselective glycosylation has been achieved by installing fused carbonate on those glycals. 3,4-O-Carbonate galactals and 2,3-O-carbonate 2-hydroxyglucals are converted into corresponding glycosides in good yields with excellent β-selectivity, resulting in 2-phenylseleno-2-deoxy-β-galactosides and 2-phenylseleno-β-mannosides which are good precursors of 2-deoxy-β-galactosides and β-mannosides, respectively.

Full text of DOI:10.1021/acs.orglett.0c00732

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Letter
Stereoselective Phenylselenoglycosylation of Glycals Bearing a
Fused Carbonate Moiety toward the Synthesis of 2‑Deoxy-β-
galactosides and β‑Mannosides
Shuai Meng, Wenhe Zhong, Wang Yao, and Zhongjun Li*
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ABSTRACT: A phenylselenoglycosylation reaction of glycal
derivatives mediated by diphenyl diselenide and phenyliodine(III)
bis(trifluoroacetate) under mild conditions is described. Stereo-
selective glycosylation has been achieved by installing fused
carbonate on those glycals. 3,4-O-Carbonate galactals and 2,3-O-
carbonate 2-hydroxyglucals are converted into corresponding
glycosides in good yields with excellent β-selectivity, resulting in
2-phenylseleno-2-deoxy-β-galactosides and 2-phenylseleno-β-man-
nosides which are good precursors of 2-deoxy-β-galactosides and β-
mannosides, respectively.
Table 2. PIFA-PhSeSePh-Promoted Glycosylation of
Galactal 5
ligosaccharides and glycoconjugates play essential roles in
1
Omultitudinous biological processes. Intense efforts have
Table 1. PIFA-PhSeSePh-Promoted Glycosylation of Glucal
1 and Galactal 2
a
entry
ROH
result
1
2
3
4
5
6
7
MeOH
EtOH
i-PrOH
n-BuOH
BnOH
6a, 95%, β only
6b, 92%, β only
6c, 90%, β only
6d, 90%, β only
6e, 92%, β only
6f, 84%, β only
a
entry
glycal
R1OH
result
CyOH
PMBOH
1
2
3
4
5
6
7
1
1
1
1
1
1
2
MeOH
EtOH
96%, 3aα:3bβ = 1:1.5
98%, 3bα:3bβ = 1:1.5
95%, 3cα:3cβ= 1:1.3
92%, 3dα:3dβ = 1:1.8
90%, 3eα:3eβ = 1:1.3
88%, 3fα:3fβ = 1:1.1
6g, 84%, β only
1
a
i-PrOH
n-BuOH
BnOH
t-BuOH
MeOH
Yield of both isomers. Ratio was determined by H NMR.
are more acid sensitive. Although direct synthesis5 and de novo
synthesis6 are known, indirect synthesis is the most commonly
used strategy for the preparation of 2-deoxy-β-glycosides.
Typically a temporary substituent such as halogen,7 ester,8
thioether,9 or selenoether10 is installed at C2 for directing the
formation of glycosidic bonds, which is removed later by
reductive cleavage. As a type of 1,2-cis glycoside, β-mannosides
98%, 4α:4β = 1:1.4
a
1
Yield of both isomers. Ratio was determined by H NMR.
been dedicated to the chemical preparation of oligosaccharides
for biological studies.2 Due to their specific structural features,
stereoselective construction of several kinds of glycosidic
linkages, such as 2-deoxy-β-glycosides3 and β-mannosides,4
are particularly challenging. Lacking C2 substituents that can
direct the anomeric selectivity makes the stereoselective
synthesis of 2-deoxy-glycosides rather difficult. Thermodynami-
cally, the formation of 2-deoxy-α-glycosides is superior to β-
anomers because of anomeric effect. In addition, without
electron-withdrawing groups at C2, the 2-deoxyglycosidic bonds
Received: February 25, 2020
https://dx.doi.org/10.1021/acs.orglett.0c00732
© XXXX American Chemical Society
Org. Lett. XXXX, XXX, XXX−XXX
A

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Scheme 1. Stereoselective Synthesis of 2-Phenylseleno-2-deoxy-β-galactosides via PIFA-PhSeSePh-Mediated Activation of 3,4-
O-Carbonate Galactals
a
b
c
Yield for isolated product. All reactions were finished in 30 min. 14 was obtained in 36% yield. 14 was obtained in 30% yield.
use of 2,6- or 3,6-lactones,16 and β-selective anomeric O-
Scheme 2. Proposed Mechanism for the Generation of 14
alkylation of mannose lactols.17 Indirect syntheses by converting
β-glucosides or β-2-ulosyl-glycosides into β-mannosides have
been developed as well.18 Despite this progress, syntheses of 2-
deoxy-β-glycosides and β-mannosides are still challenging.
Herein, we report our efforts toward the stereoselective
construction of 2-deoxy-β-glycosides and β-mannosides.
2-Phenylseleno-2-deoxy-glycosides are good precursors of 2-
deoxy-glycosides as the C2 selenoether can be cleanly removed
by reductive cleavage. However, 2-deoxy-glycosyl donors
bearing C2 equatorial selenoether may epimerize and afford α-
linkages.10b Recently, one-step α-selective glycosylation acti-
vated by the addition of electrophilic selenium species to glycals
has been reported.10a Therefore, we are motivated to develop a
method for the stereoselective synthesis of 2-deoxy-β-glycosides
based on the activation of glycals by selenium electrophile. With
the experience of the dihydroxylation of olefin mediated by
hypervalent iodine species,19 we attempted to use this type of
oxidant for the introduction of C2 selenoether. We found that
perbenzylated glucal 1 and galactal 2 reacted with simple
alcohols in the presence of phenyliodine(III) bis-
(trifluoroacetate) (PIFA) and PhSeSePh in acetonitrile at
room temperature to afford the corresponding glycosides in
excellent yields (Table 1). Moreover, the reactions showed the
potential toward the formation of β-glycosides. It has been
reported that glycosyl donors bearing carbonate7c,d,20 or
Scheme 3. Removal of C2 Phenylseleno to Obtain 2-
Deoxygalactoside
are difficult to synthesize due to the steric effect of axial C2-
substituent and anomeric effect. Several direct synthetic
strategies have been developed, including insoluble silver salt
mediated activation of mannosyl halides,11 the use of 4,6-O-
tethered mannosyl donors,12 intramolecular aglycone delivery,13
hydrogen-bond-mediated aglycone delivery,14 boronic acid or
borinic acid mediated activation of 1,2-anhydro-mannose,15 the
B
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Scheme 4. Proposed Reaction Mechanism for the Construction of β-Mannosides from 2,3-O-Carbonate-2-hydroxyglucal
glycoside 6n in 87% yield. We also surveyed the glycosylation of
5 with some sugar-derived acceptors (7−13). All of the primary
alcohols and many secondary alcohols reacted with 5 smoothly,
resulting in the corresponding β-linked disaccharides in 83−
90% yields. The coupling with sugar 10 and 11 gave disaccharide
6t and 6u in 57% and 62% with lactol 14 isolated in 36% and
30% yield, respectively. Although we conducted the reactions
with 10 and 11 again under absolutely anhydrous condition, the
results did not change much. We reasoned that the lactol 14
formed from the reactions of 5 with 10 and 11 was possibly
generated by the hydrolysis of intermediate 14a, which was
formed via the attack of 1,2-episelenonium ion by trifluor-
oacetate anion (Scheme 2). Such a side reaction was not
noticeable when the less sterically hindered acceptors (7, 8, 9,
12a/b, 13a) reacted with 5. Taken together, the glycosylation of
conformationally restricted galactal 5 with different kinds of
acceptors in the presence of PIFA and PhSeSePh in acetonitrile
provided the expected 2-phenylseleno-2-deoxy-β-galactosides,
with undetectable formation of the corresponding α-talosides.
Many commonly used protecting groups were tolerable and in
general, the glycosylation reactions afforded the products in a
short period of time with satisfactory yields. Considering that 6-
O-TBDPS may also contribute to the β-selectivity because it
provided prominent steric hindrance on β-face and favored the
attack of electrophiles from α-face, we prepared another
conformationally restricted galactal 15 bearing 6-O-Ac. The
glycosylation of 15 with acceptor 8 under the optimal condition
provided β-linked disaccharide 16 in 89% yield. This result
indicated that the excellent β-selectivity highly depended on the
restricted conformation caused by 3,4-O-carbonate moiety. To
demonstrate the subsequent removal of C2 selenoether and 3,4-
O-carbonate, compound 6a was treated with Bu3SnH and AIBN
in toluene at 110 °C followed by the deacylation in methanol to
afford 2-deoxy-β-galactoside 17 in a total yield of 91% (Scheme
3).
The success in stereoselective phenylselenoglycosylation of
galactals prompted us to use glucals bearing carbonate moiety
for the stereoselective construction of 2-deoxy-β-glucosides.
Unfortunately, our attempts to synthesizing 3,4-O-carbonate
glucals failed due to the trans- relationship of C3 and C4
hydroxyl. Meanwhile, we proposed an approach toward the
construction of β-mannosides via the phenylselenoglycosylation
of 2-hydroxy (protected by ether or ester) glucals. Although the
3,4-O-carbonate moiety could not be installed on 2-hydrox-
yglucal either due to the similar geometry with nomal glucals, the
formation of 2,3-O-carbonate-2-hydroxyglucal 18 is feasible and
its phenylselenoglycosylation could be stereoselective due to the
chiral C3 hydroxyl group (Scheme 4). Activation of 18 by
phenylselenium cation could generate two intermediates 19a
Table 3. Glycosylation of 2-Hydroxyglucals 22−25
entry
donor
result
1
2
3
4
22
23
24
25
93%, 26a
decomposed
no reaction
decomposed
Scheme 5. Cleavage of C2 Phenoseleno to Obtain β-
Mannoside
carbamate21 moiety sometimes provide excellent stereo-out-
comes in glycosylation reactions. With this in mind, we
synthesized conformationally restricted galactal 5 bearing 3,4-
O-carbonate and 6-O-TBDPS. The reactions of 5 with simple
alcohols under the aforementioned condition were conducted
and we were pleased to find that the corresponding glycosides
were obtained in high yields with excellent β-selectivity (Table
2). After optimization, we confirmed the optimal conditions as
0.65 equiv of PhSeSePh and 0.6 equiv of PIFA in acetonitrile at
room temperature.22
With the optimal condition in hands, we carried out the
glycosylation of various acceptors, including noncarbohydrate
and sugar-derived alcohols. Noncarbohydrate substrates in-
cluded simple alcohols, piperonyl alcohol, 4-benzoxyphenetha-
nol, 4-pivaloxyphenethanol, 6-azidohexanol, (S)-α-phenethyl
alcohol, (R)-α-phenethyl alcohol, 1-adamantanol, N-Boc-L-
serine methyl ester, and menthol. The reactions of galactal 5
with these noncarbohydrate acceptors all afforded the
corresponding 2-phenylseleno-2-deoxy-β-galactosides in high
yields (83−95%, Scheme 1). Notably, the glycosylation with a
tertiary alcohol, 1-adamantanol, afforded the corresponding
C
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Scheme 6. Phenylselenoglycosylation of 2,3-O-Carbonate-2-hydroxyglucals
a
Isolated yields for all the products.
graphic analysis, the C−Se bond should be equatorial based on
the 1,2-trans relationship with glycosidic bond (see Scheme 4,
20a), because it was generated by the attack of nucleophiles to
episelenonium ion (see Scheme 4, 19a). Treatment of 26a under
the condition of Bu3SnH and AIBN followed by the removal of
2,3-O-carbonate and global acetylation gave compound 27 in
90% yield (Scheme 5), which was identified as methyl 2,3,4,6-
tetra-O-acetyl-β-mannoside.25 In addition, the NMR of 27 also
agreed with its reported data.26 We did not observe the
formation of corresponding glucosides or α-mannoside. Thus,
our proposed scheme for the stereoselective construction of β-
mannosides from 2,3-O-carbonate-2-hydroxyglucal was shown
to be effective.
Scheme 7. Diastereoselective Reduction of 35f
and 19b. The subsequent attack of acceptors at the anomeric
position from the opposite side to the episelenonium ion would
produce β-linked glycoside 20a and α-linked 20b, respectively.
Due to the ring strain of 2,3-fused carbonate, the formation of
2,3-cis fused intermediate 19a and product 20a would be
favored. Subsequent reductive removal of C2 selenoether of 20a
could also be achieved in a stereoselective manner because of the
ring strain as well,23 resulting in the corresponding β-mannoside
21b.
Based on this hypothesis, we synthesized 2,3-O-carbonate
protected 22. 2,3-O-Isopropylidene-protected 23, structurally
flexible peracetylated donor 24, and 4,6-O-benzylidene
protected donor 25 were also prepared for comparison. These
four donors were subjected to the glycosylation with methanol
under the optimal condition (Table 3). Most of donor 24 was
recovered after 24 h probably due to the poor reactivity caused
by the electron-withdrawing effect of 2-O-Ac. On the other
hand, the electron-rich olefins of 23 and 25 may be too sensitive
to electrophilic species and they probably reacted with PIFA
directly, resulting in complex byproducts. Interestingly, only the
reaction using 22 as the donor afforded encouraging result. The
product 26a (Scheme 5) was identified as β-glycoside.24
Although we failed to get 26a crystallized for X-ray crystallo-
To explore the generality of this strategy, various 2,3-O-
carbonate-2-hydroxyglucal donors were subjected to the
phenylselenoglycosylation reaction. Those 2-hydroxyglucals
included 4,6-di-O-acetyl derivative 22, 4,6-di-O-benzoyl de-
rivative 28, 4,6-di-O-benzyl derivative 29, 4-O-acetyl-6-O-(tert-
butyl)diphenylsilyl derivative 30, and 4-O-(p-methoxybenzyl)-
6-O-benzoyl derivative 31. We were pleased to find that all these
donors reacted with the tested acceptors smoothly to afford the
corresponding 2-phenylseleno-2,3-O-carbonate-β-mannosides
in good to excellent yields (81−94%, Scheme 6). No isomeric
1
glucosides were detected with H NMR. In particular, the
glycosylation of donor 31 with sugar-derived secondary alcohol
13a and 13b gave the corresponding β-linked disaccharides 35f
and 35g in 83% and 81% yield, respectively. Interestingly, the
inductive effect of protecting groups at C4 and C6 did not seem
to exert much influence on the reactivity of those donors. For
example, the glycosylation of 26, 28, 29, and 30 with 1,2:3,4-di-
O-isopropylidene-α-galactose 7 produced the corresponding
D
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disaccharide 26g, 32b, 33b, and 34 in 85%, 85%, 86%, and 87%
yield, respectively. A similar phenomenon was observed when
we compared the glycosylation of 26, 28, 29, and 31 with
menthol or the reaction of 26 and 31 with 1-adamantanol. The
lack of reactivity of 2-hydroxyglucal 24 bearing 2,3-di-O-Ac and
the high reactivity of 22 bearing 2,3-O-carbonate clearly
indicated the essential role of 2,3-O-carbonate in the activation
of 2-hydroxy-glucal. Presumably, the ring strain of the bicyclic
structure containing a carbon−carbon double bond at the
bridgehead carbon was the main driving force for this type of
glycosylation. Therefore, it was not surprising that C4 and C6
substituents showed less influence on yields. In addition, the
diastereoselective reduction of disaccharide 35f was conducted
following the same procedure how we got 27 from 26a and
disaccharide 36 was obtained in an overall yield of 83% (Scheme
7). The structure of 36 was confirmed to be β-mannosyl-(1 →
2)-glucoside by comprehensive NMR experiments.27
In conclusion, PhSeSePh in the presence of PIFA promoted
the highly stereoselective phenylselenoglycosylation of glycal
derivatives bearing carbonate for the construction of 2-deoxy-β-
galactosides and β-mannosides. The typical carbohydrate
protecting groups were stable under this condition and the
reaction yields were generally high. Under the optimal
condition, conformationally restricted 3,4-O-carbonate-galactals
were converted into 2-phenylseleno-2-deoxy-galactosides with
excellent β-selectivity. An indirect synthetic strategy for the
stereoselective construction of β-mannosides has been devel-
oped via the phenylselenoglycosylation of 2-hydroxyglucals
bearing 2,3-O-carbonate. 2,3-O-carbonate protecting group was
critical to the reactivity of such 2-hydroxyglucal donors as well as
the stereocontrol of the glycosylation step and the subsequent
removal of C2 phenylseleno group. Further studies on the
application of this method in the synthesis of complex
carbohydrate molecules are now underway.
Pharmaceutical Sciences, Peking University, Beijing 100191, P.R.
China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c00732
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the National Key Technology R&D Program “New
Drug Innovation” of China (No. 2019ZX09301-106) and NSFC
(Nos. 21232002, 21772007, 81930097) and the State Key
Laboratory of Natural and Biomimetic Drugs for financial
support.
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ASSOCIATED CONTENT
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Experimental procedures, characterization data, and H,
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AUTHOR INFORMATION
Corresponding Author
■
Zhongjun Li − State Key Laboratory of Natural and Biomimetic
Drugs, Department of Chemical Biology, School of
Pharmaceutical Sciences, Peking University, Beijing 100191, P.R.
China; orcid.org/0000-0003-1642-7773; Email: zjli@
bjmu.edu.cn
Authors
Shuai Meng − State Key Laboratory of Natural and Biomimetic
Drugs, Department of Chemical Biology, School of
Pharmaceutical Sciences, Peking University, Beijing 100191, P.R.
China; orcid.org/0000-0003-4196-6496
Wenhe Zhong − State Key Laboratory of Natural and Biomimetic
Drugs, Department of Chemical Biology, School of
Pharmaceutical Sciences, Peking University, Beijing 100191, P.R.
China
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