Stereoretentive palladium-catalyzed arylation, alkenylation, and alkynylation of 1-thiosugars and thiols using aminobiphenyl palladacycle precatalyst at room temperature

Article abstract of DOI:10.1002/chem.201501050

A general and efficient protocol for the palladium-catalyzed functionalization of mono- and polyglycosyl thiols by using the palladacycle precatalyst G3-XantPhos was developed. The C-S bond-forming reaction was achieved rapidly at room temperature with various functionalized (hetero)aryl-, alkenyl-, and alkynyl halides. The functional group tolerance on the electrophilic partner is typically high and anomer selectivities of thioglycosides are high in all cases studied. New sulfur nucleophiles such as thiophenols, alkythiols, and thioaminoacids (cysteine) were also successfully coupled to lead to the most general and practical method yet reported for the functionalization of thiols.

Full text of DOI:10.1002/chem.201501050

DOI: 10.1002/chem.201501050
Communication
&
Carbohydrates
Stereoretentive Palladium-Catalyzed Arylation, Alkenylation, and
Alkynylation of 1-Thiosugars and Thiols Using Aminobiphenyl
Palladacycle Precatalyst at Room Temperature
Alexandre Bruneau, Maxime Roche, Abdallah Hamze, Jean-Daniel Brion, Mouad Alami,* and
Samir Messaoudi*[a]
search. Most of them found in nature or used in therapeutics,
exist as glycoconjugates or heterosides in which the sugars are
attached to aglycons through NÀ, SÀ, OÀ, or CÀglycosidic
bonds. When considering the importance of glycosides, partic-
ularly thioglycosides[3] in numerous fields of science, the devel-
opment of new methods to functionalize them efficiently
under simple and ecofriendly conditions is highly desirable. In
this context, we are particularly interested in the direct palladi-
um-catalyzed coupling of unprotected glycosyl thiols under
mild and operationally simple conditions. Catalytic reactions of
this nature would be of great interest for the construction of
molecules that may be sensitive to the harsh conditions that
can often be required for thioglycosidic[4] bond-forming reac-
tions.[5] In 2013, our group reported the coupling of protected
glycosyl thiols with aryl halides in the presence of Pd(OAc)2/
XantPhos as the catalytic system, NEt3 as the base in dioxane
at 1008C (Scheme 1, path a).[6] While this method represents
a notable advance, a relatively high temperature (>758C) is
usually required. To overcome this issue, we reported recently
the first method for the arylation, alkenylation, and alkynyla-
tion of unprotected glycosyl thiols at room temperature under
nickel catalysis (Scheme 1, path b).[7] This reaction was func-
tional-group tolerant and proceeded stereoselectively in good
to excellent yields. Nevertheless, we are mindful that high
nickel loading (30 mol%) and excess of (heteroaryl)halide
(2 equiv) are required for efficient coupling. Moreover, the tox-
icity of nickel salts[8] may be an inherent drawback to their use
in large-scale industrial processes. Recently, Waser et al.[9] dis-
closed an elegant method for the alkynylation of glycosyl
thiols also at room temperature. Although the procedure is ef-
ficient, it is, however, limited only to the alkynylation process
and requires the preparation of ethynyl-1,2-benziodoxol-
3(1H)one (EBX) substrates through multistep reaction sequen-
ces (Scheme 1, path c). Despite all these advances, a general
and simple method for the functionalization of glycosyl thiols
as well as other functionalized thiols at room temperature is
still desired.
Abstract: A general and efficient protocol for the palladi-
um-catalyzed functionalization of mono- and polyglycosyl
thiols by using the palladacycle precatalyst G3-XantPhos
was developed. The CÀS bond-forming reaction was
achieved rapidly at room temperature with various func-
tionalized (hetero)aryl-, alkenyl-, and alkynyl halides. The
functional group tolerance on the electrophilic partner is
typically high and anomer selectivities of thioglycosides
are high in all cases studied. New sulfur nucleophiles such
as thiophenols, alkythiols, and thioaminoacids (cysteine)
were also successfully coupled to lead to the most general
and practical method yet reported for the functionaliza-
tion of thiols.
The palladium-catalyzed Buchwald–Hartwig–Migita cross-cou-
pling reaction has become a valuable tool in industrial and
academic research for the synthesis of natural products and
novel materials including a number of pharmaceuticals cur-
rently on the market.[1] Breakthroughs in this coupling have
typically been driven by the implementation of a new class of
ligands,[2] which are able to promote reactions with a diverse
array of substrates including nitrogen-, sulfur-, and oxygen-
containing nucleophiles. Unfortunately, this process is yet to
approach generality and the goal of being able to couple any
nucleophile with any aryl or heteroaryl halide is far from ac-
complished. One of the most important tasks in this area of or-
ganometallic chemistry is to discover mild and general meth-
ods for easy introduction of unprotected polyfunctionalized
compounds into molecules with high selectivity. Among all
polyfunctional compounds in organic chemistry, saccharides
play diverse pivotal roles in biological systems, which make
them attractive as subjects for chemical and biological re-
[a] A. Bruneau, Dr. M. Roche, Dr. A. Hamze, Dr. J.-D. Brion, Dr. M. Alami,
Dr. S. Messaoudi
In light of the recent success using aminobiphenyl pallada-
cycle precatalysts in CÀN and CÀO bond-forming reactions,[10]
combined with our success using Pd(OAc)2/XantPhos catalytic
system in the coupling of glycosyl thiols with (hetero)aryl hal-
ides at 1008C,[6] we decided to explore the ability of the G3-
XantPhos precatalyst[11] (Scheme 2) to promote the construc-
tion of a CÀS bond under mild conditions. Herein, we report
for the first time, a fast, efficient and stereoretentive coupling
Univ. Paris-Sud, CNRS, BioCIS-UMR 8076
Laboratoire de Chimie Thꢀrapeutique
Equipe Labellisꢀe Ligue Contre le Cancer
LabEx LERMIT Facultꢀ de Pharmacie
5 rue J.-B. Clꢀment, Chꢁtenay-Malabry, 92296 (France)
E-mail: samir.messaoudi@u-psud.fr
mouad.alami@u-psud.fr
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201501050.
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solvents (1,4-dioxane and THF) were found to be the
most effective (entries 2 and 6). The use of other sol-
vents, such as methanol, acetonitrile, or water in-
duced a lowering of the conversion rate (entries 4, 5
and 7). In summary, the best conditions were found
to require 1 mol% of G3-precatalyst, 1 equivalent of
Et3N in dioxane or THF at room temperature for 1 h,
furnishing 3a in a 98% yield (entries 2 and 6). Sur-
prisingly, when the coupling of acetylated b-thioglu-
cose 1b with 2a was performed under our optimized
conditions, the desired product 3b was obtained
quantitatively within only 5 min (entry 8) instead of
1 h required for the coupling of 1a (entry 6). These
results indicated that polyhydroxylated functions in
1a may coordinate to the Pd0 catalyst, thus decreas-
ing its catalytic activity in the coupling of 1a, and
leading to a longer reaction time.
With a viable coupling procedure in hand, atten-
tion was turned to the generality of the process by
studying the coupling of various aglycone halides
with structurally diverse mono-, di-, and tri- glycosyl
thiol derivatives. Remarkably, this glycosidic C–S cou-
pling reaction appeared to be quite general with re-
Scheme 1. Coupling of glycosyl thiols with aryl halides.
Table 1. Optimization of the coupling of 1a,b with 2a.
of various unprotected or protected glycosyl thiols (mono-, di-,
or polythioglycosides) with aglycone halides at room tempera-
ture (Scheme 1, path d). Key to the success was the use of the
Pd G-3 precatalyst at low catalyst loading (1 mol%), which is
able to generate quickly under mild conditions the catalytically
active 12-electron XantPhos-Pd0 species (Scheme 2).
Entry
R
G3-XantPhos (x mol%) Solvent t [min] Conv. [%][b] Yield [%][c]
Our initial experiments focused on identifying optimal condi-
tions for the coupling of unprotected 1-thio-b-d-glucopyranose
1a with 4-iodoanisole 2a at room temperature. Representative
results from this study are summarized in Table 1. It was found
that the reaction of 1a (1 equiv) with 2a (1 equiv) for 15 min
in dioxane at room temperature, in the presence of G3-Xant-
Phos[11] (5 mol%), furnished the expected b-arylthioglycoside
3a in a quantitative yield (Table 1, entry 1). More interestingly,
1 mol% of precatalyst was sufficient to catalyze efficiently the
reaction affording 3a in a 98% yield (entry 2), while, incom-
plete conversion of the substrate was seen when the loading
of precatalyst was decreased to 0.1 mol% (entry 3). A brief
survey of solvents was therefore undertaken in which etheral
1
2
3
4
5
6
7
8
H
H
H
H
H
H
H
Ac
5
1
0.1
1
1
1
1
1
dioxane
dioxane
dioxane
MeOH
CH3CN
THF
15
60
60
60
60
60
60
5
100
100
30
10
20
100
30
100
98
98
–
–
–
98
–
99
H2O
THF
[a] Reaction conditions: NEt3 (1 mmol) was added to
a
mixture of
1 (1 mmol), 2a (1 mmol), and G3-XantPhos (1 mol%) in solvent (0.25m) and
the mixture was stirred at 258C. [b] Conversion was determined by 1H NMR
spectroscopy on the crude reaction mixture and is based on the chemical
shift of protons signals (ppm) at the aromatic moiety. [c] Yield of isolated
products 3.
spect to the different partners
and tolerate various functional
groups (e.g., ÀBr, ÀOTs, ÀOH, À
CN, ÀCO2Me, ÀCONR2, ÀC(Me)=
NNHTs) (Schemes 3 and 4).
As depicted in Scheme 3, 1-
thio-b-d-glucopyranose 1a was
readily coupled with aryl iodides
containing para and meta elec-
Scheme 2. Highly active G3-XantPhos precatalyst and generation of kinetically active 12-electron Pd0 species.
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kenyl- and alkynyl halides as aglycone partners. Delightfully,
when E-b-styryl bromides and a-styryl iodides were employed,
the coupling with 1a,b afforded stereoselectively the desired
alkenylthioglycoside derivatives 3n–q in excellent yields. More-
over, alkynylated thioglycoside product 3r was obtained dia-
stereoselectively in a 79% yield when 4-(bromoethynyl)benzo-
nitrile was used as the aglycone coupling partner.
Application of this procedure to the multigram-scale was
also investigated. In this context, the development of a practi-
cal and scalable method in organic synthesis is essential for
plant-scale manufacturing. Here we showed that our proce-
dure can be achieved safely by coupling 1b with 4-iodoto-
luene in a multigram-scale reactor (50 mmol) by using 1 mol%
of the precatalyst at room temperature within 10 min. Com-
pound 3e[12] was isolated in a nearly quantitative yield as
a pure product after only filtration through Celite without any
1
additional purification (see TLC in Figure 1and crude H NMR
spectra in the Supporting Information). This result clearly dem-
onstrates that this procedure can be used in a scale-up indus-
trial process.
Next, we turned our attention to the generality of the
method with respect to mono-, di-, and triglycosyl thiols. As
depicted in Scheme 4, coupling reactions proceeded cleanly in
high yields without any side reaction, such as anomerization of
the resulting arylthioglycosides. The reaction is general with re-
spect to the sugar configuration as N-acetyl-1-thio-b-d-amino-
glucopyranose, 1-thio-b-d-galactopyranose, and 1-thio-b-d-
mannopyranose give the corresponding products 4a–g in
good to excellent yields. Of note is that there were little differ-
ences in reactivity between a- and b-anomers as a 94% yield
of 3 f was obtained from the coupling of 4-iodotoluene with 1-
thio-b-d-glucopyranose compared to 74% yield of 4i obtained
from the coupling of 1-thio-a-d-glucopyranose. Additionally,
the coupling procedure is not only limited to unfunctionalized
glycosyl thiols but also works successfully with challenging 6-
bromo-1-thio-b-d-galactopyranose,[13] furnishing 4h in a good
57% yield. Compound 4h in which the C(sp3)ÀBr bond sur-
vives, is an ideal entry for post-functionalization through azida-
tion[14] and CuAAC bioconjugation[15] reactions. Finally, the effi-
ciency of this CÀS bond forming reaction was well-demonstrat-
ed by coupling more complex unprotected di- and trisaccha-
ride derivatives. Thus, 1-thio-b-d-cellobiose as well as 1-thio-b-
Scheme 3. G3-Xantphos precatalyst-catalyzed coupling of 1-thio-b-d-gluco-
pyranose with aglycone halides. Reaction conditions: Et3N (1 equiv) was
added to a solution of 1 (1 mmol), 2 (1 mmol), and G3-XantPhos (1 mol%) in
THF (0.25m) and the mixture was stirred at RT.
substituents to give thioglycosylated products 3a, 3c, and
3g–l in good to excellent yields with complete b-stereoreten-
tive selectivity. Of note, the sterically demanding ortho substi-
tution pattern influences the outcome of the coupling reaction
of 1a, furnishing the expected coupling product 3d but with
a modest 38% yield. Importantly, there is no significant impact
of protecting groups on the reactivity of the thiosugar deriva-
tives since acetate or benzoyl-protected carbohydrate 1b and
1c reacts similarly than unpro-
tected derivative 1a, furnishing
the coupling product 3b, 3e,
and 3 f in 99, 99, and 75%
yields, respectively. Of note that
compounds 3h,i revealed an ex-
cellent chemical selectivity of
the CÀI bond over the CÀBr
bond which could enjoy further
metal-catalyzed functionalization
processes. In hope of further
pushing the limit of this Pd-cata-
lyzed S-arylation reaction, we ex-
amined the coupling of 1-thio-b-
d-glucopyranose 1a,b with al- Figure 1. Multigram-scale coupling of 1-thio-b-d-glucopyranose 1b with 4-iodotoluene 2b at RT in a reactor.
Chem. Eur. J. 2015, 21, 1 – 6 www.chemeurj.org ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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CÀS bond-forming reaction could be extended to
other aryl and alkylthiol derivatives. In fact, the cou-
pling proceeds well with p-thiocresol within 5 min at
room temperature, giving the coupled product 5a in
a 99% yield (Scheme 5). We were also pleased to find
that nonaromatic thiols, in which the reductive elimi-
nation step have been shown to be significantly
slower than thiophenols,[16] are good partners for this
coupling procedure. Thus, 2-(trimethylsilyl)ethane-1-
thiol could be coupled efficiently to produce 5b in
an excellent 99% yield. Encouraged by these results,
we set out to examine the CÀS bond-forming reac-
tion using cysteine as a coupling partner. To our
knowledge, this amino acid has never been used as
a coupling partner in Buchwald-Hartwig S-arylation
reaction. Thus, reacting N-acetyl cysteine with 4-iodo-
toluene under our optimized protocol furnished the
desired coupling product 5c in a 98% yield.
In conclusion, we have demonstrated that the pal-
ladacycle precatalyst G3-XantPhos displays a high
catalytic activity for the coupling of an array of glyco-
syl thiols as well as aryl and alkyl thiol derivatives in-
cluding cysteine. The room temperature at which this
coupling is conducted provides access to a range of
glycoconjugates that are otherwise not easily accessi-
ble. The reaction is highly diastereoselective, func-
tional-group tolerant, step-economical, and proceeds
stereoselectively in good to excellent yields. The
value of this transformation has been highlighted by
the synthesis of p-tolyl 1-thio-b-d-glucopyranoside
acetate 3d in a multigram scale. We expect this
simple and general protocol to be of broad utility for
the synthesis and development of new medicinal
agents.
Scheme 4. G3-Xantphos precatalyst-catalyzed coupling of mono-, di-, and polythiosac-
charides with aglycone halides. Reaction conditions: Et3N (1 equiv) was added to a solu-
tion of thiosaccharides (1 mmol), 2 (1 mmol), and G3-XantPhos (1 mol%) in THF (0.25m)
and the mixture was stirred at RT.
Acknowledgements
The authors thank the Centre National de la Recher-
che Scientifique (CNRS) for support of this research
and MRES for a doctoral fellowships to A.B. and M.R.
The authors also thank la Ligue Contre le Cancerfor
their financial support of this research (Equipe labelli-
sꢁe). Our laboratory BioCIS-UMR 8076 is a member of
the Laboratory of Excellence LERMIT supported by
a grant from the Agence Nationale de la Recher-
che(ANR-10-LABX-33).
Keywords: arylthioglycosides
·
bond-forming
Scheme 5. Scope of the fast coupling of other aryl/alkylthiols with iodoarenes at RT.
reactions
· thiols · palladacycles · unprotected
thiosugars
d-maltotriose were readily arylated at room temperature to
give the corresponding glycoconjugates 4j–l in good yields
(51–80%). Of note is that the stereochemistry of the 1-4’O-gly-
cosidic bond in the b-diholoside 4j or in b-triholosides 4k,l re-
mained intact.
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Published online on && &&, 0000
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COMMUNICATION
Sweet and efficient: A general and effi-
cient protocol for the palladium-cata-
lyzed functionalization of mono- and
polyglycosyl thiols by using the pallada-
cycle precatalyst G3-XantPhos was de-
veloped. The CÀS bond-forming reac-
tion was achieved rapidly at room tem-
perature with various functionalized
(hetero)aryl-, alkenyl-, and alkynyl hal-
ides (see scheme).
&
Carbohydrates
A. Bruneau, M. Roche, A. Hamze,
J.-D. Brion, M. Alami,* S. Messaoudi*
&& – &&
Stereoretentive Palladium-Catalyzed
Arylation, Alkenylation, and
Alkynylation of 1-Thiosugars and
Thiols Using Aminobiphenyl
Palladacycle Precatalyst at Room
Temperature
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