Electrochemical nickel-catalyzed Migita cross-coupling of 1-thiosugars with aryl, alkenyl and alkynyl bromides

Article abstract of DOI:10.1039/d0cc01126f

Here we report a simple route towards the synthesis of thioglycosides, in which electrochemical cross-coupling is used to form a S-C glycosidic bond from protected and unprotected thiosugars with functionalized aryl bromides under base free conditions. The reaction manifold that we report here demonstrates the power of electrochemistry to access highly complex glycosides under mild conditions.

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Electrochemical nickel-catalyzed Migita cross-coupling of 1-thiosugars
with aryl, alkenyl and alkynyl bromides
Mingxiang Zhu,a Mouad Alamia and Samir Messaoudia*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
Here we report a simple route towards the synthesis of
thioglycosides, in which electrochemical cross-coupling is
used to form the S–C glycosidic bond from protected and
unprotected thiosugars with functionalized aryl bromides
10 under base free conditions. The reaction manifold that we
report here demonstrates the power of electrochemistry to
access highly complex glycosides under mild conditions.
1-Thioglycosides have emerged as
a privileged class of
glycosides with a diverse range of potential applications.1 These
15 glycomimetics are known to be more robust towards enzymatic
cleavage under biological conditions.2 Representative active
glycosides with a thioether linkage are discolosed in Figure 1,
including hSGLT1 inhibitor, ligand of lectine A, cytotoxic Hsp90
inhibitor, antimicrobial agent as well as galactin-3-inhibitors.
20 Moreover, thioglycosides are well known to be useful and
versatile reactive intermediates in organic synthesis.3
At present, for the functionalization of glycosyl thiols, various
catalytic systems based on palladium,4 nickel5 and copper6 have
been reported (Figure 1,a-b).7 Despite their high interest, these
25 methods require the use of basic conditions with high catalyst
loadings (30 mol% in the case of Ni-catalysis) or precious metals
such as Pd-catalyst with specially designed ligands.8 In addition,
an elevated reaction temperature (up to 120 °C cases of Pd- or
Cu-catalysis), and long reaction times often limit the
30 practicability or the scope of substrates. Moreover, in all these
cases the coupling is effective with only aryl iodides, however the
cross-coupling with aryl bromides is rather unexplored. To
address these issues, we have reported recently a Ni/Ru dual
photocatalyzed arylation of thiosugars with aryl iodides under
35 base-free conditions (Figure 1,c).9 However, the more available
and less expensive aryl bromides are still unreactive under these
photoredox conditions. Only few examples were reported with
yield never exceeded 43% yield. Moreover, this method was
limited to only protected thiosugars. This set of limitations clearly
40 indicates that glycosyl thiols often behave as a rather special and
challenging class of thiol nucleophiles for transition-metal-
catalyzed thio-functionalization.
a
BioCIS, Univ. Paris-Sud, CNRS, University Paris-Saclay, Châtenay-Malabry,
France Tel: + (33) 0146835887; E-mail: samir.messaoudi@u-psud.fr
45 † Electronic Supplementary Information (ESI) available: General, experimental
procedures for starting materials and 1H and 13C spectra for all new compounds.
See DOI: 10.1039/b000000x/
50 Figure 1. Examples of natural products, bioactive thioglycosides, and
catalytic strategies to access to thioglycosides 3.
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Table 1. Optimization of the coupling reaction of 1a[a]
Because of the high importance of thioglycosides, the
development of a general method for the coupling of both aryl
bromides and iodides to protected and unprotected thiosugars
under room temperature and without an external base remains a
challenging task.
5
In recent years, electrosynthesis10 has emerged as a remarkably
efficient tool for organic cross-coupling reactions through the use
of less precious catalysts, waste-free and inexpensive electric
current, thereby avoiding stoichiometric amounts of toxic and
Entry
Deviation from the standard conditions
Yield (%)b
1
none
74
54
73
71
74
0
trace
0
28
80
47
10 costly chemical reagents limiting our impact on the environment.
Usually, this method was used successfully in C−H activation
process fort the formation of C–C and C–heteroatom bonds
(C−O, C−P, and C−N) through the directing group strategy.11
However, electrochemical C–heteroatom bond formation via
15 cross coupling of nucleophiles with aryl (pseudo)halides was less
explored.12 In particular, methods which use electrosynthesis to
form C−S bonds are rare. To the best of our knowledges, only
one study from Mei et al. reported the cross-coupling reaction of
thiophenols with aryl halides.13 The authors showed elegantly
20 that this approach allows thiolation of aryl halides. However, this
method exhibited several limitations with regards to potential
applications: i) the use of a large excess of the thiophenol partner
(3 equiv) which can be prohibitive for larger scale reactions; ii)
the scope with respect to the thiols was limited to
25 unfunctionalized thiophenols, thus precluding many synthetic
applications. Moreover, the S-arylation of functionalized and
complex alkyl thiols bearing free hydroxyl or amino groups such
as thiosugars under electrochemistry has never been studied,
probably because of the polyhydroxylated complexity of
30 carbohydrates. Herein, we became interested in whether the S-
(hetero)arylation of 1-thiosugars could be performed by the
electrochemical process. The present study is presented (Figure
1).
2
3
4
5
6
7
8
9
0.3 mmol of 1a and 0.9 mmol of 2a
0.6 mmol of 1a and 0.3 mmol of 2a
2 mA, 12 h
8 mA, 3 h
No LiBr
No catalyst
No electric current
Zn instead of Mg
20 mol% Ni.cat and 20 mol% Dttbpy
DMA instead of DMF
10
11
a
Reactions conditions: Mg anode, Ni foam cathode, 1a (0.3 mmol), 2
60 (0.3 mmol), NiBr2.diglyme (10 mol%), di-tBubpy (10 mol%), LiBr (1.2
mmol), DMF (0.3 M), undivided cell, constant current = 4 mA, (Ar) room
temperature, 6 h. bIsolated yield.
With these encouraging results, we investigated next, the scope
and limitations for this electrochemical process by systematically
65 varying the nature of the bromide electrophile 2. As showed in
Table 2, all the S-arylations of tetra-O-acetylated 1-thio-β-D-
glucopyranose 1a proceeded cleanly and selectively in good
yields. Cross-coupling of 1a with aryl bromides bearing various
functions (–CN, –Cl, –F, –CF3, –CHO and –OMe) have been
70 successfully achieved under room temperature to afford the
corresponding thioglycosides (3a-m) in yields up to 87%. In
addition, the presence of an ortho substitution at the aromatic ring
of the coupling partner do not affect the coupling process as
compounds 3h and 3k were obtained in 80% and 77% yields,
To initiate this study, we conducted this electrochemical
35 thioglycosylation by coupling of tetra-O-acetylated 1-thio-β-D-
glucopyranose 1a with 4-bromobenzotrifluoride 2a as a model 75 respectively. It is noteworthy that a selectivity was observed
study under various reaction conditions. Representative results
from this study are summarized in Table 1. The reaction of 1a (1
equiv) with 2a (3 equiv) was first investigated by using constant-
40 current electrolysis at 4.0 mA in the presence of NiBr2.diglyme
when a tribromobenzene was used, and only a di-glycosylated
product 3m was obtained in 70% yield even after running the
coupling with longer reaction time (6h) and using 6 equiv of 1a.
One can be noted that, 3-bromonaphtalene is less reactive at
(10 mol%), 4,4'-di-tert-butyl-2,2'-bipyridine (di-tBubpy) (10 80 current conditions than 2-bromonaphatelene giving the desired S-
mol%), LiBr (4 equiv) in DMF at room temperature for 6 h
within an undivided cell (Table 1, entry 2). Pleasingly, these
conditions afforded the 3a in a moderate 54% yield as a single β-
naphtylglycoside 3j in only 22% yield (vs 77% with 2-
bromonaphatelene). However this yield could be increased
significantly (73% yield) when 3-iodonaphtalene. The same low
reactivity was observed with p-bromoanisole vs p-iodoanisole
45 anomer (J1, = 9 Hz) (See ESI). Interestingly, decreasing the
2
amount of the bromide partner 2a from 3 equiv to 1 equiv 85 (compound 3l, 15% vs 83%). Interestingly, couplings with
furnished the thioglucoside 3a in a good 74% yield (entry 1).
Using other anodes such as Zn was not effective (entry 9). In
addition, reaction with DMA instead DMF was less efficient and
50 gave product 3a in only 47% yield (entry 11). Interestingly, when
heteroaryl bromides derived from quinoline and pyridine have
also been successful, furnishing 3n,o in 46% and 86% yields,
respectively. Next, we moved on to investigate the reactivity of a
series of alkene and alkyne bromides. Pleasantly, both aryl- and
the current was increased up to 8mA, the reaction time was 90 alkyl- substituted alkene bromides ((E)-1-(2-bromovinyl)-4-
shortened to 3h and 3a was isolated in 74% yield (entry 5).
Finally, performing the coupling reaction with 20 mol% of
NiBr2.diglyme and 20 mol% of di-tBubpy furnished 3a in 80%
55 yield (entry 10). Negative controlling experiments demonstrated
the catalyst, the LiBr and the current are necessary (entries 6−8).
methoxybenzene, E-β-styryliodide, (E)-1-bromooct-1-ene)) and
2-bromo-1H-indene were transformed efficiently into alkenyl
thioglycosides 3p-s in excellent yields. Finally, alkynyl-
thioglycosides 3t−u were also easily prepared in good yields
95 from corresponding 1-(bromoethynyl)-4-methoxybenzene and 3-
2
|
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Table 3. Scope of 1 thio-β-glycosyls 1b-g a
Table 2 Scope of Coupling of Thioglucose 1a with Halo(hetero)arenes,
Alkenyl Halides and Alkynyl Bromides 2
a
25 Reactions conditions: Mg anode, Ni foam cathode, 1b-f (0.3 mmol), 2
(0.3 mmol), NiBr2.diglyme (10 mol%), di-tBubpy (10 mol%), LiBr (1.2
mmol), DMF (0.3 M), undivided cell, constant current = 8 mA, N2
protection, room temperature, 3 h. bIsolated yield.
One of the most important task in this area of organometallic
30 chemistry is to discover mild and general methods for easy
functionalization of polyhydroxylated compounds with high
selectivity without using any protection/deprotection sequence.
To further show the synthetic use of our protocol, we evaluated
whether the S-arylation of unprotected thiosugars could be
35 realized by this electrochemical method. To our delight, the
reaction of unprotected thio-β-D-glucose and thio-β-D-cellobiose
yielded the respective products 5a and 5b in good yields, and no
side products arising from the O-arylation were observed
(Scheme 1).
40 Scheme 1. Unprotected thiosugars and cysteine-aminoacid as thiols
a
Reactions conditions: Mg anode, Ni foam cathode, 1a (0.3 mmol), 2
5 (0.3 mmol), NiBr2.diglyme (10 mol%), di-tBubpy (10 mol%), LiBr (1.2
mmol), DMF (0.3 M), undivided cell, constant current = 8 mA, N2
protection, room temperature, 3 h. bIsolated yield.
(bromoethynyl)thiophene by this electrochemical method. One
can be noted that benzyl- or PMB- protecting groups on the
10 thiosugar are not tolerated (see SI, Figure S7).
The successful synthesis of thioglucosides 3a-u from tetra-O-
acetylated 1-thio-β-D-glucopyranose 1a and various aryl
bromides under our optimized electrochemical conditions
encouraged us to investigate other glycosyl thiols. As depicted in
15 Table 3, this coupling reaction tolerates different sugars such as
a
Reactions conditions: Mg anode, Ni foam cathode, 1g-i (0.3 mmol), 2a
(0.3 mmol), NiBr2.diglyme (10 mol%), di-tBubpy (10 mol%), LiBr (1.2
mmol), DMF (0.3 M), undivided cell, constant current = 8 mA, N2
45 protection, room temperature, 3 h. bIsolated yield
O-
benzoylated
1-thio-β-D-glucopyranose,
thio-β-D-
Finally, as part of our interest in developing new methods to
peptide and protein bioconjugation, we considered it worthwhile
to investigate the reaction of cysteine aminoacid with aryl
bromides (Scheme 1). Direct arylation of cysteine-containing
50 peptides has only been reported using the precious Pd-catalysis.14
To this end, we tested the reaction of L-cysteine with p-
galactopyranose and 1-thio-β-D-fucopyranose, which furnished
the thioglycosides 4a-c in yields up to 95%. In addition, this
coupling could be applied successfully to the more complex and
20 biologically relevant saccharide derivatives thio-β-D-cellobiose
and thio-β-D- maltotriose delivering 4d and 4e in 90% and 88%
yields, respectively.
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Authors acknowledge support of this project by CNRS,
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