Carbon nanotube-ruthenium hybrid towards mild oxidation of sulfides to sulfones: Efficient synthesis of diverse sulfonyl compounds

Article abstract of DOI:10.1039/c9cy00384c

A heterogeneous catalyst was assembled with ruthenium nanoparticles on carbon nanotubes and used in a mild oxidation method to prepare sulfones from sulfides. The system proved very efficient on the investigated substrates and the products were obtained in high yields.

Full text of DOI:10.1039/c9cy00384c

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E. N. da Silva Júnior, Catal. Sci. Technol., 2019, DOI: 10.1039/C9CY00384C.
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PAPER
Carbon nanotube-ruthenium hybrid towards mild oxidation of
sulfides to sulfones: Efficient synthesis of diverse sulfonyl
compounds
Renata G. Almeida,a Renato L. de Carvalho,a Mateus P. Nunes,a Roberto S. Gomes,b Leandro F.
Pedrosa,c Carlos A. de Simone,d Elumalai Gopi,e Valérie Geertsen,f Edmond Gravel,e Eric Dorise*
and Eufrânio N. da Silva Júniora*
AReceived 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A heterogeneous catalyst was assembled with ruthenium nanoparticles on carbon nanotubes and used in a mild oxidation
method to prepare sulfones from sulfides. The system proved very efficient on the investigated substrates and the
products were obtained in high yields.
Carbon nanotubes (CNTs) are graphene-based architectures with a
Organosulfur compounds exhibit several biological activities.12
cylindrical shape.1,2 These peculiar structures have proven useful for Aware of the biological importance of sulfur derivatives, Ferreira
several applications, as for instance, water treatment,3 nanowires4 and Cavaleiro,13 Choi and Song14 and da Silva Júnior15 groups have
and sensors.5 The use of CNTs as catalyst support is another developed the synthesis of sulfur-containing quinones of biological
important application for these nanomaterials with unique relevance. Compounds with antitumor16 and trypanocidal
advantages such as chemical, thermal, and mechanical stability in activities,15 lapachones sulfone-substituted with antibacterial
liquid media, inertness, high specific surface area, and chemically activities13 and 2-alkylthio substituted naphthoquinones14 as potent
tunable topography.6 Recently, Doris and Namboothiri groups have cholesterol acyltransferase inhibitors were described (Scheme 1B).
explored supramolecular assemblies of transition-metal
Our research group has been involved in a drug discovery
nanoparticles (e.g. Au, Pd and Rh) for performing organic program to find molecules to be used as prototypes in cancer17 and
transformations by using metal-coated CNTs as heterogeneous parasite18 treatment. Aiming at the preparation of new
catalysts under mild and efficient conditions.7 Recently, a carbon anthraquinones containing the sulfone group with potential
nanotube-copper ferrite hybrid was also described to catalyze the biological applications, we observed the lack of versatile methods
Huisgen 1,3-dipolar cycloadditions (“click” reaction).8
for the synthesis of this class of compounds. Panico in 1959 and
In this context, the mild and selective catalytic oxidation of Gattermann in 1912 described methods for the oxidation of sulfide
naphtho- and benzohydroquinones to the respective naphtho- and anthraquinones.19,20 In the latter cases, higly toxic chromium-based
benzoquinones was also performed in the presence of catalytic reagents were used, evidencing the need to search for modern and
amounts of gold or rhodium nanohybrids, providing the quinoidal efficient methodologies (Scheme 1C).
system in high yields with low catalyst loading (Scheme 1A).9,10
These reactions proved to be extremely versatile for the synthesis reactions,7 herein, we describe an efficient process for the mild
of quinonoid compounds with potential bioactivity. These results oxidation of sulfides to sulfones in broad range of
Given our recent success in terms of metal-CNT-catalyzed
a
led us to develop a new methodology for the oxidation of naphthols anthraquinones, sulfur compounds and also BODIPY derivatives. For
aiming at the formation of naphthoquinones with trypanocidal the first time, RuCNT was employed in an oxidation strategy
activity, as recently reported by us (Scheme 1A).11
involving this important chalcogen (Scheme 1D).
The RuCNT catalyst was assembled using a layer-by-layer
approach according to a previously described procedure.21 First,
multi-walled carbon nanotubes were sonicated in the presence of
amphiphilic nitrilotriacetic-diyne (DANTA) surfactants in water. This
process is a fast and effective manner to achieve supramolecular
structures with a nanoring shape at the surface of the CNTs. DANTA
is readily prepared from the commercially available pentacosa-
10,12-diynoic acid. In water, the lipophilic portion of DANTA is
adsorbed on the surface of the CNTs by simple hydrophobic
interactions. On the other hand, its hydrophilic head is oriented
outwards, at the interface with the aqueous medium. Upon UV
irradiation, the rings were subsequently polymerized, in order to
a. Institute of Exact Sciences, Department of Chemistry, Federal University of Minas
Gerais, Belo Horizonte, MG, 31270-901, Brazil. E-mail: eufranio@ufmg.br
b. Department of Chemistry and Chemical Biology, Harvard University, USA.
c. Fluminense Federal University, Volta Redonda, RJ, 27213-145, Brazil.
d. Institute of Physics, University of São Paulo, São Carlos, SP, 13560-160, Brazil.
e. Service de Chimie Bioorganique et de Marquage (SCBM) CEA, Université Paris-
Saclay 91191 Gif-sur-Yvette, France. E-mail: eric.doris@cea.fr
f. NIMBE, CEA, CNRS, Université Paris-Saclay, 91191, Gif-sur-Yvette, France
† Electronic supplementary information (ESI) available: Experimental procedures
and characterisation data for all compounds. CCDC 1898341 (1c) 1896798 (2c) and
1896800 (5). For ESI and crystallographic data in CIF or other electronic format see
DOI:
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improve the cohesion of the assembly around the nanomaterial. In RuCNT suspension was determined by inductively coupled plasma
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a second step, a polycationic polymer (PDADMAC) layer was mass spectrometry (ICP-MS). RuCNT sampDleOsI:w10e.r1e03m9/iCn9eCraYl0iz0e3d84aCt
deposited. This polymer allows better adsorption of the room temperature for 16 h using aqua regia before being analyzed
nanoparticulate transition metal deposited in a final step to afford by ICP-MS. Quantification of ruthenium was performed using
the nanohybrid (RuCNT) (Fig. 1). The characterization of the catalyst external standards. Analysis of the RuCNT nanohybrid suspension
was accomplished by Transmission Electron Microscopy (TEM) (See gave a ruthenium concentration of 0.3 mM.
Figure S1, SI) and the transition metal concentration of the aqueous
(A) Examples of nano-catalysed reactions reported by our groups (Refs 9-11):
Namboothiri and Doris
O
OH
OH
O
RhCNT
AuCNT (0.13 mol%)
(0.25 mol%)
K2CO3, CHCl3/H2O
r.t., air
CHCl3/H2O
r.t., air
O
OH
OH
O
O
(PhSe)2
RhCNT (0.25 mol%)
R1
R1
H2O2 (35% v/v)
O2 (1 atm)
i-PrOH/Hexane, r.t.
Doris and
da Silva Júnior
OH
O
(B) Biologically significant sulfone quinoidal derivatives (Refs 13-16):
O
R1
OMe O
O
N S
O
O
N
N
O
O
Me
O
N
Ph
O
S
S
O
O
R
O
OMe O
(C) Oxidations described by Panico and Gattermann (Refs 19-20):
R
Oxidations based on:
R
S
O
O S O O
H2O2 or Chromium(VI) oxide
- Cr-based oxidants are
highly toxic, corrosive, and
carcinogenic
[O]
- Limited Scope
O
O
(D) This work: RuCNT-catalyzed mild oxidation of sulfides to sulfones
- Efficient catalysis with Ru-based nanohybrids
- Wide scope - Mild conditions
R
- 8 examples
- Aryl and alkyl groups
- BODIPY derivatives
R
S
O
O
O S O O
[O]
O
CH3
[O]
S
RuCNT
S
R1
CH3
R1
O
RuCNT
- 12 examples
O
Scheme 1 Overview.
2 | Catal. Sci. Technol., 2019, 00, 1-3
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DOI: 10.1039/C9CY00384C
anthraquinones, BODIPYs and sulfur compounds.16-18,29 In this
sense, herein we have also tested H2O, ACN:H2O (1:1) and DCM:H2O
(1:1) as solvents for oxidation reactions (See Table S1). The oxidized
product 2a was not obtained when H2O or ACN:H2O (1:1) were used
as solvent, and with DCM:H2O (1:1), 2a was isolated in only 9%
yield.
The scope of this new oxidation methodology is outlined in
Scheme 2. Anthraquinones (1a-l) were prepared following the
procedure recently published by our group.14 Sulfur-containing
anthraquinones possessing different patterns of substitution
underwent oxidation to furnish sulfone derivatives 2a-2l in
excellent yields, with the exception of three compounds, i.e. 2g, 2i
and 2k, that were prepared in more moderate 60, 56, and 60 yields,
respectively. This new method proceeds with low amounts of
RuCNT (0.1 mol %) at moderate temperature and does not require
any special conditions. The reactions were performed without inert
atmosphere. The work-up is quite simple, with several of the
prepared substances 2 being purified by silica gel chromatography.
Structural assignments were based on detailed NMR analysis and
the data already reported in the literature.14,24
The superior oxidizing ability of the RuCNT/NaIO4 combination
likely originated from in situ formation of higher oxidation states of
the metal, as previously demonstrated for RuCl3 and other
transition metals.26 This ruthenium species exhibit a better oxidizing
power compared to NaIO4 taken alone,27 and can directly oxidize
sulfides to sulfones. It is to be noted that no sulfoxide was detected
in the course of our experiments. In addition, as CNT are
electronically active,28 they could actively contribute to the catalytic
performances of the nanohybrid system by stabilizing the transitory
high oxidation states of ruthenium.
Fig. 1 a) Structure of DANTA; b) Structure of PDADMAC; c) Overview of the catalytic
hybrid and RuCNT-catalyzed oxidation of sulfides to sulfones in the presence of NaIO4.
RuCNT composed of multiwalled carbon nanotube (MWCNT), DANTA, PDADMAC and
ruthenium nanoparticles. DANTA = diacetylene nitrilotriacetate amphiphile. PDADMAC
= Poly(diallyldimethylammonium chloride).
25
Among the broad list of oxidizing sources, we chose NaIO4. In
fact, NaIO4 is relatively cheap and exhibit low toxicity compared to
chromium-based chemicals or other agressive oxidants It can also
be employed in water or aqueous solvents.22 Moreover, this
periodate compound is compatible with a wide range of organic
functionalities under mild conditions.23 With the ruthenium-based
nanohybrid catalyst in hands, we performed preliminary studies
involving the reaction of 1-((trifluoromethyl)thio)anthracene-9,10-
dione 1a with NaIO4 at room temperature, 0.05 mol% of RuCNT, 1 h
of reaction but the product 2a was obtained in only 18% yield
(Table 1, entry 1). Following our strategy, we decided to investigate
the effectiveness of increasing the amount of RuCNT in the reaction
system. Pleasingly, the experiments with 0.1, 0.2 and 0.3 mol% of
RuCNT revealed impressive results (entries 2-4). In these cases, the
formation of 2a was improved as sulfone 2a was obtained in 87%
yield when 0.3 mol% of RuCNT was used (entry 4). Looking for a
further refinement aiming at minimizing the amount of the catalyst,
we decided to use 0.1 mol% of RuCNT and keep the reaction under
stirring during 24 h, but 2a was obtained in only 48% yield (entry 5).
Despite the efficiency of the catalyst at room temperature (entry 4)
we continued our efforts towards the improvement of the reaction
condition. Pleasantly, with the use of 0.1 mol% of RuCNT and by
heating reaction media at 50 °C, 84% yield of 2a was obtained after
just 1 h (entry 6). Subsequently, by using the same conditions but
75 °C, product 2a was prepared in 97% yield (entry 7). We also
performed control experiments without RuCNT and/or NaIO4
(entries 10-15) but the formation of 2a was inhibited.
Table 1 Selected optimization results.a
CF3
F3C
S
O
O
S
O O
RuCNT (X
mol%)
NaIO4 (3.0 equiv)
H2O:ACN:DCM (2:1:1)
Y
Z
h
Temp ( °C),
O
O
1a
2a
Entry
RuCNT (mol%) Temp/oC
Time/h
Yield (%)b
r.t.
r.t.
1
1
1
1
24
1
1
1
1
1
1
1
1
1
1
18
44
1
0.05
0.1
2
r.t.
48
3
0.2
r.t.
87
4
0.3
r.t.
48
5
0.1
50
84
6
0.1
75
97
7
0.1
100
100
r.t.
94
8
0.1
84
9
0.3
NR
NR
NR
NR
NR
NR
10
11c
12c
13c
14c
15
none
none
0.1
r.t.
r.t.
100
100
100
0.1
none
none
a
1a
General reaction conditions:
(0.2 mmol), RuCNT (0.1 mol%,
H O:ACN:DCM (2:1:1, 4
333 µL of 0.3 mM aqueous suspension),
mL), room temp., sealed flask, 1 h. bIsolated yields. NR = for all
2
In general, dichloromethane (DCM) and acetonitrile (ACN) are
solvents preferably used in various organic reactions involving
1a
cases starting material
was recovered. cabsence of NaIO4.
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DOI: 10.1039/C9CY00384C
R
S
R
S
O
O
R1
O O
R1
RuCNT (0.1 mol%)
NaIO4 (3.0 equiv)
H2O:ACN:DCM (2:1:1)
75 °C, 1 h
O
1
R1 = H or I
R1 = H or I
OCH3
O
2
Br
S
CH3
CF3
O O
O
O O
O
O
S
O O
O
S
O O
O
O
S
O O
O
O
S
O O
O
O
S
O
O
2a:
2b:
2c:
2d:
2e:
2f:
67%
97%
>99%
78%
88%
91%
CH3
Cl
OCH3
CH3
O
S O O
O
S
O O
O
S
O O
O S O O
O
S
O O
O
S
O O
O
I
I
O
O
O
O
O
2l:
84%
2g:
2j:
70%
60%
2h:
2i:
2k:
60%
84%
56%
Scheme 2 Synthesis of anthraquinone-based sulfone derivatives 2.
In order to further confirm that the oxidized product was
To confirm the efficiency of our method, we also selected
formed, suitable crystals of compounds 1c and 2c were obtained by simple sulfides 3 to perform the oxidation into sulfones 4. Aromatic
slow evaporation method and submitted to X-ray crystallography compounds 4a-4d were obtained in excellent 91-99% yields. Benzyl
studies. Fig. 2 shows an Ortep-3 diagram of 2c and the solved sulfide derivative 4e was also successful prepared. Only compound
structure of compound 1c was inserted in the SI.
4f was prepared in moderate yield. In general, results were
satisfactory and the products were obtained in excellent yields
(Scheme 3).
RuCNT (0.1 mol%)
NaIO4 (3.0 equiv)
O
CH3
S
3
S
R
CH3
R
O
H2O:ACN:DCM (2:1:1)
75 °C, 1 h
4
O
S
O
S
O
S
CH3
CH3
CH3
O
O
O
H3C
Br
4c:
O
>99%
4b:
4e:
91%
4a:
>99%
O
S
CH3
O
CH3
S
O
S
CH3
O
O
H3CO
Cl
4f:
67%
87%
4d:
99%
Scheme 3 Synthesis of sulfone derivatives 4.
Fig 2 ORTEP-3 projection of 2c, showing the atom numbering and displacement
ellipsoids at the 50 % probability level.
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Finally, following our strategy of developing an efficient sulfones of fluorescent compounds represents an important use of
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methodology for the oxidation of sulfides to sulfones and these probes in molecular biology,30 we submitted the respective
simultaneously the preparation of structures with potential BODIPY derivatives 5 and 7 to the preparation of their oxidized
biological applications, we have selected BODIPY derivatives 5 and 7 counterparts 6 and 8. To our delight, the RuCNT oxidation method
to evaluate the method described herein (Scheme 4). Our research was also efficient for these oxidations and the products were
group has experience in the synthesis of probes with relevance in obtained in 67 and 64% yield.
DOI: 10.1039/C9CY00384C
bioimaging studies.29 Aware that the oxidation of sulfides to
OCH3
OCH3
RuCNT (0.2 mol%)
NaIO4 (6.0 equiv)
O
S
O
S
S
S
Ph
Ph
N
N
B
N
N
B
H2O:ACN:DCM (2:1:1)
75 °C, 1 h
Ph
Ph
O
O
F
F
5
F
6:
F
67%
CH3
CH3
S
O
S
O
RuCNT (0.1 mol%)
NaIO4 (3.0 equiv)
N
N
N
N
H2O:ACN:DCM (2:1:1)
75 °C, 1 h
B
7
B
F
F
F F
8:
64%
Scheme 4 Synthesis of BODIPY derivatives 6 and 8 with potential application as fluorescent probes. ORTEP-3 projection of 5, showing the atom numbering and displacement
ellipsoids at the 50 % probability level.
Besides all the aspects discussed above and the very low
In conclusion, we have reported an efficient and reliable
catalyst loading (only 0.1 mol% of the catalyst is necessary for sulfur method for preparing sulfonyl derivatives from the oxidation of
derivatives oxidation), recyclability of RuCNT was also shown to be sulfides. The system is efficient for the oxidation of several
very efficient (Table 2). After the reaction was completed, the substrates and allowed the preparation of compounds with
catalyst was easily recovered by simple centrifugation and reused in potential biological activity in
a simple and versatile way.
subsequent oxidation reactions (Table 2, entries 1-5). After the fifth Subsequent studies are under progress in our laboratories for the
recycling, the product was obtained in 99% yield evidencing the detailed investigation of the biological potential of these
strong potential of RuCNT.
compounds and will be published in due course.
Table 2 Recycling of RuCNT catalyst.
General procedure for mild oxidation of sulfides to sulfones:
a solution of the corresponding sulfide (0.1 mmol) in
O
S
RuCNT (0.1 mol%)
NaIO4 (3.0 equiv)
To
CH3
S
H2O:ACN:DCM (2:1:1, 4 mL) was added RuCNT (0.1 mol%, 333 µL of
0.3 mM aqueous suspension). The mixture was kept under vigorous
stirring, and NaIO4 (63.9 mg, 0.3 mmol) was added. The mixture was
heated at 75 °C for 1 h, washed with a saturated solution of NaHCO3
(10 mL) and extracted with CH2Cl2 (3 x 10 mL). The organic phase
was dried with Na2SO4 and submitted to purification by column
chromatography over silica-gel, eluting with toluene.
Procedure for the recycling experiments: To a solution of 3a
(0.1 mmol) in H2O:ACN:DCM (2:1:1, 4 mL) was added RuCNT (0.1
mol%). The mixture was kept under vigorous stirring, and NaIO4
(63.9 mg, 0.3 mmol) was added. The mixture was heated at 75 °C
for 1 h, after this period, the reaction mixture was cooled to room
temperature and methanol (4 mL) was added. The mixture was
CH3
O
H2O:ACN:DCM (2:1:1)
75 °C, 1 h
3a
4a
Entry
Cycle
Yield (%)a
Fresh
1
2
3
4
5
>99
>99
>99
99
1st Recycle
2nd Recycle
3rd Recycle
4th Recycle
99
aIsolated yield.
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then transferred to Eppendorf tube (single tube) and centrifuged to
give a pellet consisting of nanohybrid and inorganic salts. The
supernatant was collected and the pellet was dispersed/centrifuged
with fresh methanol (2 × 2 mL). All supernatants were combined,
dried, and purified by chromatography over silica-gel, eluting with a
gradient mixture of hexane/AcOEt with increasing polarity to
quantitatively yield pure sulfone 4a. The pellet was washed with
water (2 × 2 mL) to remove inorganic salts from the nanohybrid.
The recovered RuCNT catalyst was used without further treatment
in subsequent recycling experiments.
This research was funded by grants from CNPq (404466/2016-8,
PVE 401193/2014-4 and PQ 305741/2017-9), FAPEMIG (PPM-
00638-16 and Rede de Pesquisa e Inovação para Bioengenharia de
Nanossistemas-RED-00282-16), FAPERJ, CAPES and INCT-Catálise.
ENSJ would also like to thank SeSRedCat and Capes-Humboldt
research fellowship programme for experienced researchers (Proc.
N° 88881.145517/2017-01). Elumalai Gopi thanks the “Enhanced
Eurotalents” program for support. The “Service de Chimie
Bioorganique et de Marquage” belongs to the Laboratory of
Excellence in Research on Medication and Innovative Therapeutics
(ANR-10-LABX-0033-LERMIT). There are no conflicts of interest to
declare.
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Catalysis Science & Technology
Paper
Bower and E. N. da Silva Júnior, Eur. J. Med. Chem., 2017,
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DOI: 10.1039/C9CY00384C
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DOI: 10.1039/C9CY00384C
Table of Contents
Carbon nanotube-ruthenium hybrid towards mild oxidation of sulfides to sulfones:
Efficient synthesis of diverse sulfonyl compounds
A heterogeneous catalyst was assembled with ruthenium nanoparticles on carbon
nanotubes and used in a mild oxidation method to prepare sulfones from sulfides in high
yields.