Methylsulfenylation of Electrophilic Carbon Atoms: Reaction Development, Scope, and Mechanism

Article abstract of DOI:10.1002/ejoc.201601613

An innovative method for the methylsulfenylation of electrophilic carbons was explored. Cheap and commercially available dimethyl sulfoxide (DMSO) was used as a source of the –SCH₃ group. Chalcone, dibenzylideneacetone, and Morita–Baylis–Hillma

Full text of DOI:10.1002/ejoc.201601613

A Journal of
Accepted Article
Title: Methylsulfenylation of Electrophilic Carbons: Reaction
Development, Scope, and Mechanism
Authors: Adriane A Pereira, Amanda A Pereira, Amanda C de Mello,
Arthur G Carpanez, Bruno A C Horta, and Giovanni Wilson
Amarante
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201601613
Link to VoR: http://dx.doi.org/10.1002/ejoc.201601613
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10.1002/ejoc.201601613
European Journal of Organic Chemistry
COMMUNICATION
Methylsulfenylation of Electrophilic Carbons: Reaction
Development, Scope, and Mechanism
Adriane A. Pereira,[a] Amanda S. Pereira,[a] Amanda C. de Mello,[a] Arthur G. Carpanez,[a] Bruno A. C.
Horta,[b]* and Giovanni W. Amarante[a]*
Dedication ((optional))
Abstract: An innovative methodology for methylsulfenylation of
electrophilic carbons is presented. Cheaper and commercially
available dimethylsulfoxide (DMSO) is now used as a source of -SCH3
group. Chalcone, dibenzylideneacetone (DBA) as well as Morita-
Baylis-Hillman (MBH) adduct derivatives were successfully
sulfenylated, giving the corresponding products with moderate to high
isolated yields. Control experiments and DFT calculations revealed
deoxygenation of DMSO process and the nucleophilic addition of a
sulphur intermediate as key steps in the entire mechanism.
described. Unfortunately, these sulfenylation reagents are
generally unstable, expensive and most likely the presence of
metal is required. Therefore, efficient and regioselective
methodologies to access β-thiocarbonyl compounds, as well as
new sulfenylation sources, have been the subject of intensive
research.
Dimethylsulfoxide (DMSO) may act as a source of –SCH3 under
some reaction conditions. It is commercially available and
significantly cheaper when compared to other sulfur rea-gents.
Methylthiolation of aryl C-H bonds,[12] aryliodides,[13] substituted
indoles,[14] flavones[15] and the synthesis of β-alkoxy methyl
sulfides[16] were developed using DMSO as the sulfur source.
Nevertheless, methylthiolation of Michael acceptors with DMSO
still remains a challenge.
The chemistry of sulfur-containing compounds has shown great
development over the last years.[1] β-thiocarbonyls are
a
remarkable class of compounds due to their intrinsic biological
properties.[2] Moreover, the presence of a stereogenic center
containing a C-S bond can be highly attractive for synthetic
purposes.[3] Sulfa-Michael addition consists of a strategy for C-S
bond formation in the preparation of complex organic molecules.[4]
It has several applications in organic synthesis, being an
interesting method for protecting double bonds in conjugated
enones.[5] Typically, 1,4-additions are catalyzed by strong bases
and Lewis acids, which may lead to undesired side reactions.[6]
Thiols are commonly used as sulfenylation agents in 1,4-addition
reactions.[7] However, over the past few years, new sulfur sources,
as well as alternative methodologies, have emerged for the
synthesis of β-thiocarbonyl compounds. For instance, a sulfur
migration in N-enoyl oxazolidine-2-thiones promoted by Lewis
acids affording β-mercapto imides.[8]
cascade reaction between 1,4-dithiane-2,5-diol and chalcones
A sulfa-Michael/aldol
catalyzed
tetrahydrothiophenes
by
bifunctional
in high
squaramide
either
affording
and
diastereo-
enantioselectivity.[9] Alternatively, sulfonyl hydrazide has
promoted tandem radical sulfenylation/cyclization reaction of N-
arylacrylamides in the presence of iodine leading to 3-
(sulfenylmethyl) oxindoles.[10] Recently, an efficient domino
process for the synthesis of thioflavanones using a copper
catalyst and xanthate as sulfur source[11] (Figure 1) has been
Figure 1. Previous approaches to β-thiocarbonyl compounds using
sulfenylation agents.
In the present study, we described a methylsulfenylation of
activated double bonds using DMSO as the sulfur source. This
innovative methodology was found during our attempts to
tricloromethylatedibenzilydene acetones (DBA’s) in the presence
of potassium trichloroacetate (KTCA) salt under microwave
irradiation. To our delight, DMSO acts not only as a solvent but
also as sulfenylation agent in this reaction.
Our studies initiated by reacting 1 equivalent of DBA and 2
equivalents of KTCA salt in presence of 10 mol% of
camphorsulfonic acid (CSA) as catalyst,[17] and 4 Å molecular
sieves (MS) in DMSO for 5 min on the microwave. No reaction
was observed. Several unsuccessful attempts varying proportions
[a]
A. A. Pereira, A. S. Pereira, A. C. de Mello, A. G. Carpanez, and
Prof. Dr. G. W. Amarante*
Chemistry Department
Federal University of Juiz de Fora
Cidade Universitária, São Pedro, Juiz de Fora, Brazil, 36036-900.
E-mail: giovanni.amarante@ufjf.edu.br
Homepage: http://www.ufjf.br/gpms/
Prof. Dr. B. A. C. Horta*
[b]
Chemistry Institute
Federal University of Rio de Janeiro
Cidade Universitária, CT Centro de Tecnologia, Rio de Janeiro,
Brazil, 21941-909
E-mail: bruno@iq.ufrj.br
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejoc.201601613
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COMMUNICATION
of DBA/KTCA salt, reaction time, power and amount of catalyst
were made (see Supporting Information). However, a slight
change in the reaction mixture showed to be pivotal for this
method. When 3 drops of acetic acid were added to the reaction
mixture at 100°C, we did observe the formation of the sulfenylated
product with 7% conversion. Notably, the amount of KTCA salt
also profoundly affects the reaction outcomes. The usage of 4
equivalent of KTCA salt was found to be crucial to improving the
reaction conversion by 40%.
Following our previous results based on the optimization involving
DBA, we decided to continue with the optimization in a less
complex α,β-unsaturated system (Table 1). As with the previous
case, the reaction does not occur if acetic acid is not added when
the temperature reaches 100°C (Entries 1 and 2).
Scheme 1. Scope of sulfenylation reaction in the presence of chalcones.
Symmetrical dibenzilydene acetone (DBA) was also considered
using 20 mol% of CSA. In spite of the presence of an extra double
bond, the product was obtained in 66%. Note that only one
addition of the methylsulfite group was observed (eq. 1).
Table 1. Optimization studies for sulfenylation of chalcones.
To demonstrate the applicability of this methodology we also
extended the scope of the reaction employing Morita-Baylis-
Hillman (MBH) adducts as substrates. However, the desired
Acetic
Chalcone/
Salt
CSA
(mol%)
Time
(min)
Conversion[b]
Entry
acid
product
(Z)-ethyl
3-(2-chlorophenyl)-2-((methylthio)methyl)
(equiv.)[a]
acrylate (A) was isolated as a mixture of diastereoisomers in 43%
yield; besides, compound (B) was also isolated (eq. 2).
1
2
1:4
1:4
1:4
1:4
1:4
1:4
1:4
1:6
1:6
1:4
1:4
1:4
1:4
1:4
-
-
30
30
5
-
10
20
20
20
20
20
20
5
-
-
3
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
9.6
14%
27%
44%
63%
32%
23%
41%
50%
91%
77%
50%
28%
4
10
15
30
40
20
30
30
30
30
30
30
5
6
7
To avoid the formation of these side products, we considered the
corresponding acyl ester derivatives 13a-h. All compounds tested
were well tolerated, giving the corresponding products in
moderate to excellent yields and with control of
diastereoselectivities (Scheme 2).
8
9
10
11
12
13
14
-
5
10
20
5
[a] Acetic acid added when the reaction mixture reached at 100 oC. [b] Measured
from 1H NMR analysis from the crude reaction mixture.
Additional experiments varying the reaction time were also
performed and a better conversion was observed in 30 minutes of
reaction (Entry 6). The use of 6 equivalents of KTCA salt
decreases the conversion (Entry 9). After extensive screening, we
evaluated the influence of the catalyst for this reaction. Finally, the
addition of 5 mol% of CSA as a catalyst is required to afford the
desired product with 91% conversion (Entry 11). Note that the
reaction does not occur in the absence of KTCA salt. The
structure of the final product was assigned by 1H NMR, 13C NMR,
HMBC and HRMS analyses.
Scheme 2. Scope of sulfenylation reaction in the presence of acyl ester
derivatives.
O-acetylated MBH adducts were also evaluated, however, only
the adducts bearing 2-Cl and 4-Br substituents afforded the
desired products in 42 and 62% (Scheme 3).
With the optimized conditions in hands, we explored the scope of
the reaction with different chalcones (Scheme 1). β-thiocarbonyl
compounds were obtained in moderate to excellent yields with
perfect regioselectivity. Notably, the reaction tolerated a variety of
substituents at different positions on the aromatic ring.
Scheme 3. Methylthiolation of O-acetylated MBH adducts.
Considering the mechanistic possibilities, a puzzling issue to
address is the fact that the reaction only takes place after the late
addition of acetic acid. If acetic acid is present from the start, no
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10.1002/ejoc.201601613
European Journal of Organic Chemistry
COMMUNICATION
this reaction condition instead of chalcones (see Supporting
Information). Since acetate is also formed, it adds to the sulfonium
cation (another barrierless process) leading to the
(Methylsulfanyl)methyl acetate ester in Figure 2a.
product is observed (see Supporting Information), indicating that
a crucial intermediate must be formed before its addition. The
species present in the reaction medium before adding acetic acid
are DMSO, KTCA salt, the substrate, the molecular sieves and
(optionally) a small amount of CSA (Figure 2).
Activation of the substrate by protonating the carbonyl group
makes it a good Michael-type acceptor and subsequent addition
of the ester via the sulfur atom takes place, forming a tetrahedral
intermediate. This intermediate reacts with another equivalent of
acetate in a SN2 substitution forming the enol tautomer of the
product. The two last steps are depicted in Figure 2b along with a
pictorial representation of the minimum energy path based on
DFT calculations. These calculations were carried out using the
M06-2X functional[19] and the 6-31++G** basis set,[20] as well as
the SMD salvation scheme,[21] and were performed using the
Gaussian 09 program[22]. The calculation results for the complete
proposed mechanism (all reaction steps in Figure 2a) are
provided in the Supporting Information along with the
computational details.
In summary, an innovative method for methylsulfenylation of
activated double bonds is described. Early combination between
the cheaper and commercially available DMSO and KTCA
o
following the addition of acetic acid at 100 C under microwave
irradiation gave the corresponding sulfenylated products in good
to high yields. Mechanism hypothesis considering both control
experiments and DFT calculations indicates the DMSO
deoxygenation process and nucleophilic addition of a sulfur
intermediate as key steps of this reaction.
Experimental Section
Representative procedure for the sulfenylation reaction: Chalcone (0.2
mmol), KTCA salt (0.8 mmol; 0.1612 g), CSA (5 mol%; 0.0023 g) and
additive of MS 4Å were added in 1 mL of DMSO. The reaction mixture was
heated in a microwave reactor (50W, reflux mode) for 30 minutes, when
the temperature reached 100° C (approximately after 2 minutes), the acetic
acid was added.
Figure 2. a) A representation of the sequence of intermediates of the proposed
mechanism. b) A pictorial representation of the reaction coordinate for the
addition and substitution steps. The barriers were drawn according to the
energies obtained by DFT calculations. The other steps of the mechanism are
described in the Supporting Information.
Supporting Information
Experimental procedures, characterization data, copies of 1H and 13C
NMR spectra for the new products as well as details of the DFT
calculations.
The removal of the molecular sieves and CSA was found to have
an impact on the reaction yields, but reaction still occurs. The
addition of the substrate only at the point at which acetic acid is
added also leads to the desired product, which leads us to
conclude that this key intermediate is formed by DMSO and
KTCA. KTCA is known to decarboxylate in DMSO even at room
temperature,[18] releasing CO2 and -CCl3 that can eventually
deprotonate DMSO forming chloroform and the Dimsyl anion
(Figure 2a). Both CO2 and CHCl3 are gases at 100°C entropically
favoring this process since the reaction is carried out in an open
system. We believe that the Dimsyl anion is the key intermediate
that acetic acid reacts with and that the presence of acetic acid
from the start prevents its formation. At this point in the proposed
mechanism, acetic acid protonates the Dimsyl anion at the
hardest site (a barrierless process), which is the oxygen atom,
forming a hydroxyl group that is further protonated, releasing
water and forming the sulfonium cation. This intermediate was
trapped and fully characterized when a fatty acid was used under
Acknowledgements
We would like to thank Brazilian agencies FAPEMIG (Research
Supporting Foundation of the State of Minas Gerais), FAPERJ
(Research Supporting Foundation of the State of Rio de Janeiro),
CAPES, CNPq and Rede Mineira de Química for financial support.
Keywords: Sulfenylation • Activated Carbons •
Dimethylsulfoxide • Microwave • DFT Calculations
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
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Text for Table of Contents
Author(s), Corresponding Author(s)*
Page No. – Page No.
Title
Layout 2:
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Microwave irradiation; Organocatalysis
A. A. Pereira, A. S. Pereira, A. C. de
Mello, A. G. Carpanez, B. A. C. Horta,*
and G. W. Amarante*
Page No. – Page No.
Methylsulfenylation of Electrophilic
Carbons: Reaction Development,
Scope, and Mechanism
Methylsulfenylation of activated carbons is now possible by using DMSO. A
combined metal-free process and microwave irradiation makes real a novel
chemoselective C-S bond formation.
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