Sulfonylation of Bismuth Reagents with Sulfinates or SO2through BiIII/BiV Intermediates

Article abstract of DOI:10.1021/acs.organomet.1c00339

Studies to explore the catalytic activities of main-group elements are attractive. We report here our study of sulfonylation of bismuth reagents with sulfinates or SO2 surrogates. Under oxidative conditions, triarylbismuthines and sulfinates were transformed into diaryl sulfones. A transition-metal-like two-electron redox process at the Bi center was achieved in this reaction. Sulfur dioxide generated in situ can also replace sulfinates to deliver the corresponding symmetric diaryl sulfones. A rational mechanism for this reaction was also proposed that involves a Bi(III)-Bi(V) manifold.

Full text of DOI:10.1021/acs.organomet.1c00339

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Sulfonylation of Bismuth Reagents with Sulfinates or SO2 through
BiIII/BiV Intermediates
Fengqian Zhao and Xiao-Feng Wu*
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ABSTRACT: Studies to explore the catalytic activities of main-group
elements are attractive. We report here our study of sulfonylation of bismuth
reagents with sulfinates or SO2 surrogates. Under oxidative conditions,
triarylbismuthines and sulfinates were transformed into diaryl sulfones. A
transition-metal-like two-electron redox process at the Bi center was achieved
in this reaction. Sulfur dioxide generated in situ can also replace sulfinates to
deliver the corresponding symmetric diaryl sulfones. A rational mechanism for
this reaction was also proposed that involves a Bi(III)−Bi(V) manifold.
ransition metal catalysis plays an important role in the
development of organic chemistry.1 Transition metals
catalyzed fluorination and oxidative coupling of arylboronic
acids and triflate salts have been developed. In addition, a
similar process of CO insertion into the bismuth center has
also been reported by our group.11 The key to this strategy lies
in suitable oxidants and nucleophiles that can be easily
exchanged and eliminated. In our further studies on the redox
reactions of bismuth, we found that sulfinates can be used as
suitable coupling partners. Herein we report the application of
the bismuth-mediated two-electron redox strategy for the
synthesis of diaryl sulfones (Scheme 1c). It is also important to
mention that Barton and co-workers reported their studies of
phenylation of enols and β-diketones with Bi reagents under
basic conditions in 1985.10f In their study, sulfonic acid and
sulfinate were tested with Bi(V) compounds as well, and the
corresponding sulfones were produced.
Sulfones play a prominent role in organic and medicinal
chemistry. They are also versatile intermediates in organic
synthesis.12 Hence, various synthetic methods have been
developed for their preparation (Scheme 1b).13 Sulfinates are
among the most commonly used reagents for the synthesis of
organosulfonyl compounds, which are easy-to-handle, stable,
and commercially or readily available solids.14 Depending on
the different reaction conditions, they have the dual ability to
serve as nucleophilic or electrophilic reagents.15 In the work
described in this paper, by the use of sulfinates as suitable
nucleophiles, a bismuth-mediated oxidative coupling for the
synthesis of aryl sulfones has been developed, in which
triarylbismuthines act as both the aryl source and the metal
T
have multiple energetically accessible orbitals, and it is easy to
generate unpaired electrons, which gives them the ability to
form stable complexes and abundant reactivity.2 In contrast,
for main-group elements, the limited available orbitals are
empty or occupied by bonding and lone pairs of electrons, and
it is difficult to create an odd-electron species by gain or loss of
one electron. Thus, they usually appear as Lewis acids or bases
in the reactions. However, with the recent development of
molecular compounds containing main-group elements in the
design, synthesis, and application, main-group elements,
especially heavy ones, exhibit properties similar to those of
transition metal elements with regard to catalytic activity.3 The
traditional distinctions caused by the electronic structures have
been challenged.
As the heaviest stable element on earth, bismuth is 103−104
times cheaper than noble metals such as Pd and Pt, although
its content in the Earth’s crust is similar.4 The low price, low
environmental and biological toxicity,5 and ability to access
various oxidation states endow Bi with a huge potential for
redox reactions. However, nonredox activation modes of
bismuth have more frequently been used in the reactions
because of the inherent obstacles of main-group elements.6 In
recent years, with the synthesis of complex and stable
organobismuth compounds, redox transformations between
different valences of bismuth have been realized, such as
oxidation with pentavalent bismuth7 and one- or two-electron
redox processes between different valences.8−10 Among them,
the two-electron redox process between trivalent and
pentavalent bismuth is the most commonly employed case.
Concerning the reaction steps, trivalent bismuth species are
oxidized to pentavalent bismuth species, and after anion
exchange and reductive elimination, the corresponding
coupling product can be obtained (Scheme 1a). On this
basis, bismuth-mediated arylation of phenols and bismuth-
Received: June 8, 2021
Published: July 8, 2021
© 2021 The Authors. Published by
American Chemical Society
https://doi.org/10.1021/acs.organomet.1c00339
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a
Scheme 1. Redox Strategies for Organobismuth Reagents
and Procedures for the Synthesis of Diaryl Sulfones
Table 1. Optimization of the Reaction Conditions
b
entry equiv of 2a
oxidant (equiv)
solvent
yield of 3aa (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
1.5
1.5
1.5
1.5
1.5
2.0
2.5
3.0
4.0
2.5
2.5
2.5
2.5
m-CPBA (1.3)
PhI(OAc)2 (1.3)
[Cl2pyrF]BF4 (1.3)
m-CPBA (1.5)
m-CPBA (2.0)
m-CPBA (2.0)
m-CPBA (2.0)
m-CPBA (2.0)
m-CPBA (3.0)
m-CPBA (2.0)
m-CPBA (2.0)
m-CPBA (2.0)
m-CPBA (2.0)
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
DMAc
MeCN
toluene
THF
60
48
4
71
77
89
94
95
98
88
93
c
98 (96 )
97
a
Reaction conditions: 1a (0.1 mmol, 1.0 equiv), 2a, oxidant, solvent
(1.0 mL), 80 °C, 15 h. Abbreviations: m-CPBA = 3-chloroperox-
ybenzoic acid; [Cl2pyrF]BF4 = N-fluoro-2,6-dichloropyridinium
b
tetrafluoroborate. Determined by GC using hexadecane as the
internal standard; 0.1 mmol of 3aa corresponds to 100% yield.
c
Isolated yield.
reaction (3ca and 3da). A triarylbismuthine bearing an amide
group at the para position could also be converted into the
desired product in moderate yield (3ka). In addition, excellent
yields of the corresponding products were produced from
substrates substituted with electron-withdrawing groups,
including halogen, ester, and trifluoromethyl (3ma−pa).
Substrates substituted with other aryl groups, such as naphthyl
and 2-thienyl, delivered the target products in 92% and 52%
yield, respectively (3qa and 3ra). When the reaction was
carried out on a 1 mmol scale, an excellent yield was also
obtained. The compatibility of this reaction with various
sulfinates was then examined. Arylsulfinates bearing different
electron-donating or electron-withdrawing groups at the para
position were well-tolerated, delivering the corresponding
products in moderate to excellent yields (3ab−ag). Moreover,
sodium 2-naphthalenesulfinate provided the target product 3ah
in good yield as well. Additionally, an alkylsulfinate was also
converted smoothly in the reaction (3qi). Unfortunately, when
sodium trifluoromethanesulfinate (CF3SO2Na) was tested, the
desired product was not detected.
To explore the selectivity of different aryl groups in the
elimination process, several unsymmetrical triarylbismuthines
were tested under the standard conditions. For 1s, which has
two phenyl groups as well as an aryl group substituted with an
electron-donating group, 3aa was obtained as the main
product, and only a 15% yield of 3ja was delivered. In
contrast, when substrate 1t with two aryl groups substituted
with electron-donating groups and one phenyl group was used,
3aa was still the main product, although the yield of 3ja was
increased. When 1s was replaced with substrate 1u containing
an aryl group substituted with an electron-withdrawing group,
3aa and 3pa were generated in almost equal amounts.
Comparison of the results of these reactions proved that aryl
groups substituted with electron-withdrawing groups are easier
to eliminate in the reaction to deliver the corresponding
products.
center through a two-electron redox process and no other
metals are used.
To begin the investigation, we started by optimizing the
model reaction using Ph3Bi (1a) (1.0 equiv) and NaSO2Tol
(2a) (1.5 equiv) as substrates and m-CPBA as the oxidant in
CHCl3 at 80 °C for 15 h, which generated aryl sulfone 3aa in
60% yield. Using other commonly employed oxidants such as
(diacetoxyiodo)benzene (PhI(OAc)2) and N-fluoro-2,6-di-
chloropyridinium tetrafluoroborate ([Cl2pyrF]BF4) did not
give better results (Table 1, entries 1−3). Moreover, NBS,
DTBP, H2O2, and cumyl hydroperoxide were checked as well,
but very little or no desired product could be detected. Then
the amounts of the oxidant and 2a were adjusted. Product 3aa
was obtained in 94% yield when 2.0 equiv of m-CPBA and 2.5
equiv of 2a were used, and continuing to increase the amounts
of the oxidant and sulfinate only slightly increased the yield
(Table 1, entries 4−9). Additionally, we evaluated various
solvents, all of which could afford the desired product in
excellent yield (Table 1, entries 10−13). Finally, 3aa was
obtained in 98% yield when the reaction was carried out in
toluene.
With the optimal conditions in hand, we initially
investigated the scope of triarylbismuthines in the reaction
with 2a. As shown in Scheme 2, various triarylbismuthines
were well-tolerated, and the corresponding products were
obtained in moderate to excellent yields. Triarylbismuthines
with various functional groups appended, such as alkyl,
methoxy, phenyl, acetoxy and allyl, were successfully converted
into the corresponding aryl sulfones in 87−96% yield (3ba−ja
and 3la). The ortho and meta substituents had no effect on the
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we envisioned that sulfur dioxide could undergo a similar
process to provide valuable sulfone products. Here Na2S2O5
was used as the source of sulfur dioxide to replace sulfinates in
the reaction. As shown in Scheme 3, the desired symmetric
Scheme 2. Substrate Scope of Triarylbismuthines and
Sulfinates
a
Scheme 3. Arylsulfonylation of Triarylbismuthines with
a
Na2S2O5
a
Reaction conditions: Ar3Bi 1 (0.1 mmol, 1.0 equiv), Na2S2O5 4 (0.4
mmol), PhI(OAc)2 (0.15 mmol), Toluene (1.0 mL), 80 °C, 15 h,
b
isolated yields. CHCl3 (1.0 mL) was used.
diaryl sulfones could be produced in moderate yields through
insertion of sulfur dioxide generated in situ, although
substrates substituted with electron-withdrawing groups
produced only biaryl byproducts in toluene. However, 5d
was obtained in 43% yield when the reaction was carried out in
CHCl3.
To gain some insight into the reaction mechanism, several
control experiments were performed. First, triphenylbismu-
thane 1a or pentavalent bismuth species 6 was reacted under
the standard conditions in the absence of oxidant. As shown in
Scheme 4a, when 1a was used, the desired product was not
detected, and 1a was almost completely recovered. In contrast,
3aa was generated in 94% yield from pentavalent bismuth 6.
Those results suggest that 1a is first oxidized to give
pentavalent bismuth, which then reacts with the sulfinate to
deliver the final product. Subsequently, to further understand
the reaction process of pentavalent bismuth and sulfinate, a
series of experiments at different temperatures were conducted
(Scheme 4b). Almost no product was detected when the
reaction was carried out below 40 °C. When the NMR spectra
at different temperatures were combined (see Scheme S2),
there were new signals different from those of 6 and the
products at room temperature. We conjecture that pentavalent
bismuth could exchange anions with the sulfinate at room
temperature and that a sufficiently high temperature is
necessary for the elimination process.
On the basis of the above studies and related literature,7c,18
we proposed a plausible mechanism as depicted in Scheme 4c.
The reaction starts with the oxidation of 1a by m-CPBA to give
pentavalent bismuth I. Intermediate I exchanges anions with
the sulfinate to provide pentavalent bismuth intermediate II,
which may be the source of the new signals in the NMR
spectrum (see Scheme S2). Finally, the final product 3 can be
obtained upon heating.
In conclusion, through a two-electron redox process
between trivalent and pentavalent bismuth, a bismuth-
mediated oxidative coupling of triarylbismuthines and
sulfinates was developed. Various aryl sulfones were obtained
in moderate to excellent yields under mild conditions without
the use of other metals. This also represents the first study on
insertion of sulfur dioxide into a C−Bi bond to deliver the
a
Reaction conditions: 1 (0.1 mmol, 1.0 equiv), 2 (0.25 mmol), m-
CPBA (0.2 mmol), toluene (1.0 mL), 80 °C, 15 h. Isolated yields are
shown. 1 mmol. 4-Bromobenzenesulfinic acid sodium salt dihydrate
(2f) was used. 4.0 equiv of NaSO2Et (2i) was used.
b
c
d
In addition to the direct arylsulfonylation of sulfinates,
multicomponent arylsulfonylation through the insertion of
sulfur dioxide is also a powerful strategy for the synthesis of
sulfones, and excellent works have been reported by the Willis,
Jiang, Wu, and Manolikakes groups.16 Our previous work
showed that carbon monoxide can be inserted smoothly into
the metal center of pentavalent bismuth. Considering the
electronic similarity of carbon monoxide and sulfur dioxide,17
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Scheme 4. Mechanistic Experiments and Proposed
Mechanism
ACKNOWLEDGMENTS
■
The authors thank the Chinese Scholarship Council (CSC) for
financial support and the analytical team at LIKAT for their
excellent analytical support.
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ASSOCIATED CONTENT
■
sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.organomet.1c00339.
General comments, general procedures, analytical data,
and NMR spectra (PDF)
AUTHOR INFORMATION
■
Corresponding Author
Xiao-Feng Wu − Leibniz-Institut fur Katalyse e.V. an der
̈
Universität Rostock, 18059 Rostock, Germany; Dalian
National Laboratory for Clean Energy, Dalian Institute of
Chemical Physics, Chinese Academy of Sciences, Dalian,
Liaoning 116023, China; orcid.org/0000-0001-6622-
3328; Email: xiao-feng.wu@catalysis.de
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Arylation of Pyridin-2(1H)-ones with Pentavalent Organobismuth
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Author
Fengqian Zhao − Leibniz-Institut fur Katalyse e.V. an der
̈
Universität Rostock, 18059 Rostock, Germany
Complete contact information is available at:
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The authors declare no competing financial interest.
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Organometallics 2021, 40, 2400−2404