Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C?S Bond Cleavage: Reaction Development and Mechanism Study

Article abstract of DOI:10.1002/asia.201701694

A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C?S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu^II intermediate, O?O bond homolysis induced C?S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C?S bond cleavage and transformations.

Full text of DOI:10.1002/asia.201701694

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with
Alcohols via C−S Bond Cleavage: Reaction Development and
Mechanism Study
Authors: Bingnan Du, Wenmin Wang, Yang Wang, Zheng-Hang Qi,
Jiaqi Tian, Jie Zhou, Xiaochen Wang, Jianlin Han, Jing Ma,
and Yi Pan
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Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with
Alcohols via C−S Bond Cleavage: Reaction Development and
Mechanism Study
Bingnan Du,[a],† Wenmin Wang,[c],† Yang Wang,[a] Zhenghang Qi,[c] Jiaqi Tian,[c] Jie Zhou,[b] Xiaochen
Wang,[a] Jianlin Han,*,[a] Jing Ma,*,[c] and Yi Pan[a]
Dedication ((optional))
Abstract: A Cu-catalyzed cascade oxidative radical process of β-
keto sulfones with alcohols has been achieved by using oxygen as
an oxidant. In this reaction, β-keto sulfones were converted into
sulfinate esters under the oxidative conditions via cleavage of C-S
bond. Experimental and computational studies demonstrate that a
new pathway is involved in this reaction, which proceeds through the
formation of the key four-coordinated Cu(II) intermediate, O−O bond
homolysis induced C−S bond cleavage and Cu-catalyzed
esterification to form the final products. This reaction provides a new
strategy to sulfonate esters and enriches the research contend of the
C−S bond cleavage and transformations.
The activation and transformations of inert chemical bonds are
fundamental scientific issues. Up to now the processes of
C−H,[1] C−C,[2] C−N[3] and C−O[4] bond cleaving reactions
catalyzed by transition metals have been well developed. In
recent years, the C–S bond cleavage and transformations have
become important in the petroleum industry and synthetic
chemistry.[5] The most developed one in this area is insertion of
a transition-metal into the C−S bond of organosulfur compounds,
leading to the corresponding C–S bond cleavage.[6] Generation
of a sulfur radical via the C−S bond homolysis in sulfones,
sulfoxides or other compounds, also has been developed for
another type of C−S bond cleavage.[7] Although significant
advances have been made in the research of C−S bond
cleavage during the past decades,[6-8] the development of
catalytic, selective C−S bond cleavage reactions is still a
challenging problem in organic chemistry.[9]
β-Keto sulfones[10] are attractive and powerful tools in
organic synthesis, which could be easily converted into various
Scheme 1. The C-S bond cleavage of β-keto sulfones.
classes of organic compounds via reactions on the methylene
moiety or the carbonyl moiety.[11] However, there are few reports
on the transformation of sulfonyl groups of β-keto sulfones.[12] In
[a]
B. Du,[†] Y. Wang, X. Wang, Prof. Dr. J. L. Han, Dr. Prof. Y. Pan
School of Chemistry and Chemical Engineering, State Key
Laboratory of Coordination Chemistry
Nanjing University
Nanjing, 210023, P. R. China
E-mail: hanjl@nju.edu.cn
2015, the Pandey group developed a Zn-promoted C−S bond
cleavage of β-keto sulfones via cyclopropanation for the
synthesis of α-methenyl ketones (Scheme 1a).[12a] Liu, Wu and
co-workers also reported a photocatalytic C−S bond cleavage of
β-keto sulfones with the radical anion as intermediate (Scheme
1b).[12b] The Li group developed a Ni-catalyzed Kumada coupling
reaction between β-keto sulfones and Grignard reagents, which
proceeded through the Ni insertion initiated C−S bond cleavage
to give the modified aryl ketones as products (Scheme 1c).[12c]
To the best of our knowledge, the transformation on sulfonyl
group of β-keto sulfones to sulfinate compounds has never been
reported until now. Herein, we report the first example on
copper-catalyzed aerobic oxidative[13] C−S bond cleavage of β-
keto sulfones to give sulfinate esters as the corresponding
products (Scheme 1d). Our combined experimental and
[b]
[c]
Dr. J Zhou
Shenzhen Research Institute of Nanjing University, Shenzhen,
518057, China
W. Wang,[†] Z.-H. Qi, J. Tian, Prof. Dr. J. Ma
School of Chemistry and Chemical Engineering, Institute of
Theoretical and Computational Chemistry
Nanjing University
Nanjing, 210023, P. R. China
E-mail: majing@nju.edu.cn
These authors contributed equally
[†]
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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computational study aims to elucidate the factors that the
transformation of sulfone into sulfinate under Cu-catalyzed
oxidative conditions with O2. A novel mechanism involving a key
four-coordinated Cu(II) intermediate for this reaction is
presented for this catalytic system. Furthermore, it should be
mentioned that the transformation of sulfone into sulfinate
ester[14] is conducted under oxidative conditions.
10
11
12
13
14
15
16
17
18
CuBr (10)
CuBr (10)
CuBr (10)
CuBr (10)
CuBr (20)
CuBr (20)
CuBr (20)
–
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
0
PhCF3 (2.0)
PhCF3 (0.5)
PhCF3 (1.0)
PhCF3 (4.0)
PhCF3 (1.0)
PhCF3 (1.0)
PhCF3 (1.0)
PhCF3 (1.0)
PhCF3 (1.0)
36
40
43
31
54
62[c]
46[d]
0
To
determine
the
reaction
parameters,
benzenesulfonylacetone 1a and 1-butanol 2d were chosen as
model substrates (Table 1). The initial combination of CuCl (10
mol %) and pyridine (1.0 equiv) in toluene was evaluated. The
reaction did happen, however, to our surprise, an unpredictable
sulfinate product 3ad was detected in 12% yield under an
oxygen atmosphere (entry 1). The reactions employing CuBr or
CuBr2 as the catalysts delivered the sulfinate product 3ad in
better yields (23% and 16%, respectively, entries 2 and 4).
However, CuI gave a disappointing result since only a trace
amount of the expected product was found (entry 3). A similar
yield was found with benzene as solvent (entry 5), while
(trifluoromethyl)-benzene provided an improved result (entry 8).
Decreasing the amount of pyridine from 1.0 to 0.5 equiv, a
slightly lower yield of product 3ad was observed (entry 9). An
improved yield was achieved by increasing the amount of
pyridine to 2.0 equiv (36%, entry 10). Entries 11-13 of Table 1
showed that the concentration of the reaction mixture had an
obvious effect on the outcome. The results clearly disclose that
the use of 1.0 mL (trifluoromethyl)benzene was the best choice,
affording a 43% yield (entry 12). Additional optimization using
different amounts of CuBr catalyst was carried out, and the
desired product was obtained in a dramatically higher yield when
20 mol % of CuBr was used (entry 14). The yield could be
further increased to 62% when 4 Å molecular sieves were added
into the reaction mixture (entry 15). Decreasing the reaction
CuBr (20)
0
[a] Reaction conditions: 1a (0.25 mmol), 1d (1.0 mmol), and the solvent, in a
flask under O2 balloon at 90 oC for 6 h. [b] Isolated yield based on 1a. [c] 200
mg 4 Å molecular sieve was added. [d] at 70 oC.
We then investigated the reaction generality of alcohol
substrates by using 1a as the standard reacting partner
(Scheme 2).
O
O
O
S
O
S
CuBr (20 mol %), pyridine (2.0 equiv)
O2, 90 oC, 6 h, 4 Å MS
R
O
+
R
OH
2a-n
1a
3a-n
O
S
O
O
S
O
S
S
O
O
O
O
3ad
, 62% yield
43% yield[b]
3aa, 46% yield[a]
[a]
3ab
3af
, 51% yield
3ac, 58% yield
O
O
O
O
S
O
S
S
o
o
S
O
O
O
temperature from 90 C to 70 C, a lower chemical yield was
found (46%, entry 16). Finally, control experiments carried out in
the absence of either catalyst CuBr or ligand pyridine failed to
O
3ag
, 39% yield
3ae, 59% yield
, 25% yield
3ah
, 58% yield
give the target product (entries 17 and 18).
O
S
Table 1. Optimization of reaction conditions.[a]
O
O
S
S
O
O
O
Cl
3ak
, 61% yield
3aj
, 52% yield
3ai, 53% yield
O
S
O
O
F
S
O
S
Entry
Catalyst (mol %)
Pyridine
(equiv)
Solvent (mL)
Yield
(%)[b]
O
O
O
CN
F
3am, 54% yield
3an, 57% yield
3al
, 55% yield
1
2
3
4
5
6
7
8
9
CuCl (10)
CuBr (10)
CuI (10)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.5
Toluene (2.0)
Toluene (2.0)
Toluene (2.0)
Toluene (2.0)
Benzene (2.0)
Anisole (2.0)
PhF (2.0)
12
23
<5
16
22
13
25
28
22
Scheme 2. Substrate scope study with variation of alcohols. (Reaction
conditions: 1 (0.25 mmol), 2 (1.0 mmol), CuBr (20 mol%), pyridine (2.0 equiv)
and PhCF3 (1.0 mL), in a flask under O2 at 90 oC for 6 h. Isolated yields. [a] 2
(2.0 mmol) at 70 oC. [b] The yield from the reaction of 2.0 mmol of 1a.)
CuBr2 (10)
CuBr (10)
CuBr (10)
CuBr (10)
CuBr (10)
CuBr (10)
Encouragingly, varieties of alcohols, such as aliphatic linear
primary and tertiary alcohols, cyclic alcohols and benzyl alcohols
were well accommodated to afford the corresponding sulfinate
products in 25-62% isolated yields. In the case of aliphatic linear
primary alcohols, high boiling alcohols, such as propanol 2c,
butanol 2d and pentanol 2e, could work well in this reaction
giving rise to 58-62% yields (3ac-ae), while the reactions of
methanol and ethanol afforded lower yields (3aa-ab). When the
PhCF3 (2.0)
PhCF3 (2.0)
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reaction scale of 1a was increased from 0.25 mmol to 2.0 mmol,
the reaction also proceeded smoothly, affording the
corresponding product 3ad in 43% yield. Notably, 2-
ethoxyethanol was also well compatible with our reaction
protocol resulting in 2-ethoxyethyl benzenesulfinate 3ag with
39% isolated yield. Interestingly, the reaction of substrate with
cyclopropyl substituent also proceeded smoothly, giving rising to
3ah in 58% yield. In particular, the alcohol 2f containing a bulky
group still could work in this reaction, however a dramatically
lower chemical yield was found (25%). This result clearly
indicates that steric hindrance effects this Cu-catalyzed oxidative
reaction. Remarkably, cyclic aliphatic alcohols were also
effective substrates for this system, and provided sulfinic cyclic
esters with moderate yields (3ai, 3aj). Other benzyl alcohols (2k-
2n) were found to be well suited to generate the products in
moderate to good yields. Of particular importance was the
tolerance of various substituents regardless of their
electronegativity, generating the products in 54-61% yields.
To gain insight into this transformation mechanism, first of all,
radical trapping experiments were carried out (Scheme 4a).
When 2.0 equiv of TEMPO or BHT was added, the reaction was
obviously suppressed, which implies that the radicals may be
generated in the current copper-catalyzed aerobic oxidative
reaction. Then, several control experiments were designed to
further investigate the reaction mechanism. As shown in
Scheme 4b, 34% yield of the sulfinate product was obtained
when benzenesulfinic acid was examined in the current system,
which implies that benzenesulfinic acid might be the active
species in this transformation. The reaction with 2-
(phenylsulfonyl)acetonitrile as substrate failed to give the
desired product, which discloses the role of the carbonyl group
not acting as the electron withdrawing group. We assign this to
the inherent enol keto tautomerism of the carbonyl compound
(Scheme 4c). In order to understand the transformation, we
have chosen 1-phenyl-2-(phenylsulfonyl)ethanone 1j as
a
substrate. Butyl 2-oxo-2-phenylacetate 3jd was obtained in 44%
yield under the standard conditions (Scheme 4d). Based on this
result, arylsulfonylacetone carbonyl group is turned into the
respective keto ester in the reaction.
Then, the generality of this Cu-catalyzed oxidative reaction
with respect to butanol 2d was examined for substituted
arylsulfonylacetone (Scheme 3). Most of the examined
arylsulfonylacetones were suitable substrates, and the
transformation proceeded smoothly to afford the corresponding
sulfinates in moderate isolated yield (49-63%, 3bd-hd). It should
be mentioned that the electronegativity of the substituents
almost showed no effect on this process, even fluoro (1c) and
methoxyl (1f) groups were well tolerated in this reaction. Quite
notably, the substrates (1g-1h) with di-substituted aromatic ring
still worked well in this reaction, and resulted in the expected
sulfinate with 57% and 50% yield respectively. Finally, further
scope examination was carried out with a benzyl group
substrate, 1-(benzylsulfonyl)propan-2-one (1i). However, it could
not be transformed to the corresponding sulfinate 3id under
current conditions.
Scheme 4. Control experiments.
To clarify the direction of oxygen atom transfer in the
reaction, an 18O labelling experiment was designed and carried
out with Me18OH. Finally, the 18O-labeled product 3aa’ was
obtained in 50% yield (Scheme 5) proving the role of oxygen in
the reaction.
Scheme 5. Isotope labelling experiment.
The possible reaction pathway of copper-catalyzed aerobic
oxidative selective bond cleavage of β-keto sulfones to
sulfonates is presented in Scheme 6. At first, β-keto sulfone
went through an enol tautomerism process to form a hydroxyl
group in β position. Then the catalyst attacked on the hydroxyl
oxygen to replace the hydroxyl hydrogen and the pyridine ligand
was removed simultaneously to generate intermediate IM1. A
six-membered ring of α-peroxo ketone (IM2) was formed
successively after O2 attacks the α-carbon position. The O-O
Scheme 3. Substrate scope study with variation of β-keto sulfone. (Reaction
conditions: 1 (0.25mmol), 2 (1.0 mmol), CuBr (20 mol%), pyridine (2.0 equiv)
and PhCF3 (1.0 mL), in a flask under O2 at 90 oC for 6 h. Isolated yields.)
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and C-S bond cleavage of IM2 went through TS1 with an energy
barrier of 23.7 kcal/mol, yielding IM3. It was a concerted process
for the cleavage of O-O and C-S bond of IM2. IM3 is a weakly
bonded complex of components, so it is easy to remove IM1p to
give IM4. Subsequently, butanol (1d) was coordinated to the
copper center of IM5p to form the intermediate IM6p. It is obvious
that IM6p went through an intramolecular hydrogen transfer
process (TS2p) with a low activation free energy barrier of 5.8
(12.4 for TS2) kcal/mol to arrive IM7p on the basis of the selected
mulliken charges given in Figure S2. Finally, the product is
obtained through the transfer of hydroxyl and alcohol oxygen
group in the intermediate IM8b.
containing coupling partner has been discussed by DFT
calculation and control experiments. The DFT calculation
discloses a novel O-O bond homolysis in copper(II)–peroxo
complexes induced cleavage of C-S bond method. This fracture
pattern enriches the knowledge of previous C-S bond cleavage.
The detailed mechanistic study and further applications are
ongoing in our laboratory.
Experimental Section
Typical procedure for Cu-catalyzed oxidative coupling reaction:
Arylsulfonylacetones 1 (0.25 mmol), CuBr (0.05 mmol) and molecular
sieve (200 mg) were added to a 25 mL schlenk tube under O2
atmosphere, followed by addition of alcohols 2 (1.0 mmol), pyridine (0.5
mmol) and PhCF3 (1.0 mL), The mixture was stirred at 90 ºC for 6 h, then
filtered and the solid was washed with Et2O. The organic solution was
concentrated by rotary evaporator. Next, crude product was purified over
a column of silica gel (eluant: petroleumether/ethylacetate) to afford the
desired product 3.
Acknowledgements ((optional))
We gratefully acknowledge the financial support from the
National Natural Science Foundation of China (Nos. 21472082,
21673111, 21772085 and 21761132021). The support from
Collaborative Innovation Center of Solid-State Lighting and
Energy-Saving Electronics, Shenzhen Virtual University Park,
the Jiangsu 333 program (for Pan) and Changzhou Jin-Feng-
Huang program (for Han) are also acknowledged.
Scheme 6. Proposed mechanism of the formation of sulfinate.
Keywords: Cu-catalyzed • C−S bond cleavage • aerobic
Beside the possible path for target product, a possible path
for the other byproduct was also provided. The proposed
mechanism for copper-catalyzed the transformation of the
carbonyl to give the butyl 2-oxopropanoate IM7b is presented in
Scheme 7 and Figure S4.
oxidation • β-keto sulfones • DFT calculation
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Scheme 7. Proposed mechanism of product α‑keto-ester
In conclusion, a copper-catalyzed aerobic oxidative selective
bond cleavage of β-keto sulfones to sulfinates has been
developed. The β-keto sulfones as a new type of sulfur
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10.1002/asia.201701694
Chemistry - An Asian Journal
COMMUNICATION
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COMMUNICATION
Bingnan Du, Wenmin Wang, Yang
Wang, Zhenghang Qi, Jiaqi Tian, Jie
Zhou, Xiaochen Wang, Jianlin Han,*
Jing Ma,* Yi Pan
Page No. – Page No.
Copper-Catalyzed Oxidative Reaction
of β-Keto Sulfones with Alcohols via
C−S Bond Cleavage: Reaction
A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols
has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones
were converted into sulfinates ester under the oxidative conditions via selective
cleavage of C-S bond. The mechanism has been investigated by experimental and
computational studies.
Development and Mechanism Study
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