Intramolecular Desulfitative Coupling: Nickel-Catalyzed Transformation of Diaryl Sulfones into Biaryls via Extrusion of SO2

Article abstract of DOI:10.1021/acs.orglett.8b02972

As a new transformation of organosulfur compounds, intramolecular desulfitative coupling of diaryl sulfones to the corresponding biaryls has been developed with the aid of nickel-NHC catalysts. This catalytic elimination of SO₂ was also applicable to alkenyl aryl sulfone to furnish the corresponding alkenyl arene.

Full text of DOI:10.1021/acs.orglett.8b02972

Letter
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
pubs.acs.org/OrgLett
Intramolecular Desulfitative Coupling: Nickel-Catalyzed
Transformation of Diaryl Sulfones into Biaryls via Extrusion of SO2
Fumiya Takahashi, Keisuke Nogi, and Hideki Yorimitsu*
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
*
S Supporting Information
ABSTRACT: As a new transformation of organosulfur compounds,
intramolecular desulfitative coupling of diaryl sulfones to the
corresponding biaryls has been developed with the aid of nickel−
NHC catalysts. This catalytic elimination of SO was also applicable to
2
alkenyl aryl sulfone to furnish the corresponding alkenyl arene.
rganosulfur compounds have occupied important
positions not only as bioactive entities and functional
this process, catalytic desulfitative couplings of arenesulfonyl
chlorides, hydrazides, and sulfinate salts have been achieved.
O
materials but also as useful building blocks or reagents in
However, these reactions are limited to intermolecular
1
6,7
organic synthesis. Among organosulfur compounds, sulfones
coupling with external reagents. To date, intramolecular
show intriguing reactivity owing to the low electron density
desulfitative coupling of unsaturated sulfones has been limited
1
,2
and the good leaving ability of the sulfonyl unit.
The Ramberg−Backlund reaction is a well-known reaction
specific to dialkyl sulfones and has been extensively studied
to a ruthenium-catalyzed reaction reported by Kamigata
8
̈
(Scheme 1, eq 2). However, this transformation only
accommodates divinyl sulfones, and its synthetic utility
remains unexplored. In light of the importance of biaryls in
the chemical community, herein, we report intramolecular
desulfitative coupling of diaryl sulfones into the corresponding
biaryls by employing nickel−NHC (N-heterocyclic carbene)
3
,4
since its discovery in 1940.
The reaction mechanism
includes intramolecular S 2 reaction of α-haloalkyl sulfones
N
followed by extrusion of SO from episulfones to provide
2
alkenes (Scheme 1, eq 1). This intramolecular process
9
,10
catalysts (Scheme 1, eq 3).
Scheme 1. Intramolecular Desulfitative Reactions
By employing 2-naphthyl 2-quinolyl sulfone (1a) as a model
substrate, we conducted optimization of the reaction
conditions (Table 1). Owing to its potential for inert bond
11
cleavage, we decided to use nickel catalysis. After extensive
screening of nickel precursors and ligands, a combination of
Ni(cod) and IMes generated in situ from IMes·HCl (Figure
2
1
) and t-BuONa was found to be effective. In the presence of
the catalyst, 1a was heated in toluene under reflux (bath temp.:
50 °C). To facilitate departure of SO , a N balloon was
1
2
2
equipped to the reaction vessel. As a result, desired coupling
product 2a was obtained in 65% NMR yield (Table 1, entry 1).
Small amounts of 2,2′-biquinolyl 3a and 2,2′-binaphthyl 4a
were also obtained as byproducts. An addition of Mg turnings,
which might reduce undesirably oxidized nickel species,
improved the yield of 2a to 74% (Table 1, entry 2). Coupling
product 2a was not obtained without either Ni(cod) or IMes,
2
whereas considerable amounts of 1a were decomposed due to
strongly basic t-BuONa and the high reaction temperature
(
Table 1, entries 3 and 4). The reaction in a closed vessel
represents fascinating replacement of the SO unit by a C−C
2
without a N balloon decreased the yield of 2a, while 1a was
almost consumed (Table 1, entry 5). Although other NHC
ligands showed comparable reactivity, mono- and bidentate
electron-rich phosphines such as PCy and dcypt did not
2
double bond. Inspired by the elegant Ramberg−Backlund
̈
technology, we envisioned exploring a new intramolecular C−
C bond-forming reaction with extrusion of SO . In particular,
2
12
3
we focused our attention on intramolecular desulfitative
work well (Table 1, entries 6−10).
coupling starting from unsaturated sulfones, considering the
2
5
recent advances in catalytic C(sp )−S bond transformations.
Arenesulfonylpalladiums or -rutheniums are known to expel
Received: September 17, 2018
SO to form the corresponding arylmetal species. By virtue of
2
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.8b02972
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Table 1. Condition Screening
a
a
a
,
b
a,c
entry
ligand
IMes·HCl
IMes·HCl
IMes·HCl
none
IMes·HCl
IPr·HCl
SIMes·HCl
L1·HCl
solvent
conv of 1a (%)
yield of 2a (%)
yield of 3a (%)
yield of 4a (%)
d
1
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
93
89
52
50
94
80
100
99
24
1
57
100
63
59
100
96
63
63
65
74
0
6
4
0
24
2
4
8
12
8
0
4
20
8
6
4
6
14
16
0
2
3
e
4
5
0
2
f
56
55
71
73
6
18
12
10
26
20
0
12
18
14
10
18
22
24
<10
6
7
8
g
9
PCy (80 mol %)
3
g
1
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
8
dcypt
0
IMes·HCl
IMes·HCl
IMes·HCl
IMes·HCl
IMes·HCl
L1·HCl
1,4-dioxane
45
41
42
33
80 (70 )
81 (71 )
DMI
PhEt
mesitylene
h
PhMe/PhEt (v/v = 1/3)
PhMe/PhEt (v/v = 1/3)
PhMe/PhEt (v/v = 1/3)
PhMe/PhEt (v/v = 1/3)
h
i
j
L1·HCl
L1·HCl
42
59
18
4
a
b
c
Determined by NMR. Calculated based on the molar amount of the 2-quinolyl ring of 1a. Calculated based on the molar amount of the 2-
naphthyl ring of 1a. Without Mg. Without Ni(cod) . Conducted in a closed tube. Without t-BuONa. Isolated yield. With 20 mol % of ligand
and 40 mol % of t-BuONa. 5 mol % of Ni(cod) , 10 mol % of ligand, and 15 mol % of t-BuONa.
d
e
f
g
h
i
2
j
2
decreased the conversion of 1a (Table 1, entry 17), which
indicates a 2-fold amount, 40 mol %, of L1 would suppress
deactivating aggregation of nickel species that are generated
through dissociation of L1 at the high temperature. Notably, a
5
9% yield of 2a was obtained even with 5 mol % of the nickel
catalyst (Table 1, entry 18).
Having optimized the reaction conditions (Table 1, entry
6), we explored the scope of aryl 2-quinolyl sulfones (Scheme
, a). Aryl sulfones bearing an electron-donating or -with-
1
2
drawing group successfully reacted to afford the desired
coupling products 2b−2h. It is noteworthy that cyano and
ester groups in 2g and 2h were tolerated during the reactions.
Figure 1. Ligands employed in Table 1. Cy = cyclohexyl.
2
-Methoxyphenyl sulfone 1i gave coupling product 2i in only
We then investigated the solvent effect. The use of 1,4-
dioxane instead of toluene lowered the conversion of 1a (Table
21% yield, probably due to the steric hindrance. Other aryl
sulfones such as 1-naphthyl and 2-thienyl sulfones 1j and 1k
were also applicable to the intramolecular coupling.
1
, entry 11). Significant amounts of byproducts 3a and 4a were
formed when DMI was employed (Table 1, entry 12).
Ethylbenzene and mesitylene having higher boiling points
were not effective (Table 1, entries 13 and 14). We inferred
that toluene acts not only as a simple solvent but also as a π-
bonded ligand that would prevent undesired aggregation of
catalytically active nickel species. Speculating that the bulkier
ethyl group in ethylbenzene and the three methyl groups in
mesitylene hampered its π-coordination to the nickel, we
envisioned that a toluene/ethylbenzene cosolvent system
would achieve a good balance between a higher reaction
temperature and effective π-coordination. As we expected, the
yield of 2a was improved when the reaction was conducted in
toluene/ethylbenzene (v/v = 1/3), and 2a was isolated in 70%
yield (Table 1, entry 15). Under the cosolvent conditions, the
We then investigated the scope of azaaryl 2-naphthyl
sulfones (Scheme 2, b). The intramolecular coupling reactions
of 1-isoquinolyl sulfones 1l and 1m successfully occurred
under the standard conditions to form biaryls 2l and 2m in
80% and 65% yields, respectively. The present catalysis was
operative on a gram scale: 1.5 g (5.7 mmol, 71%) of 2l was
obtained from 8 mmol of 1l. 2-Quinoxalyl, 2-pyrazyl, and 2-
pyridyl sulfones 1n−p were converted to biaryls 2n−p albeit in
moderate yields. The position of the C−SO bond on the
2
quinoline ring is important; 3-quinolyl and 4-quinolyl sulfones
1q and 1r resisted the reaction and were mostly recovered.
In our system, 2-azaaryl groups are necessary for catalytic
turnover. Treatment of di(2-naphthyl) sulfone (5) under the
catalytic conditions afforded 4a in only 18% yield (Scheme 3).
By means of a stoichiometric amount of the Ni−IMes
complex, the yield of 4a could be increased to 50%.
1
3
use of L1 was also effective to lead to isolation of 2a in 71%
yield (Table 1, entry 16). The reaction with 20 mol % of L1
B
DOI: 10.1021/acs.orglett.8b02972
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Scheme 2. Scope of Diaryl Sulfones
quinolyl sulfone (6) could be converted to the desired
coupling product 7 in 55% yield (Scheme 4, eq 1). On the
Scheme 4. Intramolecular Desulfitative Coupling of Alkenyl
Sulfones
other hand, divinyl sulfone 8 which was a suitable substrate in
8
Kamigata’s work was not applicable to the present coupling:
only a 12% yield of product 9 was obtained, while most of 8
was consumed (Scheme 4, eq 2).
A possible catalytic cycle is shown in Scheme 5. First, a
highly electron-rich Ni(0)−NHC complex would cleave one of
Scheme 5. Possible Catalytic Cycle
the two C−SO bonds of 1 to provide arylnickel(II) sulfinate A
2
9
a−g
and A′.
Via thermal extrusion of SO from these
2
intermediates, diarylnickel(II) species B would be then formed.
Finally, reductive elimination would afford biaryl 2 and
nickel(0) species. The 2-azaaryl ring of 1 is necessary for the
smooth desulfitative reaction probably because (1) coordina-
tion of the nitrogen to nickel would accelerate oxidative
addition and/or (2) the electron-withdrawing nature of the 2-
azaaryl ring would thermodynamically stabilize electron-rich
a
1
b
Determined by H NMR. Eight mmol scale.
Scheme 3. Intramolecular Desulfitative Coupling of
Dinaphthyl Sulfone (5)
14
diarylnickel B to facilitate the desulfitation process. The
formation of byproducts 3 and 4 would occur from A and A′.
15
Intermediate A can undergo ligand metathesis with another
A to afford di(2-azaaryl)nickel and nickel disulfinate. The
former would furnish byproduct 3 through reductive
elimination. Byproduct 4 would be generated via a similar
process from intermediate A′.
a
Conditions in Table 1, entry 2. NMR yield.
The present intramolecular desulfitative coupling was
applicable not only to diaryl sulfones but also to alkenyl aryl
sulfone. Under the standard conditions, 1-cyclohexenyl 2-
In summary, we have developed intramolecular desulfitative
coupling of diaryl sulfones by means of nickel−NHC catalysts.
Various aryl 2-azaaryl sulfones underwent the present reaction
C
DOI: 10.1021/acs.orglett.8b02972
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
to afford the corresponding unsymmetrical biaryls in a selective
manner. Moreover, this methodology was also applicable to
alkenyl aryl sulfone. The intramolecular desulfitative coupling
will open up a new avenue for the development of catalytic
transformations of sulfonyl compounds.
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ASSOCIATED CONTENT
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The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.or-
glett.8b02972.
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Detailed experimental procedures and full spectroscopic
data for all new compounds (PDF)
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́
AUTHOR INFORMATION
Corresponding Author
■
*
of C−H Bonds via Metal-Catalyzed Desulfitative Coupling: An
Alternative Tool for Access to Aryl- or Alkyl-Substituted (Hetero)-
arenes. ACS Catal. 2015, 5, 978−991. (b) Ortgies, D. H.; Hassanpour,
A.; Chen, F.; Woo, S.; Forgione, P. Desulfination as an Emerging
Strategy in Palladium-Catalyzed C−C Coupling Reactions. Eur. J. Org.
E-mail: yori@kuchem.kyoto-u.ac.jp.
ORCID
Keisuke Nogi: 0000-0001-8478-1227
Hideki Yorimitsu: 0000-0002-0153-1888
Notes
Chem. 2016, 2016, 408−425. (c) Li, H.; Sasmal, A.; Shi, X.; Soule, J.-
́
F.; Doucet, H. Halo-substituted benzenesulfonyls and benzene-
sulfinates: convenient sources of arenes in metal- catalyzed C−C
bond formation reactions for the straightforward access to halo-
substituted arenes. Org. Biomol. Chem. 2018, 16, 4399−4423.
The authors declare no competing financial interest.
(
7) Selected recent examples: (a) Skhiri, A.; Salem, R. B.; Soule, J.-
́
ACKNOWLEDGMENTS
F.; Doucet, H. Palladium-Catalysed Desulfitative Heck Reaction
Tolerant to Aryl Carbon−Halogen Bonds for Access to (Poly)halo-
Substituted Stilbene or Cinnamate Derivatives. Synthesis 2016, 48,
■
This work was supported by JSPS KAKENHI Grant Numbers
JP16H04109, JP18H04254, JP18H04409, and JP18K14212.
K.N. and H.Y. thank Toyota Physical and Chemical Research
Institute and The Asahi Glass Foundation, respectively, for
financial support. We also thank Nippon Light Metal
Company, Ltd. for providing NaOCl·5H O to prepare the
starting materials.
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DOI: 10.1021/acs.orglett.8b02972
Org. Lett. XXXX, XXX, XXX−XXX