Cross-Coupling of Aryl Trifluoromethyl Sulfones with Arylboronates by Cooperative Palladium/Rhodium Catalysis

Article abstract of DOI:10.1021/acs.orglett.9b03393

The Suzuki-Miyaura arylation of aryl trifluoromethyl sulfones via C-SO₂ bond cleavage has been developed by means of cooperative palladium/rhodium catalysis. A series of aryl trifluoromethyl sulfones and arylboronic acid neopentylglycol esters are converted to the corresponding biaryls. Mechanistic investigations suggest that (1) the rhodium catalyst mediates the transfer of the aryl ring from arylboronate to palladium, resulting in the acceleration of the transmetalation step, and (2) the C-C bond-forming reductive elimination step is the turnover-limiting step.

Full text of DOI:10.1021/acs.orglett.9b03393

Letter
pubs.acs.org/OrgLett
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
Cross-Coupling of Aryl Trifluoromethyl Sulfones with Arylboronates
by Cooperative Palladium/Rhodium Catalysis
Jun-ichi Fukuda, Keisuke Nogi, and Hideki Yorimitsu*
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
S
* Supporting Information
ABSTRACT: The Suzuki−Miyaura arylation of aryl trifluor-
omethyl sulfones via C−SO2 bond cleavage has been developed
by means of cooperative palladium/rhodium catalysis. A series
of aryl trifluoromethyl sulfones and arylboronic acid neo-
pentylglycol esters are converted to the corresponding biaryls.
Mechanistic investigations suggest that (1) the rhodium catalyst
mediates the transfer of the aryl ring from arylboronate to palladium, resulting in the acceleration of the transmetalation step,
and (2) the C−C bond-forming reductive elimination step is the turnover-limiting step.
iaryl skeletons represent a pivotal substructure in organic
chemistry and related fields including pharmaceutical and
B
agrochemical industry as well as advanced material science.
The Suzuki−Miyaura cross-coupling of aryl electrophiles with
arylboronic acid derivatives is among the most important
methodologies for the construction of biaryl skeletons.1
Besides conventional aryl halides and triflates, the Suzuki−
Miyaura arylation of less reactive aryl electrophiles containing
C−F,2 C−O,3 and C−N4,5 bonds has been emerging.
On the contrary, the Suzuki−Miyaura arylation of aromatic
organosulfur compounds has been relatively unexplored,
whereas catalytic C−S transformation has attracted much
attention in the cross-coupling arena.6 As a seminal work,
Liebeskind developed the palladium-catalyzed arylation of
arylsulfonium salts (Figure 1a, left).7,8 Although the reaction
proceeded under mild conditions due to their enhanced
reactivity, the starting sulfonium salts intrinsically suffer from
dealkylative decomposition. In 2002, Liebeskind and Srogl
accomplished Suzuki−Miyaura cross-coupling of aryl sulfides
by means of a palladium catalyst and copper thiophenecarbox-
ylate (CuTC) (Figure 1a, center).9,10 However, the applicable
substrates were limited to azaaryl sulfides such as electron-
deficient pyridyl and thiazolyl sulfides. Although Willis and Shi
independently reported the arylation of aryl sulfides with
rhodium catalysts, the reactions require carbonyl directing
groups at the ortho positions (Figure 1a, right).11
To develop a new class of Suzuki−Miyaura arylation of
aromatic organosulfur compounds, we focused on the use of a
fluorinated sulfonyl leaving group. Recently, Nambo and
Crudden accomplished the Suzuki−Miyaura arylation of
benzyl sulfones by means of the rationally designed fluorinated
sulfonyl leaving groups (Figure 1b),12 where the departing
sulfinate anions were stabilized to facilitate the C−SO2 bond
cleavage. Along this line, we envisioned that the trifluor-
omethylsulfonyl (CF3SO2−) group can be a suitable leaving
group for the Suzuki−Miyaura arylation of aryl sulfones. Here
we report the Suzuki−Miyaura arylation of aryl trifluoromethyl
sulfones with arylboronates (Figure 1c). Cooperative palla-
Figure 1. Suzuki−Miyaura arylation of organosulfur compounds.
dium/rhodium catalysis was particularly effective for efficient
conversion. Mechanistic investigations suggest that the
rhodium catalyst mediates the transfer of the aryl ring from
arylboronates to the palladium catalyst, resulting in the
acceleration of the transmetalation on the palladium center.
Received: September 25, 2019
© XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.9b03393
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
During the preparation of the manuscript, Moran also reported
the Suzuki−Miyaura arylation of aryl trifluoromethyl sulfones
under palladium−RuPhos catalysis (Figure 1d).13
We chose the reaction of phenyl trifluoromethyl sulfone
(1a) with 4-methoxyphenylboronic acid neopentylglycol ester
(2a) as a model reaction. Because Pd−NHC (N-heterocyclic
carbene) complexes showed good catalytic activity in our
previous C−S transformations,6d we performed the reaction
with 10 mol % of Pd-PEPPSI-IPr (see Figure 2 for the
effective for the reaction, and no 3aa was obtained with
RhH(PPh3)4 (entries 7 and 8).
With [RhCl(cod)]2 as the optimal cocatalyst, we continued
the optimization study with lower catalyst loadings: 2.5 mol %
of a palladium catalyst and 1.3 mol % of [RhCl(cod)]2 (Table
2; see Table S2 for details of the screening of palladium
Table 2. Screening of Conditions
entry
Pd catalyst
base
GC yield (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
Pd-PEPPSI-IPr
Pd-PEPPSI-IMes
4
4
4
4
4
4
4
none
4
4
4
LiOtBu
LiOtBu
LiOtBu
NaOtBu
KOtBu
LiOAc
Li2CO3
CsF
LiOtBu
LiOtBu
LiOtBu
LiOtBu
40
0
85
28
8
Figure 2. Structures of ligands and catalysts.
structures of ligands and metal complexes) in the presence of
LiOtBu as a base. Whereas the desired biaryl 3aa was formed,
the yield was only 27%, and 56% of sulfone 1a was recovered
(Table 1, entry 1).
0
0
65
91 , 92
0
52
78
a
b
bc
,
a
ad
,
Table 1. Evaluation of Cocatalysts
ae
,
af
,
LiOtBu
25
a
b
c
d
Concentration: 0.5 M. Isolated yield. 2.0 mmol scale. Without
e
f
[RhCl(cod)]2. 4-MeOC6H4B(OH)2 instead of 2a. 4-MeOC6H4B-
(pin) instead of 2a.
catalysts). When Pd-PEPPSI-IPr was employed, 3aa was
obtained in 40% yield, although Pd-PEPPSI-IMes entirely
entry
cocatalyst
none
CuTC
GC yield (%)
shut down the reaction (entries 1 and 2). To our delight,
14
diisopropylamino-substituted IPr (IPrNiPr2
)
was found to be
1
2
3
4
27
13
40
4
75
74
32
0
highly effective; the yield of 3aa was considerably improved to
85% by means of IPrNiPr2-ligated palladium complex 4 (entry
3). The choice of the countercation of bases has a great impact
on the yield of the product, and the yields of 3aa significantly
dropped with NaOtBu and KOtBu (entries 4 and 5).
Unfortunately, milder bases such as LiOAc and Li2CO3 were
not suitable for this reaction, whereas CsF afforded 3aa in a
moderate yield (entries 6−8). Eventually, 3aa was obtained in
91% isolated yield under more concentrated conditions (0.5
M) (entry 9). Naturally, the absence of palladium catalyst 4
did not give the product at all (entry 10). The use of the
rhodium cocatalyst again proved to be important for the high
yield of the product; 3aa was obtained in 52% yield in the
absence of [RhCl(cod)]2 (entry 11). We also tested other
arylboron reagents instead of 2a. Although 4-MeOC6H4B-
(OH)2 could also be used for the reaction, the use of the
corresponding pinacol ester, 4-MeOC6H4B(pin), resulted in a
much lower yield of 3aa (entries 12 and 13).15
CuCl(IPr)
CuCl(dppe)
[RhCl(cod)]2
[Rh(OH)(cod)]2
[RhCl(nbd)]2
RhH(PPh3)4
a
5
a
6
a
7
8
a
5 mol % of cocatalyst was used.
To facilitate the reaction, we next attempted the addition of
a metal cocatalyst to the reaction system because previous
Suzuki−Miyaura arylations of azaaryl sulfides require the
addition of CuTC.9 (See Table S1 for details of the evaluation
of cocatalysts.) The thiophilic copper salt interacts with the
thiolate anion on the palladium catalyst, resulting in the
acceleration of the transmetalation process. Although the use
of CuTC and copper−phosphine complexes lowered the yield
of 3aa, 10 mol % of CuCl(IPr) increased the yield to 40%
(Table 1, entries 2−4). Gratifyingly, in place of copper,
rhodium complexes showed good catalytic activities; the
employment of [RhCl(cod)]2 and [Rh(OH)(cod)]2 gave 3aa
in 75 and 74% yields, respectively (entries 5 and 6). On the
contrary, [RhCl(nbd)]2 (nbd = norbornadiene) was less
Having the optimized conditions in hand (Table 2, entry 9),
the reaction scope with respect to aryl trifluoromethyl sulfones
1 was investigated (Scheme 1a). Electron-rich 4-methox-
yphenyl sulfone 1b underwent the arylation, whereas higher
catalyst loadings (5.0 mol % of 4 and 2.5 mol % of
[RhCl(cod)]2) were necessary for a high yield of the product.
Several functional groups including siloxy, fluoro, benzoyl, and
B
DOI: 10.1021/acs.orglett.9b03393
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Organic Letters
Letter
(3al) was obtained in 78% yield, whereas 2- or 3-
thienylboronate 2m or 2n failed to be applied to the arylation.
Not only arylboronates but also trans-2-phenylvinylboronate
2o underwent the reaction to furnish trans-stilbene (3ao) in
moderate yield.
Scheme 1. Scope of Arylation
Instead of trifluoromethyl sulfones, heptafluoropropyl
sulfone 1k could be employed for the arylation, and the
desired product 3ka was obtained in 70% yield (Scheme 2a).
Scheme 2. Reactions of Aryl Sulfones Bearing Sulfonyl
Groups Other than Trifluoromethylsulfonyl Group
Perfluorinated sulfonyl groups proved to be essential for the
reaction; no biaryl 3ia was obtained from methyl 2-naphthyl
sulfone (1i′), resulting in the quantitative recovery of 1i′
(Scheme 2b).
As shown in Table 1, the addition of [RhCl(cod)]2 as the
cocatalyst dramatically promotes the present arylation. To
learn about the effect of the rhodium catalyst, we assessed the
kinetic profile of the arylation in the presence (4: 2.5 mol %,
[RhCl(cod)]2: 1.3 mol %) or the absence (4: 5.0 mol %) of the
rhodium catalyst. As shown in Figure 3, the initial reaction rate
(r0) of the cocatalyzed system (red) was much higher than that
of the reaction without [RhCl(cod)]2 (blue). These results
demonstrate the acceleration effect of the rhodium catalyst.
Moreover, a significantly longer induction period (until 50
min) was observed in the absence of [RhCl(cod)]2, which
a
b
5.0 mol % of 4, 2.5 mol % of [RhCl(cod)]2, 24 h. LiOH·H2O
instead of LiOtBu.
tert-butyl ester were compatible with the present arylation to
yield biaryls 3ca−fa. Unfortunately, methylsulfanyl-substituted
phenyl sulfone 1g did not undergo the reaction, resulting in the
quantitative recovery of 1g. Deactivated palladium thiolate
species might be formed via the C−SMe cleavage, resulting in
no turnover of the palladium catalyst. The methyl group at the
ortho position of 1h did not hamper the reaction to afford 3ha
in 85% yield. 2-Naphthyl sulfone 1i uneventfully took part in
the arylation to provide 3ia.
The reaction scope with respect to arylboronates 2 was then
explored (Scheme 1b). Both electron-rich and -poor
arylboronates underwent the present arylation to afford the
desired biaryls in high yield. The trimethylsilyl group on 2c
was also tolerated; the desired product 3ac was obtained in
96% yield. The employment of arylboronate 2g having an
acetyl moiety resulted in the formation of a 31% yield of 3ag
under the standard conditions. The degradation of the acetyl
group by strongly basic LiOtBu was thought to be problematic.
The use of LiOH·H2O as a milder base improved the yield of
3ag to 48%. 4-Chlorophenylboronate 2h did not participate in
the reaction; 2h was consumed by polymerization via the C−
Cl bond cleavage. The methylsulfanyl group on arylboronate 2i
was detrimental to the reaction, and both aryl sulfone 1a and
arylboronate 2i were recovered after the reaction. The
deactivation of the palladium catalyst via the C−SMe cleavage
was problematic (vide supra). The reaction with ortho-
substituted arylboronate 2k proceeded efficiently to give 2-
methyl-1,1′-biphenyl (3ak) in 82% yield. The use of 2-
furylboronate 2l did not retard the reaction, and 2-phenylfuran
Figure 3. Time profiles of the yields of 3aa with (red) or without
(blue) [RhCl(cod)]2 (with Rh: 2.5 mol % of 4 and 1.3 mol % of
[RhCl(cod)]2; without Rh: 5.0 mol % of 4).
C
DOI: 10.1021/acs.orglett.9b03393
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
implies that the rhodium catalyst would facilitate the
generation of active Pd(0) species from precatalyst 4.
Rhodium complexes readily react with arylboronates to
generate arylrhodium species.16 We thus hypothesized that
[RhCl(cod)]2 would mediate the transfer of the aryl ring from
arylboronate to the palladium catalyst to accelerate the
transmetalation step on the palladium center.
A possible mechanism based on this hypothesis is depicted
in Scheme 3. First, the palladium precatalyst 4 would be
Scheme 3. Possible Catalytic Cycle of Pd/Rh Co-Catalyzed
Cross-Coupling
Figure 4. Plots of initial reaction rate (r0) against [2a]0 with (red) or
without (blue) [RhCl(cod)]2.
the turnover-limiting step in the absence of [RhCl(cod)]2.
These indicate the intermediacy of the rhodium catalyst for the
rapid transfer of the aryl ring from arylboronate to the
palladium catalyst.
We also measured r0 against the initial concentrations of 1a
([1a]0) and [RhCl(cod)]2 ([Rh]0), respectively. (See Figures
S1, S2, S8, and S9 for details.) Under the concentrations
studied, it turned out that r0 was almost zero-order in [1a]0
and [Rh]0, respectively. These results imply that neither of the
steps, neither the oxidative addition of 1 (Scheme 3, step b)
nor the generation of arylrhodium B (Scheme 3, step e), would
be a turnover-limiting step.
On the contrary, the plot of r0 against the initial
concentration of palladium precatalyst 4 ([4]0) showed
positive dependence, and the reaction was estimated to nearly
first-order in [4]0. (See Figures S6 and S7 for details.) These
observations are consistent with the turnover-limiting step
reduced to Pd(0) via two-fold transmetalation with 2 and
subsequent reductive elimination (step a) because a much
shorter induction period was observed in the presence of
[RhCl(cod)]2 (Figure 3, red). We assume that the rhodium
catalyst would accelerate the transmetalation step, resulting in
the rapid generation of the Pd(0) species. The aryl
trifluoromethyl sulfone 1 would undergo oxidative addition
with the Pd(0) species to afford arylpalladium(II) A (step b).
Intermediate A would go through transmetalation with
arylrhodium B generated from Rh(I) species and arylboronate
2 with the aid of LiOtBu to provide diarylpalladium C (step c).
Finally, the reductive elimination from C would furnish
coupling product 3 with the regeneration of NHC−Pd(0)
(step d).
To gain further insight into the transmetalation step, we
then measured r0 while changing the initial concentrations of
2a and LiOtBu. (See Figures S3−S5 for details.)17 In the
presence of [RhCl(cod)]2, under the concentrations studied, r0
of the reaction was estimated to almost zero-order in the initial
concentration of 2a ([2a]0) (Figure 4, red).18,19 The
transmetalation step between arylpalladium A and arylrhodium
B (Scheme 3, step c) was not a turnover-limiting step.
Conversely, in the absence of the rhodium catalyst, the plot of
r0 against [2a]0 showed a positive dependence under the
concentrations studied (Figure 4, blue). The reaction was
approximately 1.6-order in [2a]0, which implies that the
transmetalation between palladium and arylboronate would be
being the reductive elimination step to afford biaryls 3
NiPr2
́
(Scheme 3, step d). Cesar found that the bulky IPr
ligand
facilitates the C−N bond-forming reductive elimination,
resulting in the acceleration of the Buchwald−Hartwig
amination with bulky amines.14 In a similar fashion, the
IPrNiPr2 ligand accelerated the turnover-limiting reductive
elimination step, and the Pd−IPrNiPr2 complex thus showed
the highest catalytic activity in our arylation.
On the basis of their mechanistic and computational studies,
Moran et al. suggested that the oxidative addition of the C−S
bond of an aryl trifluoromethyl sulfone to a Pd(0)−RuPhos
complex would be the turnover-limiting step in their system.13
On the contrary, in our system, electron-rich IPrNiPr2 ligand
would accelerate the C−S cleavage, and thus the oxidative
addition would not be a turnover-limiting step.
In conclusion, we have developed the Suzuki−Miyaura
arylation of aryl trifluoromethyl sulfones under cooperative
palladium/rhodium catalysis. The arylation herein presented
accommodates a series of aryl trifluoromethyl sulfones as well
as arylboronates to give the corresponding biaryls in moderate
to excellent yield. Kinetic measurements indicate that (1) the
rhodium catalyst mediates the transfer of the aryl ring from
D
DOI: 10.1021/acs.orglett.9b03393
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
(8) Related C−S cleaving reactions of sulfonium salts with
organoboron compounds: (a) Zhang, S.; Marshall, D.; Liebeskind,
L. S. J. Org. Chem. 1999, 64, 2796. (b) Lin, H.; Dong, X.; Li, Y.; Shen,
Q.; Lu, L. Eur. J. Org. Chem. 2012, 2012, 4675. (c) Vasu, D.;
Yorimitsu, H.; Osuka, A. Angew. Chem., Int. Ed. 2015, 54, 7162.
(d) Vasu, D.; Yorimitsu, H.; Osuka, A. Synthesis 2015, 47, 3286.
(e) Minami, H.; Otsuka, S.; Nogi, K.; Yorimitsu, H. ACS Catal. 2018,
8, 579. (f) Berger, F.; Plutschack, M. B.; Riegger, J.; Yu, W.; Speicher,
S.; Ho, M.; Frank, N.; Ritter, T. Nature 2019, 567, 223.
arylboronate to palladium, resulting in the acceleration of the
transmetalation on the palladium center, and (2) the C−C
bond-forming reductive elimination step is the turnover-
limiting step that would be accelerated by IPrNiPr2 ligand.
ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.or-
glett.9b03393.
(9) Liebeskind, L. S.; Srogl, J. Org. Lett. 2002, 4, 979.
(10) Related works on Suzuki−Miyaura coupling of activated
organosulfur compounds: (a) Liebeskind, L. S.; Srogl, J. J. Am. Chem.
Soc. 2000, 122, 11260. (b) Savarin, C.; Srogl, J.; Liebeskind, L. S. Org.
Lett. 2001, 3, 91. (c) Yu, Y.; Liebeskind, L. S. J. Org. Chem. 2004, 69,
3554.
Experimental procedures, kinetic measurements, and
spectral data (PDF)
(11) (a) Hooper, J. F.; Young, R. D.; Pernik, I.; Weller, A. S.; Willis,
M. C. Chem. Sci. 2013, 4, 1568. (b) Pan, F.; Wang, H.; Shen, P.-X.;
Zhao, J.; Shi, Z.-J. Chem. Sci. 2013, 4, 1573.
(12) (a) Nambo, M.; Crudden, C. M. Angew. Chem., Int. Ed. 2014,
53, 742. (b) Nambo, M.; Keske, E. C.; Rygus, J. P. G.; Yim, J. C.-H.;
Crudden, C. M. ACS Catal. 2017, 7, 1108. Related works: (c) Ariki,
Z. T.; Maekawa, Y.; Nambo, M.; Crudden, C. M. J. Am. Chem. Soc.
2018, 140, 78. (d) Nambo, M.; Tahara, Y.; Yim, J. C.-H.; Crudden, C.
M. Chem. - Eur. J. 2019, 25, 1923. (e) Yim, J. C. H.; Nambo, M.;
Tahara, Y.; Crudden, C. M. Chem. Lett. 2019, 48, 975.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: yori@kuchem.kyoto-u.ac.jp.
ORCID
Keisuke Nogi: 0000-0001-8478-1227
Hideki Yorimitsu: 0000-0002-0153-1888
Notes
(13) Chatelain, P.; Sau, A.; Rowley, C. N.; Moran, J. Angew. Chem.,
Int. Ed. 2019, 58, 14959.
The authors declare no competing financial interest.
́
(14) Zhang, Y.; Lavigne, G.; Lugan, N.; Cesar, V. Chem. - Eur. J.
2017, 23, 13792.
ACKNOWLEDGMENTS
■
(15) The substituents on the boron atoms of arylboron compounds
dramatically affect Suzuki−Miyaura cross-coupling. Thomas, A. A.;
Zahrt, A. F.; Delaney, C. P.; Denmark, S. E. J. Am. Chem. Soc. 2018,
140, 4401.
This work was supported by JSPS KAKENHI Grant Numbers
JP16H04109, JP18H04254, JP18H04409, JP19H00895, and
JP18K14212.
(16) Selected examples of rhodium-catalyzed transformations of
organoboron compounds: (a) Sakai, M.; Hayashi, H.; Miyaura, N.
Organometallics 1997, 16, 4229. (b) Takaya, Y.; Ogasawara, M.;
Hayashi, T.; Sakai, M.; Miyaura, N. J. Am. Chem. Soc. 1998, 120, 5579.
Direct observation of arylrhodium species from arylboronic acids:
(c) Hayashi, T.; Takahashi, M.; Takaya, Y.; Ogasawara, M. J. Am.
Chem. Soc. 2002, 124, 5052. (d) Zhao, P.; Incarvito, C. D.; Hartwig, J.
F. J. Am. Chem. Soc. 2007, 129, 1876.
(17) The measurements of the r0 were conducted after the induction
periods.
(18) In the presence of the Rh catalyst, the aryl transfer from
arylboronate to the Rh was sufficiently fast. Therefore, under the
concentration studied, a considerable y intercept was consistently
observed.
(19) In the present cross-coupling, homocoupling of arylboronates 2
to the corresponding biaryls was observed as a side reaction. The
homocoupling was accelerated by increasing [2a]0 because this
process can be second-order in [2a]0. The palladium and rhodium
catalysts were involved not only in the cross-coupling but also in the
competing homocoupling, which resulted in the apparent deceleration
of the cross-coupling by increasing [2a]0. The slightly negative slope
of the plot was consistent with these considerations.
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