Palladium-Catalyzed Arylation of Arylboronic Acids with Yagupolskii-Umemoto Reagents

Article abstract of DOI:10.1002/chem.201600991

A Pd-catalyzed Suzuki cross-coupling of arylboronic acids with Yagupolskii-Umemoto reagents was explored. In contrary to trifluoromethylations, the Pd-catalyzed reaction of R-B(OH)₂ and [Ar₂SCF₃]⁺[OTf]^- provided the arylation products (R-Ar) in good to high yields. The reaction confirms that the S-Ar bonds of [Ar₂SCF₃]⁺[OTf]^- can be readily cleaved in the presence of Pd complexes. The relatively electron-poor aryl groups of asymmetric [Ar¹Ar²SCF₃]⁺[OTf]^- salts are more favorably transferred compared to the electron-rich ones. This reaction represents the first report of utilization of [Ar₂SCF₃]⁺[OTf]^- as arylation reagents in organic synthesis.

Full text of DOI:10.1002/chem.201600991

DOI: 10.1002/chem.201600991
Communication
&
Arylation
Palladium-Catalyzed Arylation of Arylboronic Acids with
Yagupolskii–Umemoto Reagents
Shi-Meng Wang, Xiao-Yan Wang, Hua-Li Qin, and Cheng-Pan Zhang*[a]
Abstract: A Pd-catalyzed Suzuki cross-coupling of aryl-
boronic acids with Yagupolskii–Umemoto reagents was
explored. In contrary to trifluoromethylations, the Pd-cata-
lyzed reaction of RÀB(OH)2 and [Ar2SCF3]+[OTf]À provided
the arylation products (RÀAr) in good to high yields. The
reaction confirms that the SÀAr bonds of [Ar2SCF3]+[OTf]À
can be readily cleaved in the presence of Pd complexes.
The relatively electron-poor aryl groups of asymmetric
[Ar1Ar2SCF3]+[OTf]À salts are more favorably transferred
compared to the electron-rich ones. This reaction repre-
sents the first report of utilization of [Ar2SCF3]+[OTf]À as
arylation reagents in organic synthesis.
Scheme 1. Reductive trifluoromethylations with Yagupolskii–Umemoto re-
agents.
tion-metal complexes were oxidized by “+CF3” reagents to
form the desired hypervalent metal–CF3 species.[6] Neverthe-
less, similar reactions between transition metals (e.g., Pd com-
plexes) and Yagupolskii–Umemoto reagents are still unknown.
These situations seriously restrict the use of [Ar2SCF3]+[OTf]À in
an expanded field.
Yagupolskii–Umemoto reagents ([Ar2SCF3]+[OTf]À) have been
successfully used in areas of chemistry, biology, and materials
science for the direct incorporation of CF3 groups into organic
scaffolds.[1–3] These reagents, first synthesized by Yagupolskii
and co-workers at the end of 1970 s and then modified by
Umemoto, Shreeve, and others, were traditionally regarded as
electrophilic +CF3 transfer reagents.[1,2a–c] Recently, S-(trifluoro-
methyl)diphenylsulfonium salts were found to be easily re-
duced by copper, photoredox catalysts, and other reductants
(e.g., rongalite) because of their appreciable oxidation proper-
ties.[3] These discoveries consequently lead to the flourish of re-
ductive trifluoromethylation involving not only [Ar2SCF3]+
[OTf]À but also Umemoto and Togni’s reagents in the last few
years.[3h,4]
To gain some insights into this area, we initially performed
the reaction of [Ph2SCF3]+[OTf]À with [Pd(PtBu3)2] in DMF at
room temperature, 808C or 1208C for 8 h (Figure 1). Interest-
ingly, 19F NMR analysis of the reaction mixtures showed a char-
acteristic signal at d=À43.5 ppm (Figure 1), and GC-MS analy-
sis of the reaction mixture provided a distinct peak of m/z=
178.0, indicating the formation of phenyl trifluoromethyl sul-
fide (PhSCF3).[7] With the observation of PhSCF3, we proposed
Compared to Umemoto’s reagents, the Yagupolskii–Umemo-
to reagents have shown a narrow range of transition-metal
catalysis. To our knowledge, only Cu-mediated and photore-
dox-catalyzed reactions of [Ar2SCF3]+[OTf]À have been ex-
plored to date (Scheme 1).[3] Although the Pd-catalyzed CÀH
activation/functionalization with Umemoto’s reagents has
been accomplished, the Pd-catalyzed reactions of [Ar2SCF3]+
[OTf]À have been rarely studied.[5] Furthermore, the use of
Umemoto’s reagents as oxidants and CF3 sources to construct
LIrIIIÀCF3, LPdIVÀCF3 (2–4% yields), and LNiIVÀCF3 intermediates
was disclosed, in which the corresponding low-valent transi-
Figure 1. 19F NMR analysis of the reaction mixture of [Ph2SCF3]+[OTf]À and
[Pd(PtBu3)2] in DMF under N2 atmosphere. A: [Ph2SCF3]+[OTf]À (0.15 mmol),
[Pd(PtBu3)2] (0.15 mmol), DMF (2 mL), r.t., 8 h. B: [Ph2SCF3]+[OTf]À
(0.15 mmol), [Pd(PtBu3)2] (0.15 mmol), DMF (2 mL), 808C, 8 h.
[a] S.-M. Wang, X.-Y. Wang, Prof. Dr. H.-L. Qin, Prof. Dr. C.-P. Zhang
School of Chemistry, Chemical Engineering and Life Science
Wuhan University of Technology
C: [Ph2SCF3]+[OTf]À (0.15 mmol), [Pd(PtBu3)2] (0.15 mmol), DMF (2 mL), 808C,
8 h, then 1a (0.1 mmol) was added and reacted for 15 h. D: [Ph2SCF3]+[OTf]À
(0.15 mmol), [Pd(PtBu3)2] (0.15 mmol), DMF (2 mL), 1208C, 8 h.
E: [Ph2SCF3]+[OTf]À (0.20 mmol), 1a (0.1 mmol), [Pd(PtBu3)2] (5 mol%),
NaHCO3 (0.1 mmol), DMF (2 mL), 808C, 24 h.
205 Luoshi Road, Wuhan 430070 (P. R. China)
E-mail: cpzhang@whut.edu.cn
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201600991.
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that a LPdÀPh intermediate might be simultaneously formed
in the reaction. Moreover, the 19F NMR spectra of the reaction
mixture showed another negligible peak of d=À23.6 ppm,
which disappeared with elevating the reaction temperature.
This resonance might belong to “PdÀCF3” intermediates,[8] the
formation of which might be indirectly evidenced by the isola-
tion of diphenyl sulfide from the reaction mixture. All these
suggest that either the PhÀS bond or the SÀCF3 bond of
[Ph2SCF3]+[OTf]À was split in the presence of [Pd(PtBu3)2]. The
breakage of the former seems to be easier than that of the
latter according to the molar ratio of the CF3 species (PhSCF3
versus “PdÀCF3”), which was determined by 19F NMR analysis of
the reaction mixtures.
Table 1. Screening the optimized conditions for Pd-catalyzed arylation of
1a by 2a.
Entry
Catalyst
Base
Yield of 3aa [%][a]
1[b]
[Pd(PtBu3)2]
[Pd(PPh3)4]
[Pd2(dba)3]
[Pd(dba)2]
Pd/C
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
K2CO3
KF
K3PO4
NaOAc
–
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
73
34
4
5
4
36
0
47
12
0
18
37
6
10
6
2[b]
3[b]
4[b]
5[b]
6[b]
Pd(OAc)2
7[b]
PdCl2/PPh3 (30 mol%)
[Pd(PtBu3)2]
[Pd(PCy3)2]
–
8[c]
At this stage, we envisioned that [Ph2SCF3]+[OTf]À may be
a good phenyl transfer source with Pd catalysts. Thus, 4-chloro-
9[c]
10[d]
11[c]
12[c]
13[c]
14[c]
15[c]
16[c,e]
17[c,f]
18[c,g]
19[d]
20[d,h]
21[i]
phenylboronic acid (1a) was added into
a solution of
[Pd(PtBu3)2]
[Pd(PtBu3)2]
[Pd(PtBu3)2]
[Pd(PtBu3)2]
[Pd(PtBu3)2]
[Pd(PtBu3)2]
[Pd(PtBu3)2]
[Pd(PtBu3)2]
[Pd(PtBu3)2]
[Pd(PtBu3)2]
[Pd(PtBu3)2]
[Ph2SCF3]+[OTf]À and [Pd(PtBu3)2] in DMF, which was already re-
acted at 808C for 8 h, and the mixture was kept at 808C for an-
other 15 h. As expected, the Suzuki cross-coupling product
3aa was obtained in 5% yield accompanied by the homocou-
pling of 1a (7%). Nevertheless, when the Umemoto’s reagent
was used in the same reaction, no arylation product was
formed and the signal of at dꢀÀ43 ppm was scarcely ob-
served in 19F NMR spectra of the reaction mixtures (see the
Supporting Information). This is varied from those in literatures
in which both non-fluorinated aryltetramethylenesulfonium
and dibenzothiophenium salts were effective participants in
palladium-catalyzed cross-coupling reactions with organobor-
on reagents.[9] Although the Pd-catalyzed arylation of arylbor-
onic acids have been extensively investigated by a large
number of research groups around the world using aryl halides
or tosylates, azidoarenes, and diaryl iodine(III) reagents as
electrophiles,[10] the use of [Ar2SCF3]+[OTf]À as an arylation
reagent has never been reported. Herein, we disclose the first
Pd-catalyzed Suzuki cross-coupling arylation of arylboronic
acids with Yagupolskii–Umemoto reagents.
29
18
51
76
63
43
[a] Yields were determined by HPLC using 3aa as external standard. The
homocoupling of 1a was observed in most cases (0–44% yields, see the
Supporting Information). [b] Reaction conditions: 1a (0.1 mmol),
[Ph2SCF3]+[OTf]À (0.12 mmol), catalyst (0.01 mmol), NaHCO3 (0.12 mmol),
DMF (2 mL). [c] Reaction conditions: 1a (0.4 mmol), [Ph2SCF3]+[OTf]À
(0.48 mmol), catalyst (0.004 mmol), NaHCO3 (0.48 mmol), DMF (3 mL).
[d] 1a (0.1 mmol), [Ph2SCF3]+[OTf]À (0.2 mmol), [Pd(PtBu3)2] (0.01 mmol),
NaHCO3 (0.1 mmol), DMF (2 mL). [e] 608C. [f] 1008C. [g] 36 h.
[h] [Pd(PtBu3)2] (0.005 mmol). [i] Reaction conditions: 1a (0.48 mmol),
[Ph2SCF3]+[OTf]À (0.4 mmol), [Pd(PtBu3)2] (0.02 mmol), NaHCO3 (0.4 mmol),
DMF (3 mL).
It was found that the reaction of 1a (1 equiv) and [Ph2SCF3]+
[OTf]À (1.2 equiv) in the presence of [Pd(PtBu3)2] (10 mol%) and
NaHCO3 (1.2 equiv) in DMF at 808C for 24 h gave 3aa in 73%
yield (Table 1, entry 1). Beside [Pd(PtBu3)2], other Pd complexes,
such as [Pd(PPh3)4], Pd(OAc)2, [Pd2(dba)3], [Pd(dba)2], Pd/C,
Pd(OAc)2, and [Pd(PCy3)2], are also viable catalysts for the
reaction; however, providing lower yields of the products (en-
tries 2–6 and 9). The catalyst loading has considerable influ-
ence on the reaction (entries 1, 8, and 20). When the amount
of [Pd(PtBu3)2] was reduced to 1 mol%, the yield of 3aa was
decreased to 47% (entry 8). When the reaction was conducted
without Pd-catalyst, no desired product was formed (entry 10).
NaHCO3 was the suitable base for the Pd-catalyzed arylation
since the use of K2CO3, KF, K3PO4, and NaOAc led to less effi-
cient conversions (entries 11–14). The reaction with 1 mol%
[Pd(PtBu3)2] in the absence of base provided the desired prod-
uct in only 6% yield (entry 15). Furthermore, the reaction tem-
perature can affect the transformation. Both lowering (608C)
and elevating (1008C) the reaction temperature hindered the
production of 3aa (entries 16 and 17). Prolonging the reaction
time from 24 to 36 h, a comparable yield of 3aa (51 versus
47%) was obtained (entries 8 and 18). Increasing the molar
ratio of [Ph2SCF3]+[OTf]À to 1a in the presence of 10 mol%
[Pd(PtBu3)2] just slightly improved the yield of 3aa (76 versus
73%, entries 1 and 19), and the same reaction in the presence
of 5 mol% [Pd(PtBu3)2] afforded 3aa in 63% yield (entry 20).
Nevertheless, using excess arylboronic acids to work with
[Ph2SCF3]+[OTf]À gave a lower yield of 3aa (43%, entry 21).
Then,
a
combination of [Ph2SCF3]+[OTf]À (2 equiv),
[Pd(PtBu3)2] (5 or 10 mol%), NaHCO3 (1 equiv) in DMF at 808C
for 24 h was employed to test the scope of the reaction with
various arylboronic acids (1 equiv). To our delight, arylboronic
acids 1b–r with either electron-withdrawing or -donating
groups were all successfully transformed, affording the corre-
sponding arylation products 3ab–ar (Table 2) in good to high
yields. The position of substituents on the phenyl rings has
general influence on the reaction (e.g., 3ab–ac, 3ad–af, and
3ak–am). The meta-substitution also facilitated the transforma-
tion (e.g., 3ac, 3ae, 3al). Increasing the catalyst loading of
[Pd(PtBu3)2] from 5 to 10 mol% significantly improved the
yields of 3ag, 3ah, 3ak, and 3am but hardly change the yield
of 3af. The reaction is also compatible with the sensitive
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tion, the desired arylation product 3 fx was obtained
in a pure form.
Table 2. Pd-catalyzed arylation of arylboronic acids by 2a.
A final question concerns the selectivity of the Pd-
catalyzed arylation of arylboronic acids with Yagupol-
skii–Umemoto reagents bearing two different aryl
groups. Hence, the reactions of phenylboronic acid
(1x) with asymmetric [Ar1Ar2SCF3]+[OTf]À salts (2g,
2h, and 2i) were sought out (Table 4). Notably, 2g re-
acted with 1x and gave a mixture of 3bx and 4b in
83% yield, the molar ratio of which was 1:5. Treat-
ment of 2h with 1x provided a mixture of 3cx and
4b in 69% yield (molar ratio of 1:1.5), whereas the re-
action of 2i and 1x afforded 3aa and 4b in totally
87% yield with a molar ratio of 1.7:1. These data
imply that the electron-rich aryl groups of
[Ar1Ar2SCF3]+[OTf]À are slowly transferred compared
to those that are relatively electron-poor.
Based on the results above, a plausible reaction
mechanism for the Pd-catalyzed arylation of arylbor-
onic acids by Yagupolskii–Umemoto reagents was
suggested in Scheme 2. First, an oxidative addition of
[Ar2SCF3]+[OTf]À to Pd0 generates the key [ArPdIIOTf]
intermediate. Then, transmetallation of [ArPdIIOTf] by
RÀB(OH)2 in the presence of base affords [ArPd(L)R],
which undergoes reductive elimination to ultimately
produce ArÀR and regenerate the Pd0 catalyst. Be-
cause the side product Ar2S was formed in the reac-
tion mixtures, the cleavage of the SÀCF3 bond of
[Ar2SCF3]+[OTf]À inevitably occurred, which compet-
ed with the breakage of the SÀAr bond of [Ar2SCF3]+
[OTf]À and to some extent frustrated the arylation. Al-
though [PdÀCF3] intermediates might be formed in
the reaction, the trifluoromethylation products were
not observed. This may be attributed to the challeng-
ing reductive elimination of ArÀCF3 from PdII spe-
cies.[6b,8b,12] However, the details remain unclear yet.
In conclusion, we have found that the arylation of arylboron-
ic acids by Yagupolskii–Umemoto reagents can be successfully
implemented in the presence of Pd catalysts. Various arylbor-
onic acids are transformed in the reaction to give the corre-
sponding arylation products in good to high yields. The reac-
tion verifies that the SÀAr bonds of [Ar2SCF3]+[OTf]À can be
readily cleaved by Pd complexes. The relatively electron-poor
aryl groups of asymmetric [Ar1Ar2SCF3]+[OTf]À salts are more
favorably transferred compared to the electron-rich ones. This
is the first example of using [Ar2SCF3]+[OTf]À as arylation re-
agents in organic synthesis. The application of this property of
[Ar2SCF3]+[OTf]À to other conversions is currently underway in
our lab.
group of OH, which gave 3an in 65% yield. Furthermore, 1-
and 2- naphthalenylboronic acids (1s and 1t), 2-benzofuranyl-
boronic acid (1u), 4-dibenzothiophenylboronic acid (1v), and
E-styrylboronic acid (1w) were all suitable substrates in the re-
action, affording 3as–3aw in moderate yields. In the cases of
3as, 3at, and 3aw, the choice of 10 mol% [Pd(PtBu3)2] did not
promote the yields of the products.
In addition to [Ph2SCF3]+[OTf]À, other symmetric [Ar2SCF3]+
[OTf]À are also effective arylation reagents towards arylboronic
acids in the presence of [Pd(PtBu3)2] under the standard reac-
tion conditions.[11] For instance, treatment of S-(trifluorome-
thyl)diarylsulfonium triflate 2b with 4- nitrophenylboronic acid
(electron-poor, 1b), 4-methoxyphenylboronic acid (electron-
rich, 1k), or phenylboronic acid (neutral, 1x) gave the corre-
sponding arylation product 3bb, 3bk, or 3bx in good yield
(Table 3). Taking sterically less hindered 2c instead of 2b, simi-
lar reaction was observed and higher yields of the products
were achieved (3cb, 3ck, and 3cx). However, in the cases of
2e and 2 f, the Suzuki cross-coupling products were obtained
in lower yields. Even though 2 f used in the reaction contains
regioisomers which cannot be removed during the prepara-
Scheme 2. A plausible mechanism for Pd-catalyzed arylation of arylboronic
acids by Yagupolskii–Umemoto reagents.
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2 equiv), [Pd(PtBu3)2] (0.005, 0.010, or 0.015 mmol, 5 mol%),
NaHCO3 (0.1, 0.2, or 0.3 mmol, 1 equiv), and DMF (1, 2, or 3 mL) in
a nitrogen filled glovebox with stirring. The mixture was heated at
808C for 24 h, and extracted with ethyl acetate. The extracts were
washed with water, dried over anhydrous Na2SO4, and concentrat-
ed under reduced pressure. The residue was purified by column
chromatography on silica gel using petroleum ether or a mixture
of petroleum ether and ethyl acetate as eluents to give the aryla-
tion product 3. In the cases of 3aa, 3ap–u, 3bx, 3cx, and 3dx,
a solution of meta-chloroperbenzoic acid (mCPBA; 0.4, 0.8, or
1.2 mmol, 4 equiv) in DMF (1 mL) was added into the reaction mix-
ture before the extraction step to oxidize the side product Ar2S at
room temperature for 3 h in order to separate the desired ones.
Table 3. Pd-catalyzed arylation of arylboronic acids with other symmetric
S-(trifluoromethyl)diarylsulfonium salts.
Acknowledgements
We thank Wuhan University of Technology, the Natural Science
Foundation of Hubei Province (China) (2015CFB176), and the
“Chutian Scholar” Program from the Department of Education
of Hubei Province (China) for financial supports.
Keywords: arenes · cross-coupling · fluorine · sulfur · synthetic
methods
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Experimental Section
General procedure for Pd-catalyzed arylation of arylboronic
acids with Yagupolskii–Umemoto reagents
A sealed tube was charged with arylboronic acid (1; 0.1, 0.2, or
0.3 mmol, 1 equiv), [Ar2SCH3]+[OTf]À (2; 0.2, 0.4, or 0.6 mmol,
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deux, C. Wakselman, Angew. Chem. Int. Ed. 2006, 45, 1279–1282;
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Received: March 2, 2016
Published online on March 23, 2016
Chem. Eur. J. 2016, 22, 6542 – 6546
www.chemeurj.org
6546
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