Palladium-catalyzed Mizoroki-Heck-type reactions of [Ph2SRfn][OTf] with alkenes at room temperature

Article abstract of DOI:10.1039/c6cc06089g

The first Pd-catalyzed Mizoroki-Heck-type reaction of [Ph₂SR_fn][OTf] with alkenes is described. The reaction of [Ph₂SR_fn][OTf] (R_fn = CF₃, CH₂CF₃) with alkenes in the presence of 10 mol% Pd[P(t-Bu)₃]₂ and TsOH at room temperature provided the corresponding phenylation products in good to high yields. The bases that benefit the traditional Mizoroki-Heck reactions severely inhibited the transformation with [Ph₂SR_fn][OTf], whereas acids significantly improved the reaction. This protocol supplies a new class of cross-coupling partners for Mizoroki-Heck-type reactions and gains important insights into the reactivity of phenylsulfonium salts either with or without fluorine-containing alkyl groups as the promising phenylation reagents in organic synthesis.

Full text of DOI:10.1039/c6cc06089g

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Palladium-Catalyzed Mizoroki-Heck-Type Reactions of
Ph SR ][OTf] with Alkenes at Room Temperature
[
2
fn
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
a
Shi-Meng Wang, Hai-Xia Song, Xiao-Yan Wang, Nan Liu, Hua-Li Qin, and Cheng-Pan Zhang*
DOI: 10.1039/x0xx00000x
www.rsc.org/
The first Pd-catalyzed Mizoroki-Heck-type reaction of trifluoromethyaltions with [Ph SCF ]X (X = OTf, BF ) have
2
3
4
3
[
Ph SR ][OTf] with alkenes is described. The reaction of been disclosed. The reactions in regard to transition-metal-
2 fn
[
1
Ph SR ][OTf] (R = CF , CH CF ) with alkenes in the presence of mediated transformation of [Ph SCH CF ][OTf] are rarely
0 mol% Pd[P(t-Bu)3]2 and TsOH at room temperature provided known.
2
f
n
f
n
3
2
3
2
2
3
5
the corresponding phenylation products in good to high yields.
The bases that benefit the traditional Mizoroki-Heck reactions
severely inhibited the transformation with [Ph SR ][OTf],
S
The cleavage of Ph-S bond versus S-Rfn bond
2a
2
fn
OTf
=
CF3; b, CH CF3
2
2
)
Rf
n
, Rf
n
(
whereas acids significantly improved the reaction. This protocol
supplies a new class of cross-coupling partners for Mizoroki-Heck-
type reaction and gains important insights into the reactivity of
Recently, the Pd-catalyzed arylation of arylboronic acids
6
phenylsulfonium salts either with or without fluorine-containing with [Ar
SCF ][OTf] was reported. When the Umemoto’s
3
2
alkyl groups as the promising phenylation reagents in organic reagent was treated with arylboronic acid, no arylation
6
synthesis.
product was produced. This unique reactivity of [Ar
SRfn][OTf]
2
may hint of new applications of the non-cyclic
Fluorine-containing diaryl sulfonium salts are conventional fluoroalkyl(diaryl)sulfonium salts in an expanded field. On the
but useful synthetic reagents in the preparation of functional other hand, the Pd-catalyzed Mizoroki-Heck reaction of aryl
1
molecules. Such compounds have been extensively studied in halides and pseudo-halides (such as triflates, tosylates,
fluoroalkylation reactions. For example, trifluoromethyl diaryl carboxylates, diazoniums, and iodoniums) with alkenes have
sulfonium salts, known as Yagupolskii-Umemoto reagents been well documented. However, examples of the uses of
(
[Ar SCF ]X (X = OTf, BF )), were initially exploited as arylsulfoniums, arylphosphoniums, and arylammoniums as
2
3
4
+
electrophilic 2 CF3 transfer sources for
a
variety of cross-coupling partners in the same reaction are very limited
nucleophiles, and later were confirmed to be available in the despite they having been widely utilized in Suzuki-Miyaura
7
-12
reductive trifluoromethylation of alkenes, alkynes, arenes, and reactions.
others. 2,2,2-Trifluoroethyl diphenyl sulfonium salt, a less
3
Here we found that [Ph SR ][OTf] could be used as cross
2 fn
well-known reagent which was first synthesized by Umemoto coupling reagents in Mizoroki-Heck-type reactions with
4
and coworkers, was recently found to be an efficient ylide alkenes at room temperature in the presence of Pd-catalysts.
precursor and trifluoromethylcarbene source for the The reaction between 1-methoxy-4-vinylbenzene (1a) and
functionalization of aryl aldehyde, vinyl ketones, and aldimines trifluoromethyl diphenyl sulfonium triflate (2a) was tested as a
5
and olefins, respectively. Compared to Umemoto and Togni’s model reaction to determine the optimized phenylation
reagents, trifluoromethyl and 2,2,2-trifluoroethyl diphenyl conditions (see SI). At the beginning, reaction of 1a with 2a
o
sulfonium salts have shown a narrow range of applications in (1.5 equiv) at 80 C in DMF under a N atmosphere for 24 h in
2
organic synthesis. To our knowledge, almost only Cu-mediated, the presence of 10 mol% PdCl2 gave (E)-1-methoxy-4-
photoredox-catalyzed,
and
inorganic-reductant-initiated styrylbenzene (3a) in 30% yield (entry 1, Table 1). Other Pd
complexes like Pd (dba) , Pd(OAc) , and Pd(PPh ) used in the
2
3
2
3 4
o
same reaction (at 80 C) afforded 3a in 30-64% yields (entries
-4, Table 1). The reaction in the presence of 10 mol% Pd[P(t-
Bu)3]2 (at 80 C) provided 3a in 76% yield (entry 5, Table 1).
a.
School of Chemistry, Chemical Engineering and Life Science, Wuhan University of
Technology, 205 Luoshi Road, Wuhan 430070 (China)
E-mail: cpzhang@whut.edu.cn
2
o
†
Corresponding author: Cheng-Pan Zhang
o
Decreasing the reaction temperature from 80 C to room
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
temperature in the presence of 10 mol% Pd[P(t-Bu) ] , no
significant change in the yield of 3a was observed (67% yield)
3
2
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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c
o
d
(
entry 6, Table 1). Nevertheless, if the base such as NaHCO3, depicted in the parentheses. The reaction was run at 80 C. 2b
View Article Online
(
0.15 mmol) was used instead of 2a (0.15 mDmOoI:l)1.0.1039/C6CC06089G
K CO , K PO , NaOAc, DBU, or DMAP was added into a
2
3
3
4
o
mixture of 1a, 2a, Pd[P(t-Bu) ] , and DMF at 80 C or room
3 2
temperature, the Mizoroki-Heck-type reaction was frustrated,
affording 3a in 7-35% or < 1-5% yields (entries 7-10, Table 1).
In contrast, the choice of acids can facilitate the reaction.
When 1a was treated with 2a in the presence of 10 mol% TsOH
and Pd[P(t-Bu)3]2 at room temperature, 3a was obtained in
In general, bases benefit the Pd-catalyzed Mizoroki-Heck
reaction with aryl halides or pseudo-halides by neutralizing the
7
acid formed and allowing for more effective ligand recovery.
However, when [Ph SR ][OTf] (R = CF , CH CF ) were
2
fn
fn
3
2
3
employed as the cross-coupling partners, the reaction was
seriously inhibited by the use of bases. This might be
attributed to the tendency of decomposition of [Ph SR ][OTf]
8
6% yield (entry 11, Table 1). Other sulfonic or carboxylic acids
such as CF SO H, CH SO H, CH CO H, and CF CO H could
3
3
3
3
3
2
3
2
2
fn
also provide 3a in good yields (entries 12-15, Table 1). Further
studies indicated that 2,2,2-trifluoroethyl diphenyl sulfonium
triflate (2b) is a more effective participant than 2a in the
functionalization of 1a at room temperature (see SI). Reaction
of 1a and 2b without additives in the presence of 10 mol%
Pd[P(t-Bu)3]2 gave higher yield of 3a than that using 2a (84%
vs 67%) (entry 16, Table 1). Similarly, the addition of base
dramatically suppressed the cross-coupling (6% yield, see SI).
When using TsOH instead, the reaction gave 3a in a
quantitative yield (entry 17, Table 1).
13
under the basic conditions, where the breakage of S-CF3
bond of [Ph SCF ][OTf] or the defluorination of
Ph SCH CF ][OTf] via β-F elimination might happen,
2 2 3
2
3
5
[
respectively. This assumption was partially supported by
1
9
the F NMR analysis of the reaction mixtures of [Ph SCF ][OTf]
2
3
or [Ph SCH CF ][OTf], NaHCO3, and DMF at room
2
2
3
temperature, where the cations of [Ph SR ][OTf] were
2
fn
inevitably decayed (see SI).
With the optimized reaction conditions in hand, the scope of
the reaction was investigated. To our delight, styrenes with
either electron-donating or -withdrawing groups on the phenyl
rings were all smoothly converted by 2a or 2b, which gave the
cross-coupling products (3b-p) in 21-99% yields (Table 2). The
position of the substituents on the phenyl rings has
considerable influence on the reaction. Treatment of 1-
Table 1. Pd-catalyzed Mizoroki-Heck-type reaction of 2a with
a
1a
Pd-catalyst (10 mol%)
additive 10 mol%
(
)
+
S
r. .
t , DMF, 24 h, N2
MeO
CF
OTf
methoxy-2-vinylbenzene (1b) with 2a or 2b at room
1
a
3
MeO
(
1
.5 equiv)
2
3a
a
temperature under N in the presence of TsOH (10 mol%) and
2
Pd[P(t-Bu)3]2 (10 mol%) provided 3b in 70% or 75% yield,
while 1-methoxy-3-vinylbenzene (1c) similarly reacting with 2a
or 2b afforded 3c in 96% yield. Functional groups such as OAc,
b
Entry
Catalyst
Additive
none
Yield (3a, %)
c
1
PdCl2
30
30
64
30
76
67
c
2
Pd (dba)
2
none
F, Cl, Br, CN, NO
3n-p), and even the reaction between 1-iodo-4-vinylbenzene
1l) and 2a or 2b could supply 3l in 23% or 21% yield. (Note:
2
, and CHO were tolerated in the reaction (3k,
3
c
3
Pd(OAc)2
Pd(PPh3)4
none
(
c
4
none
Since 1l was completely consumed in the reaction, the
breakage of the C-I bond of 1l and/or 3l under the standard
reaction conditions might occur which led to side reaction and
poor yield of 3l). Moreover, the unconjugated olefin, enolate,
and electron-deficient alkenes are also suitable substrates to
c
5
Pd[P(t-Bu)3]
none
2
6
7
8
9
Pd[P(t-Bu)3]2
Pd[P(t-Bu)3]2
Pd[P(t-Bu)3]2
none
c
NaHCO3
K2CO3
1 (35 )
c
< 1 (7 )
the reactions. For instance, allyl acetate
(allyloxy)benzene (1r) reacting with 2b in the presence of TsOH
and Pd[P(t-Bu) at room temperature for 24 h provided 3q in
1% or 84% yield. Treatment of vinyl benzoate (1s) with 2b
(1q
)
or
c
Pd[P(t-Bu)3]
2
K3PO
4
2 (14 )
c
1
1
1
1
1
1
0
1
2
3
4
5
Pd[P(t-Bu)3]2
Pd[P(t-Bu)3]2
Pd[P(t-Bu)3]2
DBU
5 (5 )
]
3 2
6
TsOH
86 (83)
78
under the standard reaction conditions for 2 days afforded a
mixture of E- and Z-isomers of 3s in 92% yield (molar ratio of E
/ Z = 1 : 0.17). The Pd-catalyzed Mizoroki-Heck reaction of 2b
CF SO H
3
3
Pd[P(t-Bu)3]
2
CH SO H
3
3
77
o
Pd[P(t-Bu)3]2
Pd[P(t-Bu)3]2
Pd[P(t-Bu)3]2
CH CO H
82
with ethyl acrylate (1t) and methyl acrylate (1u) at 60 C for 24
3
2
h produced 3t in 74% yield and 3u in 60% yield, respectively.
The higher reaction temperature benefited the transformation
of electron-deficient conjugated alkenes since the reactions at
room temperature gave lower yields of the desired products.
Besides, acrylonitrile (1v) reacted with 2b to afford 3v in 83%
yield with a trace amount of the Z-isomer and the diarylation
CF CO H
75
3
2
d
1
6
none
84
d
1
7
Pd[P(t-Bu)3]
TsOH
> 99 (97)
2
a
Reaction conditions: a mixture of 1a (0.1 mmol), 2a (0.15 mmol),
Pd-catalyst (0.01 mmol, 10 mol%), additive (bases: 0.15 mmol; or
o
acids: 0.01 mmol, 10 mol%), and DMF (2 mL) was reacted at 80 C in product (3,3-diphenylacrylonitrile), which was determined
b
1
a sealed tube under a N2 atmosphere for 24 h.
The yield was by H NMR analysis of the isolated product (see SI).
determined by HPLC using (E)-1-methoxy-4-styrylbenzene (3a, t = Furthermore, the Suzuki-Miyaura and Mizoroki-Heck cross-
R
8
.468 min, λmax = 302.2 nm, water/methanol = 20 : 80 (v / v)) as the
couplings of 2a (or 2b) with 1w can be performed in one pot
external standard. Otherwise specified, the isolated yield is
2
| J. Name., 2012, 00, 1-3
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COMMUNICATION
(
Scheme 1). Treatment of 1w with 2a or 2b (2 equiv) at room remain unclear at this stage. Triphenylsulfonium triflate, a
View Article Online
DOI: 10.1039/C6CC06089G
1
4
temperature in the presence of 10 mol% Pd[P(t-Bu)3]2 and well-known radical precursor and photoacid generator, can
equal equivalent of NaHCO3 for 24 h provided 3w in 44% or also gave 3a in 59% yield under the standard reaction
5
7% yield, respectively, indicating the feasibility of conditions. (Methyl)diphenylsulfonium triflate (2i), the non-
simultaneous difunctionalization by phenylsulfonium salts.
fluorinated version of 2a, reacted with 1a and afforded 3a in
1% yield (vs 86% yield). Treatment of
dimethyl(phenyl)sulfonium triflate (2j) with 1a furnished 3a in
3% yield. 1-Phenyl(tetrahydro)thiophenium (2k) that was
successfully used as a cross-coupling partner in Suzuki-Miyaura
8
Table 2 Pd-catalyzed Mizoroki-Heck-type reactions of 2a or 2b
with alkenes
1
Pd[P(t-Bu)
TsOH (10 mol%)
DMF, N
, r.t., 24 h
(10 mol%)
8a-d
3
]
2
reactions
was treated with 1a to provide 3a in 9% yield
R
+
S
R
2
under the standard reaction conditions. These results suggest
that arylsulfonium triflates either with or without S-fluoroalkyl
groups can be mildly employed in Pd-catalyzed Mizoroki-Heck
cross-coupling and that the reactions with 2a and 2b works
better than those with 2c-k under the standard conditions.
OTf
R
fn
2
a or 2b
R
tB
u
a
b
3f, 99%b
3
b, R = 2-OMe, 70% , 75%
3
d, 74%b
a
b
3
3e, 76% , 79%
c, R = 3-OMe, 96% , 96%b
a
a
Table 3 Pd-catalyzed Mizoroki-Heck reaction of 2c-p with 1a
AcO
Ph
F
Cl
Pd[P(t-Bu) ] (10 mol%)
3h, 92%a
3i, 92%b
3 2
a
b
3j, 99% , 83%b,c
a
3
g, 83% , 99%
TsOH 10 mol%
(
)
+
2c-p
MeO
DMF, r.t., 24 h, N
2
MeO
1
a
3
a
Br
I
F
3
C
NC
3m, 76%a
a
b
3l, 23% , 21%
a
b
3n, 73% , 87%b,c
a
3
k, 69% , 71%
S
S
S
S
C
OTf
OTf
OTf
OTf
F
2 5
CF
2c, 8%
H
CH F
2
CH3
2e, 96%
2
AcO
PhO
2d, 79%
2
f, 1%
O
2
N
OHC
a
b
3r, 84%
b
o, 65%a,c, 89%b,c
a
b
3q, 52% , 61%
3
3p, 66% , 73%
OTf
S
S
OTf
OTf
S
S
S
Ph
O
C
2
F
5
OTf
OTf
NC
O
EtO
C
MeO
C
2
2g, 83%
2i, 81%
2
j, 13%
2k, 9%
2
v, 83%
b,d
3
s, 92%
b,c
t, 74%b,d
3u, 60%b,d
(E iso
other = 1 : 0.12 : 0.14
)
-
m
e
r
/ Z iso e
m r
/
-
2h, 59%
3
E / Z
3
=
1 : 0.17
N2
(
)
I
Ph
OTf
a
2
a
b
= CH CF ). Isolated yield. 2 days. d 60 oC.
c
was used (Rf
n
= CF ). Isolated yield. 2b was used (Rf
n
P
Ph
Ph
Br
3
2
3
BF4
I
OTf
n
, 5%
2l, 29%
2
2o, 1%, (81%)e
c
)
%, 9 %, 98%)d
7
2p, 1%
b
2m, 97% 89%
(
7
6
(
a
78%, 73%, 15%)
(
Pd[P(t-Bu) ] (10 mol%)
3
2
Yields of 3a was determined by HPLC using (E)-1-methoxy-4-styrylbenzene as the external
standard tR = 8.468 min λmax = 302.2 nm water methanol = 20 : 80
78 from
O
NaHCO (1 equiv)
3
+
v
v
.
b
S
Rf
a or
(
,
,
/
(
/
))
+
%
B
DMF, r.t., N , 24 h
2
O
OTf
2b
3w
rom
Pd(OAc)
(2 mol %) / imidazolium / THF / r.t. (Ref 15a); 73% from [Ru(bpy) ]
3
2 2
o
(1 mol%) / DMSO /
/
1 h
6
(
n
1
w
455 nm LED
);
(O
2 h Ref 15b 15 from Pd Ac 1 mol
water r.t. Ref 15c .
2
44% f
57% from 2b
2
a
/
2
0
C,
(
%
o
)
2
(
%) /
/
)
(
2
equiv
)
c
89% f
rom
Pd(II) / N HCO3 / THF / 50 C / 16 h (R f 15d)
a
e
.
d
76% f
rom
Et N / di it
a om e-
t
3
supported Pd 0.1 mol % / NMP Ref 15e ; 97% from Pd dba 0.2 mol% / thiadiazolidine oxide
(
)
(
)
2
(
)
3
(
)
Scheme 1 One-pot Suzuki-Miyaura and Mizoroki-Heck reaction of
a (or 2b) with 1w
.
mo
o
m n m crowave.
e
rom
c
c
(
0 4
l%) / Et
3
N / DMF / 200 C / 10
i
/
i
(R f 15f); 98% f
AgOA / Pd(OA )
2
/
cOH / 2 h / 110 oC (Ref 15g .
e
81% 43:57 linear/branched mixture from Pd2 dba 5 mol%
3
( ) ( ) (
2
A
)
)
/
dppp (10
mol% / NEt3 Ref 15h .
)
(
)
In addition, other phenylsulfonium salts either with or
without fluorine-containing alkyl groups were tested in the
reaction (Table 3). It was surprising that the Pd-catalyzed other commonly used cross-coupling partners in this Heck-
Mizoroki-Heck cross-coupling of (2,2- type conversion, the reactions between 1a and
difluoroethyl)diphenylsulfonium triflate (2c) with 1a under the benzenediazonium tetrafluoroborate (2l), diphenyliodonium
standard reaction conditions afforded 3a in 8% yield, whereas triflate
2m), iodobenzene 2n), or phenyl
the reaction of (2-fluoroethyl)diphenylsulfonium triflate (2d
trifluoromethanesulfonate (2o) were explored (Table 3). It was
with 1a gave 3a in 79% yield. (Ethyl)diphenylsulfonium triflate found that 2l reacting with 1a in the presence of TsOH and
To compare the efficiency of phenylsulfonium triflates with
(
(
)
(
2e), the non-fluorinated version of 2b, reacted with 1a Pd[P(t-Bu) ] in DMF at room temperature for 24 h gave 3a in
3 2
1
5a
provided
3a
in
96%
yield
(vs
>99%
2f), the fully 73%, or 15% yield). Treatment of 2m with 1a under the
fluorinated version of 2b, however, produced 3a in 1% yield. standard reaction conditions furnished 3a in 97% yield (89%
yield). 29% yield (previous complex methods supplied 3a in 78%,
15b
15c
(Pentafluoroethyl)diphenylsulfonium triflate (
15d
Treatment of (2,2,3,3,3-pentafluoropropyl)diphenylsulfonium yield in literature ). The reaction of 2n or 2o with 1a gave
triflate (2g) with 1a supplied 3a in 83% yield. The strong trace of 3a (76-98% yield by harsh methods
15e-h
). Similarly,
electronegativity of fluorine atoms and/or the tendency of β-F when 2p was treated with 1a under the standard reaction
elimination might cause these distinct differences, but the condition, 1% of 3a was obtained, which had been used as a
9a
rules of the impacts of fluorine content on the reaction still phenylation reagent at high reaction temperature. These
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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8
Non-fluorinated aryl sulfonium salts as arylatViioewnArrteicalegOennlintes
selected): (a) J. Srogl, G. D. Allred, L. S. Liebeskind, J. Am.
results imply that phenylsulfonium triflates (2a, 2b, 2d, 2e, 2g,
(
DOI: 10.1039/C6CC06089G
and 2i) are powerful cross-coupling participants in Pd-
catalyzed Mizoroki-Heck reaction with styrene at room
temperature.
Chem. Soc. 1997, 119, 12376-12377. (b) D. Vasu, H. Yorimitsu,
A. Osuka, Angew. Chem. Int. Ed. 2015, 54, 7162-7166. (c) D.
Vasu, H. Yorimitsu, A. Osuka, Synthesis 2015, 47, 3286-3291.
(d) P. Cowper, Y. Jin, M. D. Turton, G. Kociok-Kohn, S. E.
Lewis, Angew. Chem. Int. Ed. 2016, 128, 2610-2614. (e) K.
Sander, T. Gendron, E. Yiannaki, K. Cybulska, T. L. Kalber, M.
In conclusion, we have found that [Ph SR ][OTf] (R = CF3,
2
fn
fn
CH CF ) can be used as the effective cross-coupling partners in
2
3
Pd-catalyzed Mizoroki-Heck-type reaction with alkenes. The
functionalization of various conjugated and unconjugated
F. Lythgoe, E. Arstad, Sci. Rep. 2015, 5, 9941. (f) S. Donck, A.
Baroudi, L. Fensterbank, J. –P. Goddard, C. Ollivier, Adv.
Synth. Catal. 2013, 355, 1477-1482. (g) K. Hirabayashi, Y.
Nara, Y. Yamashita, K. –i. Kiyota, N. Kamigata, T. Shimizu,
Journal of Sulfur Chemistry, 2009, 30, 346-350.
alkenes by [Ph SR ][OTf] (2a, Rfn = CF or 2b, Rfn = CH CF ) in
2
fn
3
2
3
the presence of 10 mol% Pd[P(t-Bu)3]2 and TsOH at room
temperature provided the corresponding phenylation products
in good to high yields. The use of acids significantly improved
9
Aryl phosponium salts as arylation reagents (selected): (a) L.
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, and 2i are also available reagents in the reaction. All these
salts could be conveniently synthesized by the known means 10 Aryl ammonium salts as arylation reagents (selected): (a) E.
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(
see ESI). This protocol demonstrates a new class of cross-
coupling participants for Heck-type reaction and yields very
important insights into the reactivity of phenylsulfonium salts
either with or without fluorine-containing alkyl groups.
We thank Wuhan University of Technology, the Natural
Science Foundation of Hubei Province (China) (2015CFB176),
the “Chutian Scholar” Program from Department of Education
of Hubei Province (China), and the “Hundred Talent” Program
of Hubei Province for financial support.
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4
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