Palladium-catalyzed denitrogenative Hiyama cross-coupling with arylhydrazines under air

Article abstract of DOI:10.1016/j.tetlet.2015.06.095

A Pd-catalyzed denitrogenative Hiyama coupling of arylhydrazines and aryl silanes is described under mild conditions. The newly developed catalytic system does not require the use of expensive silver- or copper-based stoichiometric oxidants to obtain diaryl derivatives with high selectivity and reactivity. The reported coupling reactions are very practical as they do not require the protection of inert gas or oxygen and are tolerant to many functional groups.

Full text of DOI:10.1016/j.tetlet.2015.06.095

Accepted Manuscript
Palladium-catalyzed Denitrogenative Hiyama Cross-coupling with Arylhydra-
zines under Air
Hui Zhang, Chunjie Wang, Zhiwei Li, Ziyun Wang
PII:
S0040-4039(15)01128-4
DOI:
http://dx.doi.org/10.1016/j.tetlet.2015.06.095
TETL 46487
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
19 April 2015
22 June 2015
29 June 2015
Please cite this article as: Zhang, H., Wang, C., Li, Z., Wang, Z., Palladium-catalyzed Denitrogenative Hiyama
Cross-coupling with Arylhydrazines under Air, Tetrahedron Letters (2015), doi: http://dx.doi.org/10.1016/j.tetlet.
2
015.06.095
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Palladium-catalyzed Denitrogenative Hiyama Cross-coupling with
Arylhydrazines under Air
a,b,
a
a
a
Hui Zhang *, Chunjie Wang , Zhiwei Li , Ziyun Wang *
a
School of Chemistry&Chemical Engineering, Zhoukou Normal University, Zhoukou, 466001,
Henan, P. R. of China. E-mail: znu_zhanghui@126.com. wang_zi_yun@126.com. Fax:
+86-394-8178-5257; Tel: +86-394-8178-5255
b
Institute of Medical Chemistry, Zhoukou Normal University, Zhoukou, 466001, Henan
Abstract
A Pd-catalyzed denitrogenative Hiyama coupling of arylhydrazines
and aryl silanes is described under mild conditions. The newly developed
catalytic system does not require the use of expensive silver- or
copper-based stoichiometric oxidants to obtain diaryl derivatives with
high selectivity and reactivity. The reported coupling reactions are very
practical as it does not require the protection of inert gas or oxygen and
tolerant to the many functional groups.
Keywords:
denitrogenative
coupling,
Hiyama cross-coupling,
arylhydrazines
1

Introduction
Transition-metal-catalyzed cross-coupling reactions have provided
important innovations for synthetic chemistry over the past decades, were
considered to be the most powerful and accurate tools for the construction
1
of carbon–carbon bonds. Consequently, the vast array of reactions has
found numerous applications in both industrial and academic settings in
the synthesis of complex natural products and biologically active small
molecules. Among these modern couplings, the coupling partners can be
2
organic halides/pseudohalides and organometallic reagents. Of these
substrates, arylsilanes as transmetalation reagents offer numerous
3
advantages over aryl borates (Suzuki coupling) and aryl stannanes (Stille
4
coupling) in terms of their ready availability, low toxicity, easy workup,
good biocompatibility and stability in various chemical media (namely,
the Hiyama and Hiyama–Denmark reactions). Also, silicon can be
facilely converted into relatively harmless silica by incineration, and all
of these points have made Hiyama coupling attractive from
environmental and user-friendly points of view. Their environmentally
5
benign nature makes these reagents very attractive to organic chemists.
Traditionally, the Hiyama coupling reaction utilizes arylsilane reagents
with aryl halides or triflates for constructing asymmetrical biaryls or
multisubstituted alkenes that are structural components of various
6
pharmaceuticals and other functional materials via C-X/C-O cleavage.
2

(
Scheme 1) Thus, There is still a need for broadening the scope of
partners to achieve Hiyama-type reactions that are not obtainable through
known approaches. Recently, other coupling partners via C-S cleavage
7
have been reported. The cross-coupling of arylsilanes with arylsulfinic
salts have been demonstrated by Qi’s group and Pd(II) catalytic system
8
was particularly efficient with the assistance of TBAF to obtain biaryls.
Zhao et. al. first reported a cross-coupling reaction of arylsilanes with
9
arylsulfonyl chlorides. The Pd(0)-catalyzed reaction was proceeded
o
smoothly with the application of component solvent by 100 C under N .
2
However, the release of SO for these transformation was inevitable
2
which make it environmentally unfriendly. As a consequence, to expand
diverse electrophiles has been one of the hot topics in recent years, for the
purpose of voiding the productions of deleterious waste and more
attractive method of Hiyama coupling was proceeded via the cleavage of
C-N bond with the release of nitrogen. In 2011, Qi and coworkers
reported a practical carbon-nitrogen bond cleavage procedure for the
Hiyama cross-coupling reactions using arenediazonium salts as the
10
electrophilic reagents. Notably, aryl diazonium salts are required to be
11
freshly prepared and need to be kept in storage under zero degree.
Another alternative to aryl diazonium salts was recognized as
arylhydrazines. Arylhydrazines are low cost, ready availability, chemical
stability and extremely valuable compounds in organic chemistry that are
3

widely used for the preparation of numerous N-contained compounds, but
little attention has been paid to their use as arylating regents via
denitrogenation. Until recently, the efficiency of using arylhydrazines as
aryl source in cross-coupling reactions has been witnessed by the
1
2
13
oxidative Heck-type with olefins,
oxidative radical arylation,
14
15
Pd-catalyzed Suzuki cross-coupling, etc. However, arylhydrazine as a
coupling partner and a potential aryl source via C-N cleavage to form
16
biaryls by Hiyama coupling was rarely reported. In 2014, Kuang et al.
reported a single example for the Pd(0)-catalyzed coupling of
o
phenylhydrazine with phenyl triethoxysilane under 100 C in the yield of
6
2%, which could not rule out the possibility of homocoupling by
17
phenylhydrazine or phenylsilane. Herein, we wish to report a novel
approach to obtain diaryl derivatives with high selectivity and reactivity
from arylhydrazines and aryl silanes via Pd-catalyzed denitrogenative
cross-coupling with selective C-N bond cleavage of arylhydrazines in the
presence of CSA (camphorsulfonic acid) under mild conditions.
4

X
X = Cl, Br, I
SO Na
C-X Cleavage
SiR3
2
N2BF4
C-S Cleavage
C-N Cleavage
?
C-O Cleavage
SO Cl
NHNH2
2
This
work
OR
Scheme 1 Pd(II)-catalyzed Hiyama cross-coupling of arylsilane with
different coupling partners
Results and Discussion
Owing the low reactivity of these reagents, they typically need to be
activated by fluoride in order to generate a more reactive pentacoordinate
silicate anion for the transmetalation step. The reaction of
p-tolylhydrazine with phenyl triethoxysilane was first chosen as a model
system for optimization studies (Table 1). Initially, the reaction that was
o
carried out under 50 C for 3 h in the presence of Pd(PhCN) Cl (5 mol%)
2
2
as a catalyst in the solution of TBAF (1 M in THF) did not give the
desired product (entry 1). Although the addition of bases (such as KOAc)
or oxidants (such as AgOAc) as additives to the reaction system also
failed to afford 4-methyl-1,1'-biphenyl (entries 2–3), the presence of
5

acetic acid (1 equiv.) was tested and to our delight, afforded the desired
biaryl products in 19% yield (entry 4). In this reaction different acids
seem play key roles to promote the efficacy. When adding PivOH (2
equiv.) as additives, we were pleased to find that 4-methyl-1,1'-biphenyl
was obtained in 68% yield (entry 5). TFA (trifluoroacetic acid) and
trichloroacetic acid were observed to diminish the cross-coupling
reactions
(entries
6–7).
The
addition
of
MesCOOH
(
2,4,6-trimethylbenzoic acid) and oxalate were dramatically lowered the
yield (entries 8–9). The attempts to use sulfonic acids as additives were
successful. MsOH (methanesulfonic acid) was tested and to our delight, it
gave much better results (entry 10). Other sulfonic acids, such as TfOH
(
trifluoromethanesulfonic acid) and TsOH (4-methylbenzenesulfonic acid)
gave a comparable result (entries 11–12). Finally, we test CSA
camphorsulfonic acid) as additive and 91% yield of desired product was
(
isolated without the detection of 4,4'-dimethyl-1,1'-biphenyl by
homocoupling. (entry 13)
a
Table 1 Influence of Additives to the Reaction
b
Entry
Additive
-
KOAc
AgOAc
HOAc
Yield(%)
1
2
3
4
-
-
-
19
6

5
6
7
8
9
PivOH
TFA
trichloroacetic acid
MesCOOH
oxalate
68
54
57
35
10
81
77
83
91
10
MsOH
TfOH
TsOH
CSA
1
1
2
3
1
1
a
Reaction conditions: p-tolylhydrazine (1 mmol), triethoxy(phenyl)silane (1.2 mmol),
o
Pd(PhCN)
3
2 2
Cl (5 mol%), additives (1 mmol), TBAF (1M in THF, 1.0 ml) at 50 C for
b
hours under air unless otherwise indicated. Isolated coupling yield.
Subsquently, our investigation focused on the effect of
transition-metal-catalysts on the model reaction of p-tolylhydrazine with
o
phenyl triethoxysilane in TBAF (1M in THF) under 50 C in the presence
of CSA, and the results are summarized in Table 2. Unfortunately, with
the use of Ru, Rh and Ni precursors such as RuCl (PPh ) , RhCl(PPh )
2
3 3
3 3
and NiCl (PPh ) , no desired product was detected (entries 1-3). Various
2
3 3
Pd precursors were screened for the reaction. Pd(OAc) , PdCl , PdBr and
2
2
2
PdI were somewhat effective, giving a 78%, 73%, 71% and 74% yield of
2
4
-methyl-1,1'-biphenyl (entries 4-7). Other palladium(II) compounds with
phosphine ligands led to higher amounts of desired products (entries
-11), and the denitrogenative coupling was inhabited with Pd(0)
catalysts (entries 12-13). To our delight, Pd(CH CN) Cl served as a
8
3
2
2
catalyst to afford the desired biaryl products in 89% yield (entry 14).
Among the tested transition-metal catalysts, Pd(PhCN) Cl showed the
2
2
highest catalytic reactivity and the desired product was isolated in 91%
o
yield when the model reaction was performed in TBAF under 50 C for 3
7

h (entry 15).
a
Table 2. Influence of Catalysts to the Reaction
b
Entry
Catalyst
Yield(%)
1
2
3
4
5
6
7
8
9
RuCl (PPh )
-
2
3 3
RhCl(PPh
3
)
3
-
NiCl
Pd(OAc)2
PdCl
PdBr2
PdI
PdCl (PPh
Pd(dppf)Cl2
PdCl (dppb)
PdCl (dppe)
2
(PPh
3
)
3
-
78
73
71
74
80
84
83
86
54
58
89
91
2
2
2
3 3
)
1
0
1
2
1
2
1
1
1
1
2
3
4
5
3 4
Pd(PPh )
Pd (dba)
2
3
Pd(CH CN) Cl
3
2
2
Pd(PhCN)
2
Cl
2
a
Reaction conditions: p-tolylhydrazine (1 mmol), triethoxy(phenyl)silane (1.2 mmol),
o
catalyst (5 mol%), CSA (1 mmol), TBAF (1M in THF, 1.0 ml) uat 50 C for 3 hours
8

b
under air unless otherwise indicated. Isolated coupling yield.
With the optimized conditions in hand, we next set out to explore the
scope of the method with respect to this Pd-catalyzed denitrogenative
coupling of arylhydrazine with triethoxy(phenyl)silane. Gratifyingly, a
variety
triethoxy(phenyl)silane. Different functionalities on the phenyl ring of
arylhydrazine, whether they were electron-withdrawing or
of
arylhydrazine
successfully
coupled
with
electron-donating groups, are compatible. As shown in Table 3, this
reaction was compatible with methoxy, methyl, ethyl, cyano, nitro
substituents, and furnished the desired product in good yields (Table 3,
3
a-3e). These results implied that the electronic effect is not critical for
this transformation. Halogen substituents such as fluoro, chloro, bromo
and iodo were tolerated under the optimal reaction conditions, and the
desired products were obtained in good yields (Table 3, 3f-3i). To explore
the application of this method, we tried other active groups, hydroxyl and
amino groups all demonstrated reactivity and the products were isolated
in good yield, thus extending the potential applications of the
method(Table 3, 3j-3k). The ortho- and meta-substituted group, such as
methoxyl, can also afford a good product yield, thus showing steric
hindrance has little effect on the reaction (Table 3, 3l-3m). The naphthyl
group also worked well and the desired product was produced in an
excellent yield (Table 3, 3n). Biphenyl-2-ylhydrazine could be an
9

optional substrate for preparing o-terphenyl in the yield of 62%, which
are important precursors in material science (Table 3, 3o).
Heteroaromatic
-pyridylhydrazine and 5-hydrazinyl-1H-tetrazole were tolerated, albeit
with good yields (Table 3, 3p-3r).
substrates,
such
as
2-thienylhydrazine,
2
Table 3. Pd-catalyzed denitrogenative coupling of various arylhydrazine with
a
triethoxy(phenyl)silane
a
Reaction conditions: arylhydrazines (1 mmol), triethoxy(phenyl)silane (1.2 mmol),
10

o
Pd(PhCN)
2
Cl
2
(5 mol%), CSA (1 mmol),TBAF (1 M in THF, 1.0 ml) at 50 C for 3
b
hours under air unless otherwise indicated. Isolated coupling yield.
Encouraged by these promising results, we further applied the optimized
reaction conditions to examine the substrate scope of aryl silanes (Table
4
). Siloxane having various alkyl substituents, such as methyl and ethyl,
afforded the desired products in good yields (Table 4, entries 1-2).
Dimethoxydiphenylmethane and diethoxydiphenylmethanewere similarly
found to be suitable substrate for this transformation and gave the
corresponding biaryls in good yield (Table 4, entries 3-4). Both two
phenyl ring could participate in this coupling smoothly. Different
functionalities on the phenyl ring of triethoxysilane, whether they were
electron-withdrawing or electron-donating groups, are compatible (Table
4
, entries 5-6). Meanwhile, phenyl triethoxysilane, bearing a sterically
hindered group, such as methyl or chloro at their ortho-positions, also
underwent the reaction with good yield (Table 4, entries 7-8). Moderate
coupling yield (72% and 75%) were still able to obtain when coupled
with naphthyl and pyridinyl (Table 4, entries 9-10).
11

Table 4. Pd-catalyzed Hiyama cross-coupling reactions of phenylhydrazides with a
a
wide variety of aryl silanes
b
entry
aryl silanes
yield%
1
2
3
4
5
6
7
8
9
C H -Si(OMe)
92
6
5
3
C
6
H
5
-Si(OEt)
-Si(OMe)
(C H ) -Si(OEt)
3
95
c
(C
6
H
5
)
2
2
90
c
93
6
5 2
2
4-CH
3
C
6
H
4
-Si(OEt)
3
90
87
84
82
72
75
4-ClC H -Si(OEt)
6
4
3
2-CH
3
C
6
H
4
-Si(OEt)
3
6 4 3
2-ClC H -Si(OEt)
1-C H - Si(OEt)
1
0
8
3
1
0
3-C
6
H
5 3
N- Si(OEt)
a
Reaction conditions: phenylhydrazine (1 mmol), aryl silanes (1.2 mmol),
o
Pd(PhCN)
2
Cl
2
(5 mol%), CSA (1 mmol), TBAF (1 M in THF, 1.0 ml) at 50 C for 3
b
c
hours under air unless otherwise indicated. Isolated coupling yield. Aryl silanes (0.6
mmol).
Mechanism
The possible mechanism of the palladium catalytic system was further
verified by a series of control experiments (Scheme 2). Both CSA and
12

Pd(PhCN) Cl was indispensable to this trasnsformation, which indicate
2
2
that the reaction proceeded under Pd catalysis and the inversion of
palladiaziridine intermediate must be accelerated by acid. On the other
side, no desired products were detected under nitrogen and no better yield
of biaryls was isolated under oxygen.
Scheme 2 Control Studies for this System
Although the exact mechanism of this reaction is not clear, a proposed
pathway exemplified by incorporating one complex from each category
A–D, is shown in Scheme 3 and in agreement with the mechanistic
proposals for other related reactions. Firstly, the Pd(II) catalyst reacted
[15a]
with arylhydrazines to form an palladiaziridine intermediate A,
which
subsequently underwent oxidative insertion of Pd(0) with C-N bond to
[
18]
generate palladium(II)-centered complex B. Protonolysis of complex B
with HX resulted in aryl palladium complex C and the palladiaziridine
complex D, which is easy to decompose into nitrogen and water when
[
12a]
treated with O2.
The regeneration Pd(0) was concomitantly to formal
13

oxidative insertion to complete the catalytic cycle. The ArPdX species
then inserted into Ar-Si bond of aryl silanes via a transmetallation process
to form diarylpalladium(II) species E. Finally, reductive elimination from
intermediate E generated the cross-coupling product and Pd(0) species,
which was reoxidized to Pd(II) by O for its catalytic cycle.
2
Scheme 3 Proposed mechanism of this reaction
Conclusion
The Pd-catalyzed cross-coupling of the arylhydrazines with aryl silanes
has been achieved under mild reaction conditions. The high efficiency
and reactivity of the arylhydrazines could be attributed to the formation
of the active Pd(II) species via the release of N during the catalytic cycle.
2
The reaction was accelerated by CSA and TBAF. The application of
widely available arylhydrazine enables this transformation to be an
attractive alternative to the Hiyama-type cross-coupling to dispense with
14

additional ligands and bases.
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Acknowledgements: This work was supported by the Education Department of
Henan Province Natural Science Research Program (13B150274) and the Doctoral
Scientific Research Foundation of Zhoukou Normal University(zksybscx201105).
Graphical Abstract
A Pd-catalyzed denitrogenative Hiyama coupling of arylhydrazines and aryl
silanes is described. The reported coupling reactions are very practical as it does
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not require the protection of inert gas and tolerant to the many functional groups
with high selectivity and reactivity.
18