PdCl2(CH3CN)2-catalyzed regioselective C-H olefinations of 2-amino biaryls with vinylsilanes as unactivated alkenes

Article abstract of DOI:10.1039/c9cc02199j

The first example of palladium-catalyzed chelation-assisted C-H olefination of 2-amino biaryls using readily available vinylsilanes as unactivated olefinating reagents has been developed, affording valuable arylated vinylsilane compounds in moderate to excellent yields and with exclusive (E)-selectivities.

Full text of DOI:10.1039/c9cc02199j

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DOI: 10.1039/C9CC02199J
Journal Name
COMMUNICATION
PdCl2(CH3CN)2-catalyzed regioselective C-H olefinations of 2-
amino biaryls with vinylsilanes as unactivated alkenes
Qiao-Ying Sun, Zhao Li, Zheng Xu, Zhan-Jiang Zheng, Jian Cao, Ke-Fang Yang, Yu-Ming Cui* and Li-
Wen Xu*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
a) divergent functionalization of arene C-H with vinylsilane
The first example of palladium-catalyzed chelation-assisted C-H
olefination of 2-amino biaryls using readily available vinylsilanes as
unactivated olefinating reagents has been developed, affording the
valuable arylated vinylsilane compounds with modest to excellent
yields and exclusive (E)-selectivities.
H
TMS
TMS
syn
alkylation
silylation
TMS
olefination
+
trans
TMS
H
TMS
TMS
branch
H

H

Recently,
the
transition-metal-catalyzed
direct
functionalization of inert C-H bond has attracted growing
interest in terms of its atom economy and step economy.1
Among the diverse carbon-carbon bond-forming reactions, the
intermolecular oxidative coupling of the arene C-H bonds with
alkenes (Fujiwara-Moritani reaction)2 represents an even more
powerful strategy to access a variety of valuable arylated
alkenes in comparison with Mizoroki-Heck reaction3 which uses
the expensive aryl halides or their equivalents as starting
materials. The principal challenge lies that achieving the site-
selective activation of a specific C-H bond is difficult due to the
less pronounced reactivity differences of ubiquitous C-H bonds
in organic molecules. A typical strategy to address this issue is
this work
b)
: selective oxidatvie coupling
H
ligandfree
SiR3
Pd(II)
DG
DG
H
+
operationally simple
highly siteselective
easily modifiable
SiR3
DG =
NH2, MeNH
E-isomer
Scheme 1 TM-catalyzed C-H functionalization with vinylsilanes.
Vinylsilane derivatives are valuable synthetic intermediates in
organic synthesis.10 Obviously, one of the most efficient and
straightforward approaches to them is the direct coupling of
inert C-H bonds with vinylsilanes or alkynylsilanes11 under metal
catalysis. However, to the best of our knowledge, there have
been no successful examples on the highly selective
intermolecular oxidative coupling of the arene C-H bonds with
vinylsilanes. In the field of C-H activation, vinylsilanes have been
reported to couple with (hetero)arene C-H bonds divergently,
serving as alkylation,12 silylation,13 and olefination14 reagents
(Scheme 1). Even in dehydrogenative C-H olefination reactions,
up to three reactive sites in one molecule of vinylsilane can be
accessible, not to mention those in arenes. Consequently, it is
extremely difficult to totally control the region- and stereo-
selectivity. To date, only sparse examples of vinylsilanes
involved in the direct C-H olefination reactions9c,9h have existed,
yet the unsatisfactory results substantially hampered the
synthetic utility of this strategy. As part of our continuous
interest in catalytic C-H activation,15 herein, we report a new
and general method toward (E)-styrylsilane derivatives16
through palladium-catalyzed site-selective olefination of arenes
C-H with readily available vinylsilanes as a family of unactivated
alkenes.
to
develop
various
directing
group-assisted
C-H
functionalization4 which has enabled the efficient ortho-,5
meta-,6 and para-selective7 olefination of the arene C-H bonds.
In addition to palladium, other metals4,8 have been employed to
catalyze this transformation. Despite the impressive advances
in this type of olefination reaction, most of successful cases are
restricted to highly reactive alkenes such as acrylates,
acrylamides, vinyl sulfones, and styrenes. Reports on chelation-
assisted C-H olefination with the unactivated or electronically
unbiased alkenes are limited.9 Thus, the development of new
chelation-assisted C-H olefination reactions from easily
available unactivated olefins to produce synthetically useful
arylated alkenes is in great demand.
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry
of Education, Hangzhou Normal University, Hangzhou 311121, P. R. China
Fax: (+86)-571-28865135; phone: (+86)-571-28865135; e-mail:
ym_cui@hznu.edu.cn or liwenxu@hznu.edu.cn.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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DG
DG
We commenced our investigation with the exploration of
suitable directing groups to promote the ortho olefination of
arenes C-H with vinyltrimethylsilane. As demonstrated in
Scheme 2, most of screened directing groups (such as amide,
amine, oxime ether, pyridine, phosphine oxide, etc.) led to
either traces of products or no reaction at all. Notably, the rigid
bidentate directing group aminoquinolinamide failed to provide
the target olefinated product although it was found to be
effective in cobalt-catalyzed C-H olefination with unactivated
aliphatic alkenes.9e To our delight, when 2-N-methylamino
biaryl was tested, the desired olefinated product was afforded
in 45% yield while the carboxylic acid seemed to be a promising
directing group (30% yield).
View Article Online
i-Pr
O
H
L
TMS
Pd(OAc)2/
TMS
DOI: 10.1039/C9CC02199J
+
BocHN
OH
AgOAc, MeOH
40 oC, 24 h
L
2a
1
3
DG =
O
H
O
O
S
O
NH2
N
N
NH2
N.R.
N
OMe
OH
HN
N.R.
30%a
N.R.
trace
N.R.
N.R.
O
N
O
N
N
N
N
H
PPh2
O
H
O
NH
N.R.
45%a
N.R.
N.R.
N.R.
trace
Scheme 2 Comparison of different directing groups. Reaction conditions: 1 (0.5
mmol), 2a (1.5 mmol), Pd(OAc)2 (10 mol %), L (20 mol %), AgOAc (3 equiv),
methanol (5 mL), at 40 oC under air atmosphere. a Isolated yields.
we then turned our attention to survey a range of reaction
parameters to optimize this transformation with 1a as the
substrate (Table 1). Initially, the coupling reaction was
conducted in the presence of Pd(OAc)2 and Boc-Val-OH (L) in
MeOH using AgOAc as the oxidant. The desired olefinated
product 3a was obtained in 66% isolated yield (entry 1). A
solvent survey illustrated that DCE provided the product higher
than other commonly utilized solvents (entries 1-10). Next, an
array of palladium catalysts were briefly examined in DCE, and
PdCl2(CH3CN)2 proved to be the most efficient catalyst for this
olefination reaction (entries 11-14). Further improving the
performance of the coupling reaction using other oxidants
instead of AgOAc failed because most of starting material 1a
was recovered (entries 15 and 16). It was noteworthy that the
olefination reaction also proceeded smoothly even without
amino acid ligand (entry 17) or with decreased amount of
catalyst and oxidant (entry 18). To clarify the influence of chiral
ligand on configuration of product, we determine the ee value
of 3a. Unfortunately, only racemic olefinated product was
obtained. After the detailed screening of reaction parameters,
the optimized reaction conditions are 3 mol % PdCl2(CH3CN)2, 3
equiv of vinylsilanes, and 2 equiv of AgOAcin DCE at 40 oC under
air atmosphere.
Table 1 Effect of catalyst, solvent, and oxidant a
Palladium
oxidant
L
/
NHMe
H
NHMe
TMS
i-Pr
O
TMS
+
solvent
BocHN
OH
40 oC, 16 h
2a
L
1a
3a
entry
1
2
3
4
5
6
7
8
palladium
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(CF3CO2)2
PdCl2
Pd(acac)2
PdCl2(CH3CN)2
PdCl2(CH3CN)2
PdCl2(CH3CN)2
PdCl2(CH3CN)2
PdCl2(CH3CN)2
L(mol%)
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
0
solvent
MeOH
t-AmOH
CF3CH2OH
HFIP
oxidant yield(%)b
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
BQ
66
75
26
46
45
54
62
77
61
82
33
67
10
THF
MTBE
dioxane
toluene
DCM
DCE
9
10
11
12
13
14
15
16
17
18c
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
94
Having established the optimal reaction conditions for the
synthesis of 3a, we then studied the scope17 of the C-H
olefination reaction with respect to vinylsilane partners
(Scheme 3). In general, vinylsilanes with different substituents
on silicon atom and trimethyl(1-phenylvinyl)silane afforded the
corresponding products (3b-3d and 3f) with high yields.
Furthermore, 3e bearing a reactive chloromethyl group prone
to attack by the amine was also produced in 63% yield.
trace
trace
99
O2
AgOAc
AgOAc
0
98
a Reaction conditions: 1a (0.5 mmol), 2a (1.5 mmol), Palladium (10 mol %), L (20 mol %),
oxidant (3 equiv), solvent (5 mL), at 40 oC under air atmosphere. b Isolated yields. c Using
Palladium (3 mol %) and oxidant (2 equiv).
The generality17 of this olefination reaction for substituted 2-
aminobiaryl compounds was further systematically investigated
(Scheme 4). The methyl and phenyl groups on the upper and
bottom aromatic rings had minor influence on reaction results
(3g-3k and 3n). substrate bearing electron-withdrawing chloro
atom on the bottom ring appeared to be more reactive than
that with electron-donating methoxy group on the same
Position, furnishing the products 3m and 3l in 87% and 60%
yields, respectively. However, the steric effect became
pronounced in the case of di-substituted substrates 1i and 1j:
while the substrate with remote 2,4-dimethyl groups
underwent smooth reaction and gave excellent yield (3n), the
sterically hindered substrate containing a fluoro atom ortho to
NHMe
SiEt3
NHMe
SiPh3
NHMe
SiMe3
3a
, 99% yield
3c
, 86% yield
3b
, 71% yield
Cl
NHMe
NHMe
SiMe3
MeHN
SiPh2Me
Si
Ph
3d
3f
, 74% yield
, 88% yield
3e
, 63% yield
Scheme 3 Scope of vinylsilanes.
2 | J. Name., 2012, 00, 1-3
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(3 equiv)
TMS
DOI: 10.1039/C9CC02199J
NHMe
H
NHMe
TMS
NHMe
PdCl2(CH3CN)2 (3 mol%)
NHMe
TMS
TMS
NHMe
TMS
AgOAc (3 equiv)
DCE, 40 oC, 24 h
3a
92% yield
1a
1.16 g, 5 mmol
3i
, 80% yield
3h
, 78% yield
3g
, 92% yield
NHMe
NHMe
NHMe
NHMe
I
TMS
Ph
TMS
TMS
H2
NIS
Pd/C
4
5
NHMe
72% yield
98% yield
3k
,
3k
CCDC 1882245
NHMe
, 81% yield
3j
, 99% yield
TMS
MeI
NHMe
H
NMe2
NHMe
TMS
NHMe
TMS
K2CO3
H2SO4
TMS
TMS
Cl
MeO
6
7
56% yield
3m
, 87% yield
69% yield
3l
, 60% yield
3n
, 88% yield
N
NaN
MeHN
MeHN
NHMe
TMS
MeHN
N
(1.2 equiv)
NHMe
Si Cl
Si
N
N
TMS
SiEt3
N
DMF, 100 oC, 14 h
F
8
OMe
3q
3o
3p
, 66% yield
, 46% yield
66% yield
, 28% yield
Scheme 5 Scale-up preparation and derivatization of products.
NH2
MeHN
NHMe
TMS
Si
Si
products (3v-3x) were obtained in moderate yields but with
poor E/Z ratio, illustrating that the directing group has a vital
influence on the geometry of the products.
3r
, 48% yield
3s
, 66% yield
To investigate the efficiency and practicality of this protocol,
gram-scale synthesis of product 3a was carried out (Scheme 4).
Pleasingly, negligible deviation in the yield was observed. The
utility of the developed site-selective olefination was further
highlighted by selective transformations of the functional
groups in the products (Scheme 4). The straightforward
methylation of the amine directing group was easily realized in
the presence of iodomethane. It is worth mentioning that
arylated vinylsilanes are versatile synthetic intermediates and
the alkene moiety could be selectively converted into various
substituents. For example, upon the treatment of 3g with Pd/C
catalyst under hydrogen atmosphere, the reduction product
was formed in 98% yield. The silyl group can be removed to
produce terminal alkene 6 or underwent smooth iodination,
delivering the highly reactive iodoalkene 4. In addition, triazole
fragment was introduced by nucleophilic substitution of 3 with
1,2,4-triazole sodium salt.
In summary, we have developed an efficient palladium-
catalyzed amino-chelation-assisted olefination of arene C-H
bonds. This strategy features ligand-free and mild reaction
conditions, good functional group tolerance, and good site-
selectivity, representing a reliable and practical route to
functionalized arylated vinylsilanes. The resulting olefination
products exhibited diverse synthetic applications. Further
studies on asymmetric olefination of C-H bonds with this type
of unactivated vinylsilanes are ongoing.
NHMe
TMS
NHMe
TMS
TMS
TMS
3u
3t
, 43% yield
, 30% yield
Ph
CO2H
TMS
CO2H
TMS
CO2H
TMS
3v
3w
3x
total yield: 56%
(E/Z = 2/1)
total yield: 62%
(E/Z = 1/1)
total yield: 54%
(E/Z = 3/1)
Scheme 4 Scope of arenes
the olefination position was converted into 3o in moderate
yield. As expected, selective mono-olefination of two identical
reactive C-H bonds for substrates is difficult and the products
(3p and 3q) were formed in much lower yields. Moreover, the
substrate with a free amine as the directing group was
compatible with the reaction conditions, albeit with moderate
isolated yields (3r).
Subsequently, we studied the substrate scope toward the one
pot sequential double olefination. To ensure high yields of
double olefinated products, we tuned the ratio of substrates
relative to vinylsilanes under the aforementioned optimal
conditions. The double olefination products were afforded in
acceptable yields using 3 equiv of biaryls for 3s or olefinating
reagents for 3t and 3u. It should be noted that exclusive (E)-
isomers were formed in the cases of the olefinated products
(3a-3u), as confirmed by the X-ray structure of 3k.18 However,
when the substituted phenylacetic or biary carboxylic acids
were subjected to the present C-H olefination, the linear
We thank the financial support from the National NSF of
China (No. 21503060, 21472031, and 51303043).
This journal is © The Royal Society of Chemistry 20xx
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Chem. Soc., 2013, 135, 7567; (b) S. Lee, H. Lee and K. L. Tan, J.
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