Controlled mono-olefination: Versus diolefination of arenes via C-H activation in water: A key role of catalysts

Article abstract of DOI:10.1039/c8gc00790j

Herein, we report the olefination of arenes via C-H activation in water instead of in expensive and pollution-causing organic solvents. In this process, the catalysts were shown to play a key role in controlling mono- and diolefinations. More specifically

Full text of DOI:10.1039/c8gc00790j

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DOI: 10.1039/C8GC00790J
Journal Name
ARTICLE
Controlled mono-olefination versus diolefination of arenes via C-
H activation in water: A key role of catalysts
Hailong Zhang,a Zhongzhen Yang,a Qiang Ma,a Jinxin Liu,a Yang Zheng,a Mei Guanb* and Yong Wua*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Herein, we report the olefination of arenes via C-H activation in water instead of expensive and pollution-causing organic
solvent. In this process, the catalysts play a key role in controlling mono- and diolefination. More specifically, [Ru(p-
cymene)Cl2]2 gives mono-olefinated products predominantly while [Cp*RhCl2]2 selectively affords diolefinated products.
Importantly, the usage of catalysts is few ([Ru(p-cymene)Cl2]2 5 mol %, [Cp*RhCl2]2 1 mol %) and the reaction time is
significantly shortened from tens of hours to tens of minutes. Additionally, the new methodology tolerates a variety of
functional groups and olefins in moderate to good yields and can be applied to a gram scale synthesis at a low catalyst
loading.
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alkenylation of aromatic compounds reported by Y. Ogiwara,
Introduction
During the past decades, transition-metal-catalyzed direct C-
H bond functionalization has become one of the most
sustainable and straightforward methods in organic synthesis
chemistry.1 By avoiding tedious and costly preparation of pre-
activated starting materials, such method has been
a
streamlined synthetic strategy to replace C-H bond by C-C, C-N,
C-O, C-Si, C-P, C-S or C-X ( X = halogen) bonds.2 Among the
most promising strategies, previous sp2 C-H bond activation
was achieved by using various late transition-metal complexes
(e.g., Ru, Rh, Co, and Ir) in expensive and pollution-causing
organic solvent for tens of hours.3 In order to make olefination
more eco-friendly and economically, it is better to avoid
organic solvent and shorten the reaction time. It is known that
water is the ideal substitute as it is abundant, non-polluting,
non-toxic and non-inflammable.
Scheme 1. C-H olefination of arene
also afforded the diallylated coupling products.7 What
's more,
The majority of the current sp2 C-H activation reactions gave
mono-olefinated products predominantly.4 Some studies
reported the production of both mono- and diolefinated
products of arenes, yet the mono- or diolefination were
uncontrollable. For example, Y. Matsuura and co-workers
synthesized the ð-conjugated aromatic compounds with
alkenyl acetates along with three extra diarylethene-type
products.5 Similarly, in the work of Y. Takahama et al, who
reported the sp2 C-H bond allylation of 1-phenylpyrazole, 16%
diallylated product was accompanied by 73% monoallylated
there were also some reports of the selective catalysis for
mono- and diolefination via C-H activation. For instance,
Nobuyoshi and co-workers reported the rhodium-catalyzed
mono- and di-vinylation of 1-phenylpyrazoles via controlling
the amount of Cu(OAc)2·
H2O.8 X. W. Li et al and D. Maiti et al
separately reported the selective mono- and diolefination
through C-H activation controlled by solvent.9,10 In 2011, M.
Miura and co-workers published their work on rhodium-
catalyzed regioselective olefination controlled by substrates.11
Thereafter, C. J. Li and co-workers also reported the rhodium-
catalyzed tandem dehydrogenative coupling-michael addition,
where the 3-substituted and 3,7-disubstituted products were
selectively obtained using different olefines.12 However,
protocols for the selective synthesis of mono- and diolefinated
products, catalyzed by different catalysts with full control,
remained to be explored to our best knowledge.
product.6
Ruthenium-catalyzed
ortho-selective
C-H
a.Key Laboratory of Drug-Targeting of Education Ministry and Department of
Medicinal Chemistry, West China School of Pharmacy, Sichuan University
Chengdu, 610041, P.R.China. E-mail:wyong@scu.edu.cn; Fax:+8602885503666
b. West China Hospital, Sichuan University, No. 37. GuoXue road, Chengdu 610041
Footnotes: A more detailed optimization of the reaction condition is listed in the in
Supporting Information
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d
H2O (0.5 mL), [Ru(p-cymene)Cl2]2 (1 mol %), e [Cp*RhCl2]2 (5 Vmieowl A%rt)icHle2OOn(l0in.e5
mL) , f [Cp*RhCl2]2 (1 mol %) H2O (0.5 mL) , (Detail condition screens are in Table S
1).
DOI: 10.1039/C8GC00790J
1,2,3-trizaoles have been widely applied in medicinal,
peptidomimetic and fine chemistry because of its special
chemical and medicinal properties.13 For organic synthesis, the
1,2,3-triazole motifs have also been used as a handy directing
group in the ortho C-H bond functionalization, including ortho-
sulfonamidation,14 acylation,15 acyloxylation,16 alkoxylation,17
halogenation,18 arylation19 and so on. In addition, we have also
been working on the C-H activation of 1,2,3-trizaole since
recent years.20 Inspired by those successes and our continuous
interests in C-H activation, herein we report the controllable
mono- and diolefination of arenes via C-H activation that are
carried out in water within tens of minutes. The catalysts play
a key role in controlling the mono- and diolefination, where
features of our methodology include (a) the solvent was water,
(b) the reaction time was reduced from hour- scale to minute-
scale, (c) the amount of catalysts was a little, (d) the
controllable mono- and diolefination of arenes catalyzed by
different transition metals via C-H activation were achieved for
the first time, and (e) the reaction tolerated a broad range of
substrates and olefins in satisfactory yields with excellent
selectivity even in gram-scale.
Results and discussion
Our initial experiment was carried out with 2-phenyl-1,2,3-
[Ru(p-cymene)Cl2]2
gave
mono-olefinated
products
triazole
[Cp*Rh(MeCN)3][SbF6]2, the corresponding products were
isolated separately, giving 51% of 3a and 34% of 3a'
(1a) and styrene (2a) in water. Catalyzed by
predominantly while [Cp*RhCl2]2 selectively afforded the
diolefinated products. The notable
,
respectively (Table 1, entry 1). In order to increase the
conversion of 1a and the selectivity for 3a, different catalysts
were screened. It was found that [Ru(p-cymene)Cl2]2 could
produce 3a predominantly with a yield of 83%, while the yield
of 3a' was 14%. In contrast, [Cp*RhCl2]2 afforded 3a' in 68%
yield along with 22% of 3a (Table 1, entries 2-5). In regard of
the amount of 2a, the use of 2 equiv of 2a provided the
optimal results for mono-olefination, while 4 equiv of 2a was
required to get the optimal results for diolefination (Table 1,
entries 6-7 and 16-18). The reaction time was also successfully
shortened from tens of hours to tens of minutes (Table 1,
entries 8-10 and 18-20). Furthermore, when water was
decreased, the dose of [Ru(p-cymene)Cl2]2 was successfully
reduced to 5 mol % (Table 1, entries 11-14).
Table 1. Optimization of the reaction condition.a
Time
(min) 3a/3a' (%)
Yields b of
entry 2a
Catalyst
1
2
3
4
5
6
7
8
9
10
11c
12d
13d
14d
15
16
17
18
19
20
21e
22f
23f
24f
2
2
2
2
2
1
3
2
2
2
2
2
2
2
2
1
3
4
4
4
4
4
4
4
[Cp*Rh(MeCN)3][SbF6]2
[Cp*Co(MeCN)3][SbF6]2
[Cp*IrCl2]2
900
900
900
900
900
900
900
450
120
60
60
60
90
120
60
60
60
60
30
10
10
10
20
51/34
-/-
41/-
22/68
83/14
52/28
80/17
82/16
71/12
86/9
[Cp*RhCl2]2
Table 2. Reaction scope of mono-olefination of 1,2,3-triazolea,
[Ru(p-cymene)Cl2]2
[Ru(p-cymene)Cl2]2
[Ru(p-cymene)Cl2]2
[Ru(p-cymene)Cl2]2
[Ru(p-cymene)Cl2]2
[Ru(p-cymene)Cl2]2
[Ru(p-cymene)Cl2]2
[Ru(p-cymene)Cl2]2
[Ru(p-cymene)Cl2]2
[Ru(p-cymene)Cl2]2
[Cp*RhCl2]2
b,c
85/8
61/7
56/14
59/17
21/53
34/48
16/76
4/94
7/92
6/91
9/81
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
36/57
19/77
4/93
[Cp*RhCl2]2
30
a
The reaction conditions of mono-olefination: 1a (0.2 mmol), 2a (0.4 mmol),
[Ru(p-cymene)Cl2]2 (10 mol %), AgNTf2 (0.04 mmol), Cu(OAc)2·H2O (0.2 mmol) in
H2O (0.5 mL) were stirred at 120 oC; The reaction conditions of diolefination: 1a
(0.2 mmol), 2a (0.8 mmol), [Cp*RhCl2]2 (10 mol %), AgNTf2 (0.04 mmol),
a
The reaction conditions: 1a (0.3 mmol), 2a (2 equiv), [Ru(p-cymene)Cl2]2 (5
b
Cu(OAc)2·H2O (0.8 mmol) in H2O (0.5 mL) were stirred at 120 oC. Yield of
c
mol %), AgNTf2 (0.2 equiv), Cu(OAc)2·H2O (1 equiv) in H2O (0.5 mL) were stirred
products isolated after column chromatography. [Ru(p-cymene)Cl2]2 (5 mol %)
2 | J. Name., 2012, 00, 1-3
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b
c
b
at 120 oC for 60 min; Isolated yield. The remaining of reaction is starting
materials.
for 30 min. Isolated yield. c isolated as an inseparable mixtureV. idewThAertricelme Oainnliinneg
of reaction is starting materials.
Thereafter, we also screened theDOsuI:b10s.t1r0a3t9e/C8sGcoCp00e790oJf
diolefination of 1,2,3-triazole under the optimal condition. As
shown in Table 3, various substrates of 1,2,3-triazole provided
the desired products in moderate to good yields. For example,
the para-substituted substrates with methyl and tert-butyl
underwent this reaction to furnish the corresponding products
3b' and 3c' in 87% and 91% yields, respectively. In contrast, the
triazoles, substituted with chlorine (3d'), bromine (3e'), phenyl
In contrast to [Ru(p-cymene)Cl2]2, the dose of [Cp*RhCl2]2
could even be decreased to 1 mol % by extending the reaction
time from 10 min to 30 min (Table 1, entries 21-24).
Accordingly, the reaction condition of mono-olefination was
optimized as follows: 1a (0.2 mmol), 2a (0.4 mmol), [Ru(p-
cymene)Cl2]2 (5 mol %), AgNTf2 (0.04 mmol), Cu(OAc)2·H2O
(0.2 mmol) in H2O 0.5 mL at 120 C for 60 min; The reaction
condition of diolefination was optimized as follows: 1a (0.2
mmol), 2a (0.8 mmol), [Cp*RhCl2]2 (1 mol %), AgNTf2 (0.04
o
(
3f'), trifluoromethyl (3g') and cyano (3h') provided the desired
products in lower yields with prolonged the reaction time.
However, for the 1,2,3-triazole substituted with nitro, 3i was
the predominant product even the reaction time was
prolonged from 60 min to 240 min. Obviously, the para-
substitued substrates containing electron-donating groups
were more effective than those with electron-withdrawing
groups. The electronic effects of substrates on this
diolefination reaction were also applicable to meta-substitued
1,2,3-triazoles (1i
styrenes, including methyl (1n), tert-butyl (1o), trifluoromethyl
1p), fluoro (1q) and nitro (1r), were reacted with 1a under
the optimal conditions to produce the desired products 3n -3r',
and the yields were all over 60% except for 4-nitrostyrene (1r),
which gave mono-olefinated product predominantly. It was
possible that the strong electron-withdrawing groups
deactivated the ring towards the second olefination.
Unreactive 1-octene was also probed to produce the
corresponding product 3s
ethyl and t-butyl acrylate predominantly afforded the
diolefinated products 3t and 3u , the probable explanation
o
mmol), Cu(OAc)2
·
H2O (0.8 mmol) in H2O 0.5 mL at 120 C for
30 min.
Under the optimized conditions in hand, the substrate scope
of mono-olefination of 1,2,3-triazole via C-H activation was
explored. As shown in Table 2, a variety of substituted 1,2,3-
triazoles were readily furnished in moderate to high yields. For
example, 1,2,3-triazoles containing electron donating groups
-1k). Additionally, different para-substituted
(e.g., Me and t-Bu) afforded the desired products 3b, 3c and 3j
in 86%, 86% and 84% yields, respectively. 1,2,3-triazoles
containing electron withdrawing groups (e.g., Cl, Br, Ph, CF3,
CN and NO2), irrespective of their positions (ortho, meta or
para), were also compatible and gave the desired products
(
'
(
3d-3i, 3k and 3l) when the reaction time was prolonged.
Intriguingly, 1,2,3-triazoles with substituents at different
positions of the aromatic ring all showed high selectivities
towarding mono-olefination. Also, different olefins were
reacted with 1a. Para-substituted styrenes, including methyl
1n), tert-butyl (1o), trifluoromethyl (1p), fluro (1q) and nitro
1r), were reacted with 1a under the optimal conditions. They
all smoothly gave the desired products 3n-3r in 57%-73%
yields. Furthermore, unreactive 1-octene was also tested to
produce the corresponding product 3s, and the yield was 67%.
' with the yield of 58%. Furthermore,
'
'
(
(
could be that the weak coordination between the metal center
and ester allowed the metal to dissociate so that the directing
group could rotate and catalyze the olefination at the other
free ortho-position.
Table 4. Scope of mono- and di-olefination of different direct
Table 3. Reaction scope of diolefination of 1,2,3-triazole a,b,c,d
groups in water a,b
a
The reaction conditions: 4 (0.3 mmol), 2a (2 equiv), [Ru(p-cymene)Cl2]2 (5
mol %), AgNTf2 (0.2 equiv), Cu(OAc)2·H2O (1 equiv) in H2O (0.5 mL) were stirred
a
The reaction conditions: 1a (0.3 mmol), 2a (4 equiv), [Cp*RhCl2]2 (1 mol %),
b
at 120 oC for 300 min. The reaction conditions: 4 (0.3 mmol), 2a (4 equiv),
AgNTf2 (0.2 equiv), Cu(OAc)2·H2O (4 equiv) in H2O (0.5 mL) were stirred at 120 o
C
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[Cp*RhCl2]2 (1 mol %), AgNTf2 (0.2 equiv), Cu(OAc)2·H2O (4 equiv) in H2O (0.5 mL)
cymene)Cl2]2 and [Cp*RhCl2]2, respectively. The results
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were stirred at 120 oC for 30 min. c Isolated yield.
indicated that ortho-C-H bond activationDisOaI: 1r0e.v10e3r9s/iCbl8eGpCr0o0c79e0sJs.
Additionally, the intermolecular competition experiments
Next we also explored the reaction scope using various
directing groups. As shown in Table 4, 2-phenylpyridine, 2-
phenylpyrimidine, 1-phenylpyrazole, 3-methylbenzaldehyde O-
between the different para-substituted triazoles (1b and 1g
)
were carried out. The results showed that the competitiveness
methyl oxime and N-methylbenzamide were reacted with 2a of 1b was slightly higher than that of 1g in mono-olefination.
and the products 4a
good yields, respectively. However, 3-methylbenzaldehyde O-
methyl oxime 1d and N-methylbenzamide 1e
predominantly afforded mono-olefinated products 4d and 4e
predominantly, rather than diolefinated products 4d' and 4e'
under the diolefination conditions. In addition, 1-(pyrimidin-2-
yl)-1H-indole and 2-phenylpyrimidine 1-oxide were also found
to be unreactive and did not afford the corresponding
-4e, 4a'-4c' were obtained in moderate to
Specifically, electron-rich substrate 1b was slightly more
effective than electron-poor substrate 1g. In contrast, such
preference was more obvious in diolefination. This suggested
that electron-donating substrates might be more reactive than
electron-withdrawing substrates in general (Scheme 4).
(
)
(
)
products 4f and 4g
.
Scheme 4. The intermolecular competition experiments
between different triazoles 1b and 1g
To further understand the reaction, we then carried out a
reaction of 3a catalyzed by [Cp*RhCl2]2 (Scheme 5). When 3a
was reacted with styrene in the reaction conditions of
diolefination, 3a' was obtained in 84% yield. Furthermore, 3a
was also detected in diolefination reaction and the proportion
decreased as the reaction time increases (Table 1, entries 22-
24). Those results indicated that the monoolefinated product
3a is an intermediate in the formation of the diolefinated
product 3a'. Hence, the diolefination might be a two-step
process rather than a collaborative process. Otherwise, the
mono-olefinated product 3a would not be detected under the
Scheme 2. Gram-scale mono- and diolefination of 1,2,3-
triazole at low catalyst loading
The remarkable advantage of the selective mono- and
diolefination for arenes was demonstrated by the gram-scale-
reaction with a very low catalyst loading (Scheme 2). Therefore,
this method could be useful in production, given its short
reaction time and the use of green solvent.
diolefination condition, as well as the formation of 3a' from 3a
.
Scheme 5. The further reaction of 3a catalyzed by [Cp*RhCl2]2.
Scheme 3. The H/D exchange experiments of 1a
.
To study the possible mechanism, the H/D exchange
experiments (Scheme 3) were performed by treating 1a with
D2O in H2O. The 1H-NMR analysis showed that 52% and 41% of
the ortho-C-H in 1a were deuterated catalyzed by [Ru(p-
4 | J. Name., 2012, 00, 1-3
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Scheme 6. The competition experiment between 1a and 3a
.
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DOI: 10.1039/C8GC00790J
Fig. 1 The possible reaction mechanism.
Moreover, the competition experiment between 1a and 3a
was conducted. They were reacted with superfluous 1-(tert-
butyl)-4-vinylbenzene at 120 oC for 10 min (Scheme 6). The
ratio of products 3c and 5a was 5.3 : 1. Therefore, it was more
difficult for 3a to react with 1-(tert-butyl)-4-vinylbenzene to
afford 5a. And the results indicated that the second step of
diolefination is more difficult than the first step.
unprecedented reaction provides a new approach to the
synthesis of valuable unsaturated aromatic compounds in drug
discovery and material science.
Experimental
General Procedure for the Synthesis of 3a
Based on the above results and previous related studies,4,21-
23
a possible mechanism was proposed and shown in Fig. 1
.
Firstly, chloride ions in catalysts were trapped by silver,
splitting the dimer into a monomer. The active species
was formed by exchanging the ligand with acetate.
Subsequently, the active species and 1a was combined to
activate the C-H bond through concerted metalation-
deprotonation (CMD) to afford the intermediate . On the
other hand, the C-H bond activation by species A' might follow
the electrophilic aromatic substitution (SEAr). The difference
between C-H bond activation might be the reason behind the
A 15mL sealed tube were charged with 2-phenyl-2H-1,2,3-
triazole 1a (14.5 mg, 0.1 mmol), styrene 2a (20.8 mg, 0.2
mmol), [Ru(p-cymene)Cl2]2 (3 mg, 0.005 mmol), AgNTf2 (7.7 mg,
A (A')
A
0.02mol), Cu(OAc)2·H2O (20.0 mg, 0.1 mol), and H2O 0.5 mL.
o
The mixture were stirred at 120 C for 60 min and monitored
by TLC. Then cooled down to ambient temperature. The
B
mixture was extracted with diethyl ether (3
× 5 mL) and then
the combined organic extracts were washed with brine (2
×
10 mL) and dried with sodium sulfate. The solvent was
evaporated in vacuo and the residue was further purified by
selectivity of rhodium and ruthenium. Then,
generated after losing a proton, followed by the coordination
with styrene to afford
takingplace to form the C-Ru bond (
which would afford olefinated product 3a after β-hydride
elimination. At the same time, ) was also released and
then turned to ) after reductive elimination, which would
be reoxidized to form ) again by Cu(OAc)2·H2O to close the
C (C') was
D
(D'). Next, the insertion was flash chromatography of silica gel (silica gel, acetone /
E
) (the C-Rh bond E'),
petroleum ether = 1:200), affording the product 3a
.
F (F'
General Procedure for the Synthesis of 3a'
G (G'
A (A'
A 15mL sealed tube were charged with 2-phenyl-2H-1,2,3-
triazole 1a (14.5 mg, 0.1 mmol), styrene 2a (41.6 mg, 0.4
mmol), [Cp*RhCl2]2 (0.6 mg, 0.001 mmol), AgNTf2 (7.8 mg, 0.02
catalytic cycle. After another catalytic cycle, 3a' was provided.
mol), Cu(OAc)2·H2O (80.0 mg, 0.4 mol), and H2O 0.5 mL. The
Conclusions
mixture was stirred at 120 oC for 30 min and monitored by TLC.
Then cooled down to ambient temperature. The mixture was
In summary, we reported the transition metal controlled
mono- and diolefination of arenes via C-H activation in water.
The mono- and diolefinated products were selectively afforded
by ruthenium and rhodium, respectively. The reaction time
was drastically reduced to tens of minutes from tens of hours
in previous methods. The reaction showed a broad substrate
scope and provided the desired products in satisfactory yields
with excellent selectivity even in the gram-scale. This
extracted with diethyl ether (3
combined organic extracts were washed with brine (2
×
5 mL) and then the
10
×
mL) and dried with sodium sulfate. The solvent was
evaporated in vacuo and the residue was further purified by
flash chromatography of silica gel (silica gel, acetone /
petroleum ether = 1:150), affording the product 3a'
.
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11 S. Mochida, K. Hirano, T. Satoh, M. Miura, J. Org. Chem, 2011,
Conflicts of interest
There are no conflicts to declare.
View Article Online
76, 3024.
12 A. Renzetti, H. Nakazawa, C.J. Li, RSC. Adv, 2016,
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13 For selected examples, see: (a) K. F. McClure, M. Jackson, K.
O. Cameron, D. W. Kung, D. A. Perry, S. T. M. Orr, Y. X. Zhang,
J. Kohrt, M. H. Tu, H. Gao, D. Fernando, R. Jones, N. Erasga, G.
Q. Wang, J. Polivkova, W. H. Jiao, R. Swartz, H. Ueno, S. K.
Bhattacharya, I. A. Stock, S. Varma, V. Bagdasarian, S. Perez,
D. Kelly-Sullivan, R. D. Wang, J. Kong, P. Cornelius, L. Michael,
E. Lee, A. Janssen, S. J. Steyn, K. Lapham, T. Goosen, Bioorg,
Med. Chem. Lett, 2013, 23, 5410; (b) S. Ryo, N. Dai, F. Aya, N.
S. Rie, A. Masahito, H. Nobutaka, O. Hiroshi, A. Yuko, K. Daiji,
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Acknowledgements
We are grateful for support from the National Natural
Science Foundation of China (NSFC) (grant number 81573286,
81373259 and 81773577 ).
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Green Chemistry
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DOI: 10.1039/C8GC00790J
Catalysts-controlled mono- and diolefination of arenes via C-H activation in water within tens
of minutes