Nickel-Catalyzed Denitrated Coupling Reaction of Nitroalkenes with Aliphatic and Aromatic Alkenes

Article abstract of DOI:10.1002/adsc.201600586

A simple and practical denitrated coupling reaction of nitroalkenes with various alkenes using a nickel catalyst and triethoxysilane [(EtO)₃SiH] as reducing agent was achieved. Under mild reaction conditions, both aliphatic and aromatic alkenes could react with nitroalkenes to obtain a series of olefins with different functional groups in satisfactory yields under an air atmosphere, which were previously difficult or impossible to access. (Figure presented.).

Full text of DOI:10.1002/adsc.201600586

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DOI: 10.1002/adsc.201600586
Nickel-Catalyzed Denitrated Coupling Reaction of Nitroalkenes
with Aliphatic and Aromatic Alkenes
a
a,
a,
Na Zhang, Zheng-Jun Quan, * and Xi-Cun Wang *
a
College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, Peopleꢀs
Republic of China
E-mail: quanzhengjun@hotmail.com or wangxicun@nwnu.edu.cn
Received: June 4, 2016; Revised: July 15, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201600586.
[
11]
Abstract: A simple and practical denitrated cou-
workers. Following this pioneering work, Cui et al.
pling reaction of nitroalkenes with various alkenes
reported the Fe/PhSiH -catalyzed reductive coupling
3
using
a
nickel catalyst and triethoxysilane
of b-nitroalkenes with unactivated alkenes under an
[
12]
[
(EtO) SiH] as reducing agent was achieved. Under
argon atmosphere (Scheme 1).
In this process the
3
mild reaction conditions, both aliphatic and aromat-
ic alkenes could react with nitroalkenes to obtain
a series of olefins with different functional groups
in satisfactory yields under an air atmosphere,
which were previously difficult or impossible to
access.
nitro group was cleaved and alkylated styrene deriva-
tives were obtained.
A detailed analysis of the reported literature dis-
closed that many strategies have been developed for
the synthesis of alkenes. There are three widely em-
ployed methodologies for the routine and reliable for-
[
13]
mation of alkenes including Wittig reaction,
Julia
[
14]
[15]
Keywords: denitrated coupling; nickel catalyst; ni-
troalkenes; triethoxysilane
olefination, and the Peterson reaction. These re-
actions rely on the requisite phosphonium salts, sul-
fone and silyl-substituted organometallic starting ma-
terials. The transition metal-catalyzed Heck reaction
is another powerful method for access to styrenes, but
[16]
always suffers from a limited substrate scope,
Nitroalkenes are an important class of synthetic inter- Given the importance of alkylated styrene molecules
[
17]
mediates, which have been applied in the preparation in natural products and pharmaceuticals,
we were
[
1]
of a wide variety of organic compounds, such as bio- attracted to the idea of developing a simple, readily
[
2]
logical compounds and pharmaceuticals. Nitroal- available catalyst system for denitrated coupling reac-
kenes are usually synthesized by the Henry reaction, tions of nitroalkenes with alkenes.
[
3]
involving carbonyl compounds and nitroalkanes, fol-
lowed by subsequent dehydration of the resulting b-
nitro alcohol. Due to the electron-withdrawing nature
of the nitro group, nitroalkenes have been widely
used for adjacent carbon-carbon double bond forming
[
4]
[5]
reactions like the Michael reaction, cycloaddition,
[
6]
Morita–Baylis–Hillman reaction,
metal-mediated
[
7]
coupling reactions,
even for the generation of
hydroxylamines, nitroalkanes,
[8]
[9]
oximes,
amines, and nitroso compounds.
aliphatic
[
5a,b]
Furthermore, the
nitro group can be transformed into other important
functionalities, allowing the nitro group to serve as
[
10]
a transient activating functional group. As a repre-
sentative example, nitroarenes were applied as amine
sources in the olefin hydroamination through a cas-
cade procedure of reduction and radical interception
in the presence of an Fe-catalyst, silane, Zn and HCl Scheme 1. A new C–C bond formation method via cross-
(
aq.), which was firstly realized by Baran and co- coupling.
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Herein we described a Ni-catalyzed denitrated cou- different silanes, such as tetramethyldisilazane
pling reaction of nitroalkenes with various alkyl- and (TMDS), polymethyl-hydro-siloxane (PMHS), regret-
arylalkenes
under
mild
reaction
conditions tably, 3a was not detected (Table 1, entries 7 and 8).
(
Scheme 1). The method is distinguished by its readily When PhSiH was replaced by (EtO) SiH, an im-
3
3
available, cheaper and environmentally friendly re- provement in the yield to 80% was observed. Also
ductant and wide substrate scope. Both aliphatic and when the reaction was run under inert gas protection
aromatic alkenes were applied in the reaction. Silox- we obtained the same results (Table 1, entry 9).The
anes, which with Si–O bond is considered as being reaction conditions were also screened by changing
a good alternative to silanes, are air stable as reducing the amount of catalyst and the proportion of 1a and
[18]
agent.
2a (Table 1, entries 10–12), and the best yield was ach-
Initially, our study commenced with the reaction of ieved with 1a:2a=1:2. Then, we reduced the reaction
b-nitrostyrene 1a and unactivated styrene 2a to search time and found that the reaction could go to comple-
for a potent catalyst system and suitable reaction con- tion in 4 h (Table 1, entries 13 and 14). In summary,
ditions. When the reaction was subjected to Ni(acac)2 we chose the reaction conditions of Ni(acac)2
or (EtO) SiH conditions in EtOH at 608C, no product (15 mol%) and (EtO) SiH (2.0 equiv.) in EtOH under
3
3
was observed (Table 1, entries 1 and 2). Gratifyingly, an air atmosphere at 608C as the optimal reaction
the combination of Ni(acac) and (EtO) SiH in EtOH conditions.
2
3
at 608C gave the desired reductive coupling product
After establishing optimal reaction conditions, we
3
a in 78% yield (Table 1, entry 3). Standard methods performed the reducing coupling with a wide range of
of identification showed that the nitro group had aromatic olefin substrates. The scope is broad with
been cleaved and the product was a tertiary alkylated regard to both partners (Table 2). Various sterically
styrene derivative. This result encouraged us to fur- diverse aromatic olefins such as donor and electron-
ther optimize the reaction conditions. First, various deficient substrates were found to undergo reducing
metal salts were examined as catalyst for the transfor- coupling with nitroalkene 1a in good yields (3a–3f).
mation and Ni(acac) was found to be the most effec- Then we examined the reaction of various substituted
2
tive one (Table 1, entries 3–6). We next examined the nitroalkenes with unsubstituted styrene 2a. A series
of para-, and ortho-donating substituted nitroalkenes
[
a]
participated in the reducing coupling to afford the
products (3g, 3h, 3j) in moderate to good yields.
Again, para- and ortho-chloride substituted nitroal-
kenes also served as viable coupling reaction and af-
forded products 3i and 3k. Interestingly, when a nitro-
alkene containing a furyl ring was utilized in this re-
ductive coupling, the process delivered the desired
alkene 3l in 63% yield.
Table 1. Screening of the reaction conditions.
Entry Catalyst
mol%)
Silane
(2 equiv,)
Time
[h]
Yield
[b]
Then, we investigated a variety of nitroalkenes 4 as
vinylation reagents to react with aliphatic alkenes 5
(
[%]
(
Table 3). The reactions with substituents including
1
2
3
4
5
6
7
8
9
1
1
1
1
1
–
(EtO) SiH
–
12
12
12
12
12
12
12
12
12
12
12
12
8
–
–
78
70
–
–
–
–
79
54
79
43
76
76
3
methyl, methoxy, fluoro, chloro, and bromo were ach-
ieved in moderate yields in this protocol (6a–6f and
6h, 6i). Whereas the one derived from nitro-substitu-
tion nitroalkene failed to participate in the reaction
generating the corresponding product 6g in trace
yield. Moreover, aliphatic alkenes such as octene, cy-
clohexene and allylbenzene were amenable to this
transformation delivering the corresponding products
Ni(acac) (15)
Ni(acac) (15) (EtO) SiH
Fe(acac) (15) (EtO) SiH
CuSO (15)
CoCl (15)
Ni(acac) (15) TMDS
Ni(acac) (15) PMHS
Ni(acac) (15)
Ni(acac) (10) (EtO) SiH
Ni(acac) (20) (EtO) SiH
Ni(acac) (15) (EtO) SiH
Ni(acac) (15) (EtO) SiH
2
2
3
2
3
(EtO) SiH
4
3
(EtO) SiH
2
3
2
2
[
c,d]
PhSiH3
2
0
1
2
3
4
2
3
6
j–6l in good yields. Notably, hydroxy, ether, and even
2
3
[
[
e]
f]
carbonyl groups (6m–6o) were well tolerated in this
process, thus offering opportunities for further deriva-
tization. Additionally, a di-substituted alkene (6-meth-
ylhept-5-en-2-one) served as viable electron-with-
drawing substrate in this reductive coupling providing
tertiary alkylated styrenes 6r–6t in moderate yields.
Moreover, a heteroaryl-furan nitroalkene also pro-
duced the corresponding compound in moderate yield
(6p, 6q). This reveals that a wide range of alkylated
alkenes can be prepared easily under mild reaction
2
3
2
3
Ni(acac) (15) (EtO) SiH
4
2
3
[
a]
Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), EtOH
(2 mL), 608C.
b]
[
[
[
[
[
Isolated yields are reported.
Reaction run under air.
Reaction run under nitrogen.
equiv. 2a was used.
equiv. 2a were used
c]
d]
e]
f]
1
3
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[a]
Table 2. Substrate scope of arylalkenes.
[
[
a]
b]
Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), Ni(acac) (15 mol%), (EtO) SiH (2 equiv.), EtOH (2 mL), 608C, 4 h, air.
Isolated yields are reported.
2
3
[a]
Table 3. Substrate scope of alkylalkenes.
[
[
a]
b]
Reaction conditions: 4 (0.2 mmol), 5 (0.4 mmol), Ni(acac) (15 mol%), (EtO) SiH (2 equiv.), EtOH (2 mL), 608C, 4 h, air.
Isolated yields are reported.
2
3
conditions and with readily available starting materi- Omission of Ni(acac) completely shut down the reac-
2
als.
tivity and the starting materials were recovered, dem-
The C–C coupling of nitroalkenes with alkenes onstrating the necessity for the Ni catalyst. Moreover,
using Ni-catalysis was expected to proceed through when a radical scavenger 2,2,6,6-tetramethylpiperi-
[
11,12]
a radical mechanism,
and preliminary mechanistic dine 1-oxyl (TEMPO) or a radical inhibitors 2,6-di-
investigations supported this assumption (Scheme 2). tert-butyl-4-methylphenol (BHT) was added, the re-
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B, placing the Ni atom on the more substituted
carbon atom. The dissociation of B delivers Ni(I) spe-
cies C and alkyl radical D, which is trapped by nitro-
alkene 1 to generate the b-nitro radical E. The se-
quential elimination of E would furnish the alkylated
styrene products (3 or 6) and a nitro radical which
would reoxidize C to an Ni(II) species to enable the
catalytic cycle.
In summary, we have developed a denitrated C–C
coupling reaction of nitroalkenes with various alkyl-
and arylalkenes using a Ni catalyst and (EtO) SiH as
3
reducing agent under mild reaction conditions. Com-
[
12]
pared with the previous works,
this method is
a better choice and has some obvious advantages. Ar-
omatic olefins could also show satisfactory reactivity
under these conditions. Besides, the carbonyl group is
also tolerated in this reaction and the high stability of
Ni(acac) and (EtO) SiH toward air and moisture
2
3
allows the reaction to be conducted under an air at-
mosphere. Therefore, this method provides a rapid
and efficient access to alkylated styrene derivatives,
from simple and readily available starting materials.
Scheme 2. Control experiments.
ductive coupling product 3a was not observed. These
control experiments suggest that the reaction pro-
ceeds via a radical pathway.
Experimental Section
On the basis of the above observations and litera-
[11,12]
ture reports,
a plausible mechanism for this reac- General Experimental Procedure for the Synthesis of
tion is proposed (Scheme 3). Initially, Ni hydride A Compounds 3 and 6
was generated from Ni(II)-catalyst and triethoxysi-
lane, then it regioselectively adds to alkene 2 to form
A mixture of nitroolefin (0.2 mmol), alkene (0.4 mmol),
Ni(acac)2 (15 mol%), (EtO) SiH (2 equiv.), and EtOH
3
(
2 mL) was heated at 608C for 4 hours under an air atmos-
phere. After completion of the reaction as monitored by
TLC, the reaction mixture was cooled to room temperature
and extracted between water and ethyl acetate. The com-
bined organic layers were dried over anhydrous MgSO and
4
concentrated under reduced pressure to get the crude prod-
uct. This was purified by silica gel column chromatography
using EtOAc:hexane as eluents to afford the corresponding
product.
Acknowledgements
We are thankful for the financial support from the NSFC of
China (Nos. 21362032, 21362031 and 21562036) and Gansu
Provincial Department of Finance.
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Nickel-Catalyzed Denitrated Coupling Reaction of
Nitroalkenes with Aliphatic and Aromatic Alkenes
Adv. Synth. Catal. 2016, 358, 1 – 6
Na Zhang, Zheng-Jun Quan,* Xi-Cun Wang*
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