Nickel-Catalyzed Alkylarylation of Activated Alkenes with Benzyl-amines via C?N Bond Activation

Article abstract of DOI:10.1002/chem.201800543

A nickel-catalyzed alkylarylation of active alkenes with tertiary benzylamines was achieved by charge-transfer-complex promoted C?N bond activation. The reaction proceeded through initial Ni-catalyzed C?N bond activation, followed by sequential radical addition, redox and proton abstraction with cleaved amine moiety in the absence of oxidant, and provides an efficient method to prepare various alkyl-substituted oxindoles and dihydroquinolinones in good yields.

Full text of DOI:10.1002/chem.201800543

A Journal of
Accepted Article
Title: Nickel-Catalyzed Alkylarylation of Activated Alkenes with
Benzylamines via C-N Bond Activation
Authors: Hanmin Huang, Hui Yu, and Bin Hu
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To be cited as: Chem. Eur. J. 10.1002/chem.201800543
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10.1002/chem.201800543
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Nickel-Catalyzed Alkylarylation of Activated Alkenes with Benzyl-
amines via C-N Bond Activation
Hui Yu, Bin Hu,* and Hanmin Huang*
Abstract: A nickel-catalyzed alkylarylation of active alkenes with
tertiary benzylamines was achieved via charge-transfer complex
promoted C-N bond activation. The reaction proceeds through initial
Ni-catalyzed C-N bond activation, followed by sequential radical
addition, redox and proton-abstraction with cleaved amine-moiety in
the absence of oxidant, which provides an efficient method to
prepare various alkyl-substituted oxindoles and dihydroquinolinones
in good yields.
(Scheme-1a).[9] Our mechanistic experiments suggested that the
C-N bond of the in-situ formed amine-I2 complex is capable of
extracting a single electron from Ni(0) in the absence of external
oxidant to generate a benzylic radical. In this context, we
questioned whether the method for generation of benzylic
radicals via charge-transfer complex promoted C-N bond
activation could be integrated with Ni-catalyzed alkene
difunctionalization.[10] Such a manifold would offer a possibility of
achieving coupling reactions via inert bond activation with even
the strongest simple C-N bonds.
Benzylic radicals are versatile intermediates that have been
extensively utilized in synthetic organic chemistry.[1] In these
processes, efficient methods for the generation of the reactive
benzylic radicals are required. Among a variety of reactions
initiated with benzylic radicals,[2] the oxidative activation of sp3 C-
H bonds of alkylarenes via hydrogen atom abstraction has been
demonstrated as one of the most popular methods to access
such kind of species. However, stoichiometric amounts of strong
and expensive oxidants such as TBP and NSFI are general
required. Moreover, almost in all of these reactions, a large
excess of alkylarenes was required as the benzylic radical
source, or even as a solvent. Therefore, the development of
efficient alternative methods to generate benzylic radicals would
be valuable.
The C-N bond is one of the most ample chemical bonds and
widely exists in organic molecules and biomacromolecules.[3]
The formation and transformation of C−N bonds are among the
central topics in organic chemistry, organometallic chemistry,
and biochemistry.[4,5] Although two kind of useful nucleophiles
could be generated via the cleavage of one C-N bond of simple
amines,[5] compared to the extensive studies on the activation of
C−H bond,[6] the studies on the transition-metal-catalyzed C−N
bond activation of simple amines is less explored because of the
lack of suitable active frontier orbitals that could readily accept
the d-electron from transition-metal center.[7] Our group has
pursued the development of efficient strategies to cleave C-N
bond of simple tertiary amines via transition-metal catalysis.[8]
One promising strategy for activation of benzylic C-N bond by
formation of amine-I2 charge-transfer complex has been
developed and successfully applied in the Ni-catalyzed direct
insertion of CO into the C-N bond of simple benzylamines
Successful realization of this goal, however, would require
the identification of suitable alkene substrates to adopt the
following reaction mechanism (Scheme-1b). Firstly, the radical B
generated from the amine-I2 charge-transfer complex could be
reacted with the functionalized alkene via two sequential radical
addition reaction to produce intermediates C. The intermediate
C should be capable of reducing the Ni(I) to recycle the Ni(0)-
catalyst via single-electron transfer (SET). Meanwhile, the
proton contained in the oxidized intermediate C should be
removed by the cleaved amine-moiety (R2N-) to produce the
desired product. Herein, we report
a novel Ni-catalyzed
arylbenzylation of activated alkenes via C-N bond activation, in
which the easily available and inexpensive benzylamines were
utilized as benzyl source (Scheme-1c). The reaction can be
carried out in the absence of strong oxidants and the cleaved
Scheme 1. Ni-catalyzed difunctionalization of activated alkenes via C-N bond
activation
[a]
[b]
[c]
Mr. H. Yu, Prof. B. Hu, and Prof. H. Huang
State Key Laboratory for Oxo Synthesis and Selective Oxidation,
Lanzhou Institute of Chemical Physics, Chinese Academy of
Sciences, Lanzhou 730000, P. R. China
E-mail: hcom@licp.cas.cn; hanmin@ustc.edu.cn
Prof. H. Huang
Hefei National Laboratory for Physical Sciences at the Microscale,
and Department of Chemistry, Center for Excellence in Molecular
Synthesis, University of Science and Technology of China, Chinese
Academy of Sciences, Hefei, 230026, P. R. China
Mr. H. Yu
amine-moiety was used as a base to promote the reaction and
avoids to use a large excess of starting materials. It is worth
noting that this method represents one of efficient ways to
synthesize a variety of alkylated oxindoles and dihydroquino-
linones, which are important in natural products and biologically
active compounds (Scheme-1c).[11,12]
University of Chinese Academy of Sciences, Beijing 100049, P. R.
China
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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Initially, the cyclization of N,N-diisopropyl benzylamine (1a)
and N-methyl-N-phenylmethacrylamide (2a) was chosen as a
model reaction for the optimization investigation (Table 1, for
more details see the SI). To our delight, when NiCl2 was utilized
as a catalyst precursor and L1 as a ligand at 150 oC in the
presence of catalytic amount of I2, the desired oxindole 3aa was
obtained in 83% isolated yield (Table 1, entry 1). Further
evaluation of the nickel source (Table 1, entries 2-4)
demonstrated that both Ni(0) and Ni(II) could be utilized as the
catalyst precursor and the NiI2 stood out as the best one to
deliver the desired product in 91% isolated yield (Table 1, entry
3). Furthermore, the impact of the ligands was carried out with
NiI2 as a catalyst precursor, revealing that the inexpensive and
commercially available Xantphos was the most effective ligand
for this reaction to give the desired product 3aa in 92% isolated
yield (Table 1, entry 5). Several representative solvents such as
toluene, dioxane, DMSO and 2-PrOH were also screened, but
they afforded lower yields of 3aa (entries, 9–12). Control
experiments demonstrated that no reaction occurred when the
reaction was conducted in the absence of I2 and only 14% yield
of 3aa was obtained in the absence of Ni catalyst, indicating the
critical importance of the I2 and Ni catalyst for activation of the
C−N bond (entries, 13–14).
as substituents, the cyclization adduct 3aa could be obtained in
good yields in optimized reaction conditions (Table 2, entries 4
and 9). When other nitrogen groups, such as N(CH3)2, NEt2,
N(n-Pr)2, N(n-Bu)2, N(allyl)2, NPh2 and NCy2 were installed in the
benzyl skeleton, the conversion was dramatically decreased
under other identical reaction conditions. The relatively lower
activity of these substrates might be attributed to the difficult
cleavage of the corresponding C-NR2 bonds. Considering the
distinct reactivity of different benzylamines,
a variety of
benzylamines with two isopropyl groups attached on the N-atom
were subjected to the optimized conditions to investigate its
Table 2. Substrate scope of benzylamines [a]
a]
Table 1. Screening of reaction conditions [
Entry
1
[Ni]
Ligand
L1
Solvent
anisole
anisole
anisole
anisole
anisole
anisole
anisole
anisole
toluene
dioxane
DMSO
2-PrOH
anisole
anisole
Yield (%)
NiCl2
NiBr2
NiI2
87 (83)
88
2
L1
3
L1
94 (91)
74
4
Ni(cod)2
NiI2
L1
5
Xantphos
BINAP
DPPF
PPh3
94 (92)
72
6
NiI2
7
NiI2
39
8
NiI2
50
9
NiI2
Xantphos
Xantphos
Xantphos
Xantphos
L1
46
10
11
12
13[b]
14
NiI2
65
NiI2
0
NiI2
11
NiCl2
-
0
L1
14
[a] Reaction conditions: 1a (2.0 mmol), 2a (0.5 mmol), [Ni] (0.05 mmol), L1
(0.12 mmol, L1 = 2-(Diphenylphosphino)benzoic acid), I2 (0.1 mmol), anisole
(2 mL), 150 oC, 24 h. Yield was determined by GC using n-hexadecane as an
internal standard and isolated yields were given within parentheses; [b] without
I2.
Having established the optimized reaction conditions, the
reactivity of benzylamines with different substituents on the
nitrogen atom were firstly investigated under the standard
conditions. As summarized in Table 2, tertiary benzylamines
containing different groups on the nitrogen atom gave the
desired product 3aa in distinctly different yields (Table 2, entries
1-9). For the benzylamines with isopropyl (i-Pr), and benzyl (Bn)
substrate scope and generality. As shown in Table 2, the
reaction is compatible with a wide range of benzylamines to
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afford different oxindole 3ba−3ma in good to excellent yields.
Typical functional groups, such as alkyl, halides, ether, ester,
ketone, and cyano were compatible with this method (Table
2, entries 10-21). However, strong electron-withdrawing
substituent –NO2 gave the corresponding product in
moderate yield under the modified reaction conditions (Table
2, entry 22). In addition to phenyl-substituted amines,
naphthyl-substituted amines were also compatible with this
reaction, generating the corresponding adducts 3oa and 3pa
in good yields (Table 2, entries 23 and 24). To our great
delight, the hetero-aryl-substituted amines, such as N-
isopropyl-N-(thiophen-2-ylmethyl)-propan-2-amine and N-
(furan-2-ylmethyl)-N-isopropylpropan-2-amine, were also
proceeded smoothly to provide the desired products in
moderate to good yields (Table 2, entries 25 and 26).
Furthermore, α-substituted benzylamines 1s and 1t were
found to be compatible with these reaction conditions (Table
2, entries 27 and 28).
various benzylamines 1 containing different substituents on
the phenyl ring reacted with acrylamide 2q leading to the
unexpected six-membered ring dihydroquinolinones 3 in good
to excellent yields (Table 4, entries 1-8). Apart from phenyl-
substituted amines, naphthyl-substituted amines were also
compatible with this reaction, generating the corresponding
adducts in good yields (Table 4, entries
9 and 10).
Furthermore, the heteroaryl-substituted amine was also
compatible with this transformation, providing the
corresponding cycloaddition product 3qq in 69% yield (Table
4, entry 11). Although two diastereoisomers were produced in
these reactions, the two isomers could be isolated by simple
chromatography (see SI).
Table 4. Cyclization reaction of benzylamine and acrylamide to dihydroqui-
nolinones [a]
The scope of the reaction with respect to N-
arylacrylamides 2 is summarized in Tables 3. A series of
substituents regardless of electron-donating or -withdrawing
properties other than strong electron-withdrawing nitro on the
phenyl ring were well tolerated, providing the desired adducts
3ab-3ai in moderate to good yields (67-84%).[13] Functional
groups, such as alkyl, halides, ether, cyano, and nitro were
compatible with this method, giving ample opportunities for
further elaboration by transition-metal-catalyzed coupling or
other reactions. Notably, meta-substituted substrates 2c gave
a mixture of two regioisomers. In addition to the methyl group,
the acrylamides bearing a Ac, phenyl and benzyl protecting
groups on the N-tether also afforded the corresponding
oxindoles 3ak, 3al, 3am in 46%-77% yields. Furthermore, the
acrylamides bearing phenyl, benzyl and hydrogen groups at
the α-position also gave the corresponding products 3an-3ap
in moderate to good yields (40-82% yields).
Table 3. Substrate scope of alkenes [a],[b]
In conclusion, we have developed
a novel nickel-
catalyzed arylbenzylation of activated alkenes with tertiary
benzylamines via charge-transfer complex promoted C-N
bond activation. The reaction proceeds through initial Ni-
catalyzed C-N bond activation, followed by sequential radical
addition, redox via single-electron transfer and proton-
abstraction with cleaved amine-moiety in the absence of
oxidant to provide the products in good yields. This reaction
creates a new method to construct a variety of bioactive
molecules containing benzylated oxindole and dihydroquino-
linone moieties. Further investigation of this transformation is
in progress.
Acknowledgements
This research was supported by the National Natural Science
Foundation of China (21672199 and 21790333), the CAS
Interdisciplinary Innovation Team, the Anhui provincial Natural
In addition to α-substituted acrylamide, we were pleased
to find that β-substituted acrylamide 2q can also be employed
as substrates. Under the slightly modified reaction conditions,
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Synthetic method
Hui Yu, Bin Hu,* and Hanmin Huang*
__________ Page – Page
Nickel-Catalyzed
Alkylarylation
of
Activated Alkenes with Benzylamines via
C-N Bond Activation
Charge-transfer complex: A nickel-catalyzed alkylarylation of active alkenes with
tertiary benzylamines was achieved via charge-transfer complex promoted C-N bond
activation. The reaction proceeds through initial Ni-catalyzed C-N bond activation,
followed by sequential radical addition, redox and proton-abstraction with cleaved
amine-moiety in the absence of oxidant, which provides an efficient method to prepare
various alkyl-substituted oxindoles and dihydroquinolinones in good yields.
This article is protected by copyright. All rights reserved.