Nickel-catalyzed C-H/N-H annulation of aromatic amides with alkynes in the absence of a specific chelation system

Article abstract of DOI:10.1039/c7sc01750b

The Ni-catalyzed reaction of aromatic amides with alkynes in the presence of KOBu^t involves C-H/N-H oxidative annulation to give 1(2H)-isoquinolinones. A key to the success of the reaction is the use of a catalytic amount of strong base, such a

Full text of DOI:10.1039/c7sc01750b

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DOI: 10.1039/C7SC01750B
Journal Name
ARTICLE
Nickel‐Catalyzed C‐H/N‐H Annulation of Aromatic Amides with
Alkynes in the Absence of a Specific Chelation System
Received 00th January 20xx,
Accepted 00th January 20xx
Atsushi Obata, Yusuke Ano, and Naoto Chatani*
t
DOI: 10.1039/x0xx00000x
The Ni‐catalyzed reaction of aromatic amides with alkynes in the presence of KOBu involves C‐H/N‐H oxidative annulation
to give 1(2H)‐isoquinolinones. A key to the success of the reaction is the use of a catalytic amount of a strong base, such as
www.rsc.org/
t
KOBu . The reaction shows a high functional group compatibility. The reaction with unsymmetrical alkynes, such as 1‐
arylalkynes gives the corresponding 1(2H)‐isoquinolinones with a high level of regioselectivity. This discovery would lead to
the development of Ni‐catalyzed chelation‐assisted C‐H functionalization reactions without the need for a specific
chelation.
two types, depending on the oxidation state of the key
Introductionꢀꢀ
catalytic species. In the case of a Ni(0)‐catalyzed system, the
coordination of an N(sp ) atom to the nickel(0) center,
2
The direct functionalization of C‐H bonds has emerged as an
increasingly valuable tool for step‐economical organic
synthesis. A wide variety of transition metal complexes,
including Pd, Ru, Rh, and Ir can be used as catalysts in a variety
followed by the oxidative addition of an N‐H bond to give
8,9
complex
through σ‐bond metathesis to generate the cyclometalated
complex with concomitant generation of the formal “H ”,
A
,
where the cleavage of a C‐H bond proceeds
1
B
2
of catalytic functionalizations of C‐H bonds. Nickel‐catalyzed
which is then trapped by a hydrogen acceptor, such as an
C‐H functionalizations have recently become a subject of great
interest, owing to the low cost of the reaction, the use of
readily available nickel, and the uniqueness of the reaction.
However, the functionalization of C‐H bonds catalyzed by Ni
complexes was limited to C‐H bonds in specific aromatic
systems, such as pyridine or activated pyridine derivatives,
perfluorinated benzene, azoles, and indoles, all of which
contain an acidic C‐H bond. No general and reliable system for
the nickel‐catalyzed functionalization of non‐acidic C‐H bonds
in benzene rings was available. In 2011, we reported on the
Ni(0)‐catalyzed reaction of aromatic amides that contain a 2‐
alkyne. In the Ni(II)‐catalyzed system, the coordination of an
2
N(sp ) atom to a nickel(II) center followed by a ligand exchange
gives complex
through a concerted metalation deprotonation mechanism
CMD), generates a cyclometalated complex . After the
metalacycle or is formed, various reagents can then be
C, which, after the cleavage of a C‐H bond
(
D
B
D
2
used in the remainder of the reaction. Irrespective of the
2
mechanism, the role of the N(sp ) atom is to bring the nickel
3
catalyst into close proximity to the NH bond by coordination,
followed by the formation of a covalent N‐Ni bond via
oxidative addition or ligand exchange. The nickel atom in the
pyridinylamine moiety as a directing group, with alkynes,
leading to the production of isoquinolinones. In 2013, we also
4
resulting intermediates A and C is now sufficiently close to
activate ortho C‐H bonds, which are then cleaved. Thus, the
formation of a covalent N‐Ni bond is a key step in the
activation of C‐H bonds in the Ni‐catalyzed bidentate chelation
system. In the case of Pd, Ru, Rh, and Ir‐catalyzed reactions, a
wide variety of chelating groups are known to function as
directing groups that are capable of activating C‐H bonds. Even
the weak coordination of a heteroatom to these metals can
promote the activation of C‐H bonds. In sharp contrast, when
the heteroatom is weakly coordinated to nickel, the C‐H bonds
are not activated. Because of this, the pre‐coordination of an
reported on the Ni(II)‐catalyzed C‐H alkylation of aromatic
amides that contain an 8‐aminoquinoline moiety as a directing
5a
group, with alkyl halides. Since then, significant advances in
Ni(II)‐catalyzed C‐H functionalization reactions that involve the
use of a bidentate chelation system have been reported by
5‐7
many other groups, as well as our group. A newly developed
chelation system in which a bidentate directing group is used is
now recognized as a powerful and reliable strategy for
developing Ni‐catalyzed C‐H functionalizations. The presence
2
of both N(sp ) and NH groups is crucial for the reaction to
2
N(sp ) atom to the nickel center is required to allow the nickel
to come into close proximity to the N‐H bonds to form an N‐Ni
proceed. The reactions reported to date can be classified into
bond.
Department of Applied Chemistry, Faculty of Engineering, Osaka University,Suita,
Osaka 565‐0871, Japan
†
Electronic
Supplementary
Information
(ESI)
available.
See
DOI: 10.1039/x0xx00000x
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Journal Name
The reaction of the aromatic amide 1a with 5 equivalents of
View Article Online
DOI: 10.1039/C7SC01750B
diphenylacetylene in the presence of Ni(OTf) (10 mol%) and
2
PPh (20 mol%) in toluene (0.25 mL) at 160 °C for 14 h gave 2‐
3
(
6
4‐methoxyphenyl)‐3,4‐diphenyl‐1(2H)‐isoquinolinone (2a) in
7% NMR yield (entry 1 in Table 1). It was found that the
catalytic activity of Ni(cod) is comparable to that for Ni(OTf)2
2
(
entry 2). Among the ligands examined (entries 3‐5), PPh was
3
the ligand of choice. Although the use of 4,4'‐di‐tert‐butyl‐2,2'‐
bipyridine resulted in a higher yield of 2a than phosphine
ligands, a small amount of the saturated product 3a was also
formed (entry 6) The reaction proceeded efficiently in the
Scheme 1 Key steps for the activation of C‐H bonds by nickel complexes in a presence of a strong base (entries 7 and 8). In sharp contrast,
bidentate‐chelation system. For simplicity, groups that are not involved in the
transformation, such as ligands and reagents, are omitted.
no reaction took place when weak bases were used (entries 9
and 10). Finally, the use of m‐xylene (0.6 mL) as the solvent
and an alkyne (10 equivalents) gave 2a in 89% isolated yield
ꢀ
A bidentate chelation system using 2‐pyridinylamine and 8‐
(
entry 14).
aminoquinoline as the directing group is recognized as a
powerful and reliable strategy for developing new types of Ni‐
catalyzed C‐H functionalizations. However, elaborating these
directing groups into useful functional groups is not an easy
a
Table 1. Ni‐catalyzed reaction of aromatic amide with diphenylaceylene.
Ph
Ph 1.25 mmol
OMe
Ni(OTf)2 10 mol%
PPh
KO Bu 20 mol%
O
OMe
1
0
20 mol%
O
3
task. Our next target involves the use of a simpler directing
group instead of strong and specific directing groups, such as
t
N
N
H
toluene 0.25 mL
Ph
2
‐pyridinylamine and 8‐aminoquinoline groups. Our working
160 C, 14 h
Ph
hypothesis is that if a strong base could be used, the anion
generated by the deprotonation of an amide NH would easily
react with the Ni(II) catalyst to produce a new bond between N
1a 0.25 mmol
2
a
NMR Yields
recovered 1a
Entry
Notes
2a
and Ni, as in
C‐H activation, as mentioned above, C‐H bond cleavage would
then take place, with the generation of the metalacycle . In
the case of a Ni(0) catalyst, the nickel complex would be
expected to participate in the oxidative addition of C‐H bonds
F, which would function as a key intermediate for
1
2
-
67% (61%)
31%
27%
Ni(cod)2
63% + 3a 8%
G
3
4
PCy3
PBu3
55%
56%
31%
35%
H
5
P(OPh)3
0%
71%
9,11
to generate complex
N(sp ) atom to a nickel center would be required.
I
.
Thus, no pre‐coordination of an
tBu
tBu
2
6
72% + 3a 4%
4%
N
N
ꢀ
t
7
8
9
LiO Bu
62%
37%
24%
KOMe
KOAc
K3PO4
71% + 3a 5%
no reaction
no reaction
1
0
1
1
m-xylene
140 C
63%
33%
27%
17%
12
69% + 3a 6%
1
3
4
m-xylene, alkyne 10 equiv
81%
1
m-xylene 0.6 mL, alkyne 10 equiv 90% (89%; 2a:3a = 39:1) 4%
OMe
O
N
Scheme 2 Working hypothesis.
3a
Ph
ꢀ
Ph
ꢀ
We recently realized such a reaction. Herein, we report on the
Ni‐catalyzed oxidative annulation of C‐H bonds in aromatic
amides with alkynes, leading to the production of 1(2H)‐
isoquinolinones. A specific directing group is not required for
the success of the reaction. A key to the success of the
a
The number in parenthesis refers to the isolated yield.
The effect of substituents on the amide nitrogen was
examined under optimized reaction conditions (entry 14 in
Table 1). Aryl groups containing both electron‐donating and
electron‐withdrawing groups gave the corresponding
isoquinolinones in high yields, while alkyl groups, such as
methyl and tert‐butyl groups gave the corresponding products
in poor yields.
1
2
reaction is the use of a catalytic amount of KOBut.
Results and Discussion
2
| J. Name., 2012, 00, 1‐3
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Journal Name
ARTICLE
a
2
Reaction conditions: amide (0.25 mmol), alkyne (2.5 mmol), Ni(OTf) (0.025
View Article Online
O
t
mmol), 4,4'‐di‐tert‐butyl‐2,2'‐bipyridine (0.05 mmol), KOBu (0.05 mmol) in m‐
xylene (0.6 mL) at 160 °C for 48 h. Isolated yields. The number in parenthesis
refers to regioselectivity. The reaction was carried out under the conditions
DOI: 10.1039/C7SC01750B
R
R = 4-MeOC H (2a)
89%
87%
78%
b
6
4
N
R = Ph (4a)
R = 4-CF C H (4b)
c
3
6 4
Ph
shown in entry 14 in Table 1.
Ph
Scheme 3 Effect of substituents on the amide nitrogen
a,b
The scope of this oxidative annulation reaction was
investigated with respect to the amide used (Table 2). The
reaction shows a broad substrate scope and a high functional
group tolerance. Various functional groups, including methoxy,
dimethylamino, cyano, fluoride, and trifluoromethyl groups
were tolerated. In the case of meta‐trifluoromethyl‐
substituted aromatic amides 1l, the less hindered C‐H bond
was exclusively activated to give 2l in 91% isolated yield as a
single isomer. On the other hand, in the case of the meta‐
methyl‐substituted aromatic amide 1m, a 2:1 mixture of
regioisomers 2m was obtained.
The scope of alkynes was also examined (Scheme 3). Although
terminal alkynes did not give the corresponding
isoquinolinones, various internal alkynes were applicable to
the reaction. When 1‐phenyl‐1‐propyne was used as the
alkyne under the standard reaction conditions, the product
yield of 2r was moderate (26% yield) and a regioisomeric
mixture (3:1) was produced. Gratifyingly, after screening
various reaction parameters, the reaction was dramatically
improved to give a 77% yield with a high degree of
regioselectivity (>50:1) when 4,4'‐di‐tert‐butyl‐2,2'‐bipyridine
Table 2. Scope of amides
OMe
OMe
OMe
OMe
OMe
OMe
O
O
N
N
Me
Ph
Bu
Ph
Ph
Ph
Ph
2
2
2
b 67%
2c 68%
O
O
N
N
tBu
Ph
Ph
Ph
Ph
d 88%
2e 60%
O
N
O
N
Me N
Ph
MeO
Ph
2
Ph
Ph
f 80%
2g 83%
OMe
OMe
OMe
O
N
O
N
was used as the ligand instead of PPh . The regioselectivity
3
was not affected by electronic effects of substituents on the
NC
Ph
F3C
Ph
aromatic ring of both amides and alkynes, as in 2r
, 2s, 2t, and
Ph
Ph
2
u.
The use of 4,4'‐di‐tert‐butyl‐2,2'‐bipyridine also
h 71%c
2
2i 68%
dramatically improved the product yield of 2x in the reaction
of 1a with 4‐octyne. The use of the unsymmetrical
OMe
OMe
OMe
O
N
Me
O
N
dialkylacetylene gave nearly a 1:1 ratio of regioisomers of 2y
.
a,b
Table 3 Scope of alkynes.
F
Ph
Ph
Ph
Ph
2j 69%
2k 81%
OMe
OMe
O
N
O
N
Me
F3C
Ph
Ph
Ph
Ph
Ph
2
m 81% (2:1)d
2
l 91%
Me
O
N
O
Me
MeO
N
Ph
Ph
OMe Ph
2o 56%
2
n 76%
OMe
OMe
O
N
O
O
N
Ph
Ph
Ph
Ph
2
p 74%c
2q 32%
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ARTICLE
Journal Name
a
Reaction conditions: amide (0.25 mmol), diphenylacetylene (2.5 mmol), Ni(OTf)
2
View Article Online
DOI: 10.1039/C7SC01750B
t
(0.025 mmol), PPh
3
(0.05 mmol), KOBu (0.05 mmol) in m‐xylene (0.6 mL) at
b
c
d
1
60 °C for 14 h. Isolated yields. For 48 h. The number in parenthesis refers to
regioselectivity.
Scheme 8 Proposed mechanism.
Scheme 4 Competition experiments.
Scheme 5 Deuterium labeling experiments.
To gain mechanistic insights into the reaction, some additional Although the material balance was not high, it was found that
experiments were conducted. We performed a competition an alkyne functions as, not only a two‐component coupling
experiment using 4‐methoxy‐ and 4‐trifluoromethyl‐ partner, but also hydrogen acceptor (Scheme 6).ꢀ
substituted aromatic amides (Scheme 4). However, no
significant difference in electronic effects between the two
substituents was observed.
ꢀ
Deuterium‐labeling experiments were also carried out
(Scheme 5). No H/D exchange was observed both in the
product and the recovered amide, even at the ortho‐position,
indicating that the cleavage of C‐H bonds is irreversible. These
results are completely different from those obtained when an
5
8
‐aminoquinoline directing group was used. In addition, a KIE
of 3.7 was determined, suggesting that the cleavage of C‐H
bonds is the rate determining step.
Scheme 6. Detection of alkenes.
4
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ARTICLE
1
4
The para‐methoxyphenyl group was successfully removed. The (Scheme 8). The oxidative addition of the ortho C‐H bond
View Article Online
DOI: 10.1039/C7SC01750B
treatment of 2a with BBr3 followed by PhI(OAc)2 in gives a seven‐membered nickelacycle
N, which then permits
CH CN/THF/H O gave the 3,4‐diphenylisoquinolin‐1(2H)‐one the insertion of an alkyne to give the complex
O
(Scheme 9).
3
2
(
5).
Complex O undergoes reductive elimination and protonation
t
by BuOH to afford the isoquinolinone with the regeneration of
t
Ni(0) and KOBu with the concomitant formation of an alkene.
Based on the above findings, this alternative mechanism
cannot be excluded.
Conclusions
In summary, we report on the development of a new system
for C‐H functionalizations catalyzed by nickel complexes. In the
past, an N,N‐bidentate chelation system was the only reliable,
Scheme 7. A removal of para‐methoxyphenyl group.
A proposed mechanism for the above reaction is shown in general, and powerful system for developing Ni‐catalyzed C‐H
6
a,b
Scheme 8. The mechanism involves two paths. The Ni(II) functionalizations.
The above findings show that aromatic
complex initiates the first path (left scheme). A proton is amides with a simple directing group can also participate in
t
abstracted from an amide by KOBu to generate the amidate the Ni‐catalyzed C‐H functionalization. The reaction displays a
anion
E, which reacts with Ni(II) to give the complex
F
. The broad substrate scope and has a high functional group
cleavage of the ortho C‐H bonds gives the nickelacycle
G,
tolerance. A specific directing group, such as 2‐pyridinylamine
followed by the insertion of an alkyne into a N‐Ni bond, which and 8‐aminoquinoline is not required for the reaction to
then undergoes reductive elimination to give the proceed. A key to the success of the reaction is the use of a
t
isoquinolinone and Ni(0). Ni(0) cannot be oxidized to Ni(II) catalytic amount of KOBu , which forms an N‐Ni bond which
under the reaction conditions employed. However, the main permits the C‐H bond to be activated. Nickel‐catalyzed
catalytic cycle in which Ni(0) is the key catalytic species synthesis of isoquinolinones with the extraction of CO or N or
2
initiates the reaction (right scheme). The amidate anion
reacts with Ni(0) to give a nickel complex , which is the aromatic ring has been reported. Our new system has the
sufficiently reactive to undergo oxidative addition to generate potential for applications to new types of Ni‐catalyzed
the nickel hydride species because the complex is sufficiently functionalization of C‐H bonds, which continues to be a
The successive insertion of an alkyne into H‐ challenging issue
Ni and C‐Ni bonds gives the complex . Reductive elimination
E
the cleavage of C‐halogen bonds that are already present on
15
H
I
1
1,13
electron rich.
L
t
followed by protonation by BuOH affords the isoquinolinone
with the regeneration of Ni(0) and KOBu with concomitant
Acknowledgements
t
This work was supported, in part, by a Grant‐in‐Aid for
Scientific Research on Innovative Areas "Molecular Activation
Directed toward Straightforward Synthesis" from The Ministry
of Education, Culture, Sports, Science and Technology, and by
JST Strategic Basic Research Programs “Advanced Catalytic
Transformation Program for Carbon Utilization (ACT‐C)” from
Japan Science and Technology Agency (JPMJCR12YS).
formation of an alkene.
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DOI: 10.1039/C7SC01750B