Co(II)/Cu(II)-cocatalyzed oxidative C-H/N-H functionalization of benzamides with ketones: A facile route to isoindolin-1-ones

Article abstract of DOI:10.1039/c9cc02661d

A cobalt and copper catalyzed reaction protocol has been developed to achieve the oxidative C-H/N-H annulation of benzamides containing an 8-aminoquinoline moiety as the directing group with ketones. Structurally diverse isoindolin-1-ones were furnished by the reaction of various substituent benzamides with ketones.

Full text of DOI:10.1039/c9cc02661d

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
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DOI: 10.1039/C9CC02661D
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Co(II)/Cu(II)-cocatalyzed oxidative C–H/N–H functionalization of
benzamides with ketones: a facile route to isoindolin-1-ones
Xi Zhou,a Hongyan Xu,a Qiaodan Yang,a Hua Chen,a Shoufeng Wang,b and Huaiqing Zhao*,a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A
cobalt and copper catalyzed reaction protocol has been attention by taking advantage of their cheap availability and
developed to achieve the oxidative C–H/N–H annulation of outstanding catalytic efficiency,7 cobalt complexes were also
benzamides containing 8-aminoquinoline moiety as the directing exploited to catalyze the oxidative annulation of electron-
group with ketones. Structurally diverse isoindolin-1-ones were deficient olefins with benzamides by Ackermann and
furnished by the reaction of various substituent benzamides with Jeganmohan.8 But alkenes usually accompany some side-
ketones.
reactions such as self-polymerization and isomerization in
reactions. To overcome the limitation, other reagents were
explored to applying to the synthesis of different isoindolin-1-
ones. We noticed that diazo compounds,9 and alkynes 10 could
afford the corresponding target products.
Isoindolin-1-one is an essential heterocyclic structural unit
which is widely discovered in various natural and bioactive
compounds (Figure 1).1 Therefore, the synthesis of organic
compounds containing the structural moiety is to encourage
synthetic chemists’ efforts. Conventionally, the intramolecular
lactamization of ortho-aminomethyl benzoic acids is a well-
known approach.2 However, this transformation usually is
achieved with prefunctionalized substrates under harsh
conditions, and suffers from more waste by-products. In the
past decades, transition-metal catalyzed C–H functionalization
strategies as the straightforward, atom-economic and
powerful synthesis protocol has been proverbially applied to
constructing important targets.3 For example, the well-
developed transition-metal catalyzed C–H carbonylation was
applied to the construction of isoindolin-1-ones, whereas this
transformation usually requests the participant of the toxic CO
gas.4 Thus it can be seen that transition-metal catalyzed C–H
functionalization was also proved to be powerful tools for the
synthesis of isoindolin-1-ones.5 Owing to their high catalytic
activity and functional group compatibility, Rh(III) complexes
were widely utilized to synthesize isoindolin-1-ones by the
reaction of benzoic amide derivatives with alkenes.6 But
rhodium as a precious and rare transition metal is not an ideal
catalyst due to the economic considerations. Thus the earth-
abundant and inexpensive cobalt catalysts attract more
On the other hand, the strategy for forming alkenes in situ
was adopted to enlarge the application of alkenes. Recently,
more efforts to achieve transition-metal catalyzed
dehydrogenative desaturation of various compounds
generating olefins have been made.11 For example, saturated
ketones could be utilized to provide the desired alkenes with
the aid of transition-metal catalysts.12 Su’s group contributed
more interesting works on transition-metal catalyzing
dehydrogenation of saturated ketones and then olefin reaction
sequence, including Pd or Rh/Cu catalyzed β-arylation of
ketones with benzoic acids or (hetero)arenes as arylating
reagents,13 and Cu catalyzed β‑functionalization of saturated
ketones with different nucleophiles.14 As for the facile
methods for the construction of β-arylated ketones, Dong and
Li have developed the Pd-catalyzed dehydrogenative
desaturation of ketones and successive β-arylation reaction
with various aromatic sources.15 Recently, Dong has realized
the Pd-catalyzed β-alkylation of ketones with simple alkyl
bromides.16 We were encouraged by the versatility of ketones
as the efficient precursor of alkene and anticipated to employ
ketones to accessing isoindolin-1-one derivatives. Herein, we
describe a novel approach to the synthesis of substituted
isoindolin-1-ones
via
manipulating
copper-catalyzed
dehydrogenation of ketones and cobalt-catalyzed oxidative C–
H/N–H annulation of aromatic amides.
a. School of Chemistry and Chemical Engineering, University of Jinan, Jinan,
Shandong, 250022, P. R. China. E-mail: chm_zhaohq@ujn.edu.cn.
b. Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials,
School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022,
P. R. China.
Me
Me
O
O
NH
Me
Cl
N
N
N
N
N
Me
O
Electronic Supplementary Information (ESI) available: See DOI: 10.1039/x0xx00000x
Antipsychotic activity
Pagoclone
Fig. 1 Two biologically active molecules containing isoindolinone moiety
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Table 1 Optimization of the reaction conditionsa
reaction but the exact role of PPh3 is unclear now. Various
solvents and reaction temperature were also investigated and
View Article Online
DOI: 10.1039/C9CC02661D
Co(OAc)2 (15 mol%)
Cu(OAc)2 (5 mol%)
PPh3 (5 mol%)
O
Me
O
Me
Q
O
N
Me
N
H
Et
DCB was certified to be the better solvent for the present
N
Ag2CO3 (2.5 equiv.)
TEMPO (1.0 equiv.)
DCB, 110 oC, 21 h
+
H
O
Me
o
reaction, at 110 C (entries 13-17). Reducing the amount of
1a
2a
3a
standard conditions
ketone 2a, the yield decreased to 63%, revealing that a higher
concentration of 2a appears to be necessary to improve this
transformation (entry 18). Finally, the reaction was performed
under air and led to a lower yield of product (entry 19).
Consequently, the reaction was carried out under inert
atmosphere in order to obtain a better conversion.
Entry
1
2
3
4
5
6
7
8
Variations of standard conditions
none
Yield (%)b
76
0
without Co(OAc)2
without Cu(OAc)2
Co(acac)2
36
39
57
70
30
38
75
46
42
53
56
30
0
Co(OAc)2 (10 mol%)
Co(OAc)2 (20 mol%)
AgOAc (5 equiv.)
Ag2O (2.5 equiv.)
Ag2CO3 (3.0 equiv.)
Cu(OAc)2 (10 mol%)
PPh3 (10 mol%)
without PPh3
PhCl instead of DCB
DCE instead of DCB
TFE instead of DCB
100 oC
The scope with respect to amide substrates was first
evaluated with ketones under optimal conditions or modified
standard conditions as shown in Scheme 1. The reaction of
unsubstituted benzamide with 4’-methylpropiophenone or 4’-
fluoropropiophenone could generate the corresponding
product in a moderate yield whether PPh3 exists or not (3b and
3c). The structure of 3b was further confirmed by the X-ray
crystallography (CCDC 1904901). Aromatic amides containing
one or two methyl groups at different position provided the
desired products in fair to good yields (3d-3i). The
intramolecular competition reaction of meta-methyl
substituted benzamides gave the preferential isomer of 3e as
the major product, due to the steric hindrance of methyl
group. Notably, chloro as an electron-withdrawing group at
different position of benzamides led to moderate conversion
(3k-3n). The reaction of 1n gave the desired product 3n as the
major isomer, which was similar with the reaction of 1e. The
9
10
11
12
13
14
15
16
17
18
19
52
57
63
58
120 oC
2a (3 equiv.)
air atmosphere
aUnless otherwise noted, all the reactions were run with 1a (0.15 mmol)
and 2a (3.5 equiv.) in DCB (0.75 mL) for 21 h, 110 oC, N2 atmosphere.
TEMPO = 2,2,6,6-Tetramethylpiperidine-1-oxyl, DCB = 1,2-Dichlorobenzene,
DCE = 1,2-Dichloroethane, TFE = 2,2,2-Trifluoroethanol. bIsolated yield.
reactivity of substrates bearing
a trifluoromethyl group
Given the reported copper-catalyzed dehydrogenation of
delivered the desired products in moderate to good yields (3o-
3p). We also scaled up the reaction of 1p to 1.5 mmol and
obtained the product 3p in 58% isolated yield. The
transformation of naphthyl amide also occurred in 58% yield
(3r). We also examined the heteroaryl such as thienyl amide in
this catalytic system, but the reaction could not furnish the
14
ketones12d, and cobalt catalyzed N, N’-bidentate directing
group-assisted C–H bond functionalization reactions,7d, 17 we
selected the easily available copper and cobalt compounds as
co-catalysts and the reaction of amide 1a and ketone 2a as a
model reaction to examine the practicability of this method for
the synthesis of isoindolin-1-ones. And we noted that 8-
aminoquinoline as the directing group was chosen to assist C–
H activation by Daugulis in 2005.18 The reaction, where
Co(OAc)2/Cu(OAc)2 was employed as catalysts and
Ag2CO3/TEMPO was utilized as oxidants, gratifyingly, furnished
the desired product 3a in 76% yield (Table 1, entry1). Then a
series of control experiments was conducted to investigate
influence factors of this reaction (Table 1 and SI). At first, there
was no desired product detected when cobalt acetate was
ignored, indicating that the cobalt salt as a catalyst is vital to
accomplish the reaction (entry 2). Then the absence of copper
acetate in the reaction resulted in a dramatical decrease in the
product yield, suggesting that copper catalyst is also essential
to achieve the better conversion (entry 3). There was no
improvement in the product yield when different cobalt salts
and the diverse amount of cobalt acetate were employed in
the reaction (entries 4-6). Silver salts were also evaluated and
silver carbonate was demonstrated to furnish the better result
(entries 6 and 7). Increasing the dosage of Ag2CO3, there was
no obvious influence on the reaction (entry 9). We
subsequently adjusted the amount of copper acetate and PPh3
and found that the yield clearly decreased and the amide 1a
was (entries 10-12). The effect of PPh3 was obvious to the
Co(OAc)2 (15 mol%)
Cu(OAc)2 (5 mol%)
PPh3 (5 mol%)
O
Q
O
O
N
R
N
Et
R
H
R1
Ag2CO3 (2.5 equiv.)
TEMPO (1.0 equiv.)
DCB, 110 oC, 21 h
N
+
H
O
R1
3
1
2
O
O
O
Q
Q
Q
Me
N
N
O
N
O
O
3c, 62%b
3b, 54%b
3a, 76%
Me
Me
F
X-ray of 3b
O
Q
N
O
O
O
Q
Q
Q
Me
N
Me
N
N
O
O
O
O
OMe
Me
Me
Me
Me
Me
F
3d, 51%b
3g, 61%
Me
3e, 45%
3f, 82%
O
O
O
O
Q
N
Q
Q
Q
Me
Me
Me
Cl
N
Me
N
N
O
O
O
O
MeO
Me
Cl
Me
Me
Me
Cl
Me
Me
3k, 52%c,d
3j, 72%c
3h, 57%b
3i
, 78%
Q
O
O
O
O
Q
Q
Q
N
N
N
N
O
O
O
O
Cl
F3
Me
C
Cl
Me
Me
Me
3n, 50%c
3o
b
3m, 40%b,c
, 45%
3l, 46%c,d
O
O
O
Q
Q
O
Q
N
N
F3
C
O
N
O
F3
C
Me
F
3q, 50%b
3r
, 58%
Me
3p, 83% (58%)b,c,e
Scheme 1 Scope of amide substrates. aReaction conditions: 1 (0.15 mmol), 2 (3.5
equiv.), DCB (0.75 mL), 21 h, 110 oC, N2, isolated yield. bIn the absence of PPh3.
cAg2CO3 (3.0 equiv.). dReaction temperature: 120 oC. e1p (1.5 mmol), the isolated
yield in parentheses.
2 | J. Name., 2012, 00, 1-3This journal is © The Royal Society of Chemistry 20xx
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Journal Name COMMUNICATION
corresponding product and further research is in progress.
To investigate the reactivity of various ketones, we selected
amide 1a as one reactant after exploring the compatibility of
amides (Scheme 2). Propiophenone gave the expected product
in 63% yield (4a) when 3.0 equivalents of silver carbonate
were used in the catalytic system. This protocol is also
applicable to a series of ketones bearing either electron-
donating or -withdrawing substituents on the benzene ring of
View Article Online
DOI: 10.1O039/C9CC02661D
OMe
N
OMe
O
Me
O
H
O
NH
Me
O
CAN
N
Me
2a
standard conditions
N
H
CH3CN/H2
O
N
Me
Me
5, 60% yield
4p, 75% yield
1s
Scheme 3 Removal of the directing group.
O
(a)
O
O
Co(OAc)2 (15 mol%)
Cu(OAc)2 (5 mol%)
PPh3 (5 mol%)
+
Ag2CO3 (2.5 equiv.)
TEMPO (1.0 equiv.)
propiophenones. Notably, propiophenones containing
a
2b
2b'
2b
0.2 mmol
methyl or methoxy group on different positions of benzene
rings could furnish the desired isoindolin-1-one derivatives in
moderate to good yields (4b-4d). We noted that the
propiophenones containing F, Cl and Br at different positions
of benzene rings also delivered the desired product under
modified reaction conditions by removing PPh3 or increasing
Ag2CO3 (4e-4k). Remarkably, the compatibility of halogen
groups on the benzene ring provides a feasible chance for
further transformation to synthesize other compounds.
Unfortunately, a trifluoromethyl substituent on 4-position of
benzene in propiophenone only provided the desired product
in only 35% yield (4l). Other reaction conditions were also tried
but there was no demonstrable improvement on this reaction
32%
33%
Standard conditions:
Conditions 1 without Co(OAc)2
68%
67%
:
Conditions 2 without Co(OAc)2 and TEMPO: No observed
100%
Conditions 3 without Cu(OAc)2 7%
:
93%
O
(b)
Co(OAc)2 (15 mol%)
Cu(OAc)2 (5 mol%)
PPh3 (5 mol%)
Q
Me
O
O
N
Me
Q
N
H
+
Ag2CO3 (2.5 equiv.)
TEMPO (1.0 equiv.)
DCB, 110 oC, 21 h
O
H
1a
2b'
4a, 52% yield
Scheme 4 Control experiments.
standard conditions (Scheme 4b). Subsequently, isotope
labelling experiments were also performed and the results
suggest that the C–H cleavage of phenyl amides is nearly
irreversible under the reaction conditions. And the one-pot
competitive kinetic isotope effect (KIE) value (1.43) and the
parallel KIE value (1.17) were observed, and the results suggest
the C–H cleavage in this reaction was unlikely involved in the
rate-limiting step (see ESI).19
of
4’-(trifluoromethyl)propiophenone.
Additionally,
heteroaromatic ketones such as 2-propionylthiophene and 2-
methyl-5-propionylfuran were demonstrated to undergo this
reaction (4m and 4n). Interestingly, aliphatic ketone, namely 3-
pentanone, could be transformed to the corresponding
product in 37% yield (4o). 8-Amino-5-methoxyquinoline
benzamide (1s) reacted with 2a to give the product 4p in 75%
yield. The auxiliary group can be removed affording
heterocycle 5 in 60% yield (Scheme 3).
On the basis of the above experiments and the reported
cobalt catalyzed C–H bond functionalization8, 17, 20 and copper-
catalyzed the dehydrogenation of saturated ketones,14
a
plausible mechanism for the Co/Cu catalyzed oxidative C–H/N–
H functionalization was proposed in Scheme 5. The Co(II)
species I is generated from cationic Co(II) coordinating to the
nitrogen of substrate amide 1, and then is oxidized to Co(III)
complex by Ag(I). Subsequently, the Co(III) species activates
the C–H bond to deliver a cyclometalated intermediate II
through an ortho-C–H cleavage of benzamide.20 The olefin
which derives from the dehydrogenation of ketone catalyzed
by Cu/TEMPO/Ag2CO3 inserts into C–Co bond leading to the
formation of intermediate III that undergoes β-hydrogen
elimination and reduction elimination producing IV and Co(I)
species. And then the cobalt (I) species is oxidized to Co(II) by
silver salt in the catalytic system, and intermediate IV
undergoes the intramolecular Michael addition to afford the
To gain some primary insight to the mechanism of this
reaction, some related experiments were carried out (Scheme
4 and ESI). Control experiments about the desaturation of
ketone 2b were performed and the results indicate that
Cu(OAc)2 and TEMPO are crucial to form the olefin and Ag2CO3
could improve the formation of the olefin (Scheme 4a). Then
the reaction of 2b’with 1a afforded 4a in 52% yield under the
O
Co(OAc)2 (15 mol%)
Cu(OAc)2 (5 mol%)
PPh3 (5 mol%)
Q
Me
O
O
N
Me
R
N
H
Et
R
N
Ag2CO3 (2.5 equiv.)
TEMPO (1.0 equiv.)
DCB, 110 oC, 21 h
+
H
O
4
1a
2
O
O
O
O
Q
Q
Q
Q
product 3.
Me
Me
Me
Me
N
N
N
N
O
O
O
O
OMe
O
Me
Q
N
OMe
4a, 63%c
4d, 53%
H
4c, 50%
4b, 72%
O
Ag+
H
1
Q
O
O
O
O
Co(II)
N
Q
N
Q
N
Q
N
Q
N
Me
Me
Me
O
H+
O
Me
O
O
O
O
F
Cl
R
3
[Co(I)]
4g, 53%b
4h, 70%b,c
N
4e, 72%b
4f
, 50%
b
F
Cl
N
[Co]
Michael
addition
O
O
O
O
I
Q
Q
Q
Me
Q
N
Me
Me
Me
N
N
N
O
O
O
O
Ag+
Cl
Cl
Br
O
O
4i, 46%b
4l, 35%b
4j, 51%b
CF3
Br
4k, 73%b,c
N
N
H
O
O
O
N
Q
Me
Q
O
N
R
Me
[Co]
Me
N
Q
N
N
O
O
N
O
II
S
O
Cu(OAc)2
TEMPO
O
R
IV
R
Me
Et
4o, 37%c,d
4m, 62%
N
4n, 51%
[Co]
Ag2CO3
-H elimination and
reduction elimination
O
O
Scheme 2 Scope of ketone substrates. aReaction conditions: 1a (0.15 mmol), 2
(3.5 equiv.), DCB (0.75 mL), 21 h, 110 oC, N2, isolated yield. bIn the absence of
PPh3. cAg2CO3 (3.0 equiv.). dReaction temperature: 120 oC.
2
H
III
O
R
Scheme 5 Proposed mechanism of the transformation.
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3
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5
6
For selected examples, see: (a) R. Manoharan and M.
View Article Online
In summary, we have first developed an efficient protocol
for cobalt/copper-catalyzed oxidative C–H/N–H annulation of
various amides with different saturated ketones, hence
Jeganmohan, Chem. Commun. 2015, 51, 2929; (b) X. Wu, B.
Wang, S. Zhou, Y. Zhou and H. Liu, ACSDCOaIt:a10l..12003197/C, 97C, C20429646;1D
(c) S. W. Youn, T. Y. Ko, Y. H. Kim and Y. A. Kim, Org. Lett.
2018, 20, 7869; (d) L.-Y. Fu, J. Ying, X. Qi, J.-B. Peng and X.-F.
Wu, J. Org. Chem. 2019, 84, 1421.
For selected examples, see: (a) F. Wang, G. Song and X. Li,
Org. Lett. 2010, 12, 5430; (b) F. W. Patureau, T. Besset and F.
Glorius, Angew. Chem., Int. Ed. 2011, 50, 1064; (c) C. Zhu and
J. R. Falck, Chem. Commun. 2012, 48, 1674; (d) J. Zhou, B. Li,
Z.-C. Qian and B.-F.Shi, Adv. Synth. Catal. 2014, 356, 1038; (e)
Y. Lu, H.-W. Wang, J. E. Spangler, K. Chen, P.-P. Cui, Y. Zhao,
W.-Y. Sun and J.-Q. Yu, Chem. Sci. 2015, 6, 1923; (f) Z. Zhou,
G. Liu and X. Lu, Org. Lett. 2016, 18, 5668; (g) W-W. Ji, E. Lin,
Q. Li and H. Wang, Chem. Commun. 2017, 53, 5665; (h) Y.
Zhang, H. Zhu, Y. Huang, Q. Hu, Y. He, Y. Wen and G. Zhu,
Org. Lett. 2019, 21, 1273.
providing
a step-economical access to isoindolin-1-one
derivatives. This protocol is to possess a broad scope of
substrates and good functional group compatibility. In this
transformation, inexpensive and easily available cobalt and
copper compounds were utilized as catalysts, and TEMPO and
silver carbonate were employed as oxidants. Further efforts
will be devoted to expanding the ketones and amides scope
and exploring the application of this protocol.
Financial support from Shandong Provincial Natural Science
Foundation, China (ZR2016JL009), National Natural Science
Foundation of China (21302184) and University of Jinan is
highly appreciated. We gratefully acknowledge Prof. Di Sun
(Shandong University) for X-ray crystal analysis.
7
For selected recent reviews on cobalt catalysts, see: (a) K.
Gao and N.Yoshikai, Acc. Chem. Res. 2014, 47, 1208; (b) M.
Moselage, J. Li and L. Ackermann, ACS Catal. 2015, 6, 498; (c)
T. Yoshino and S. Matsunaga, Adv. Synth. Catal. 2017, 359,
1245; (d) Y. Kommagalla and N. Chatani, Coord. Chem. Rev.
2017, 350, 117.
Conflicts of interest
8
9
(a) W. Ma and L. Ackermann, ACS Catal. 2015, 5, 2822; (b) R.
Manoharan and M. Jeganmohan, Org.Lett. 2017, 19, 5884.
For selected examples, see: (a) T. K. Hyster, K. E. Ruhl and
T.Rovis, J. Am. Chem. Soc. 2013, 135, 5364; (b) B. Ye and
N.Cramer, Angew. Chem., Int. Ed. 2014, 53, 7896; (c) Y.
Zhang, D. Wang and S. Cui, Org. Lett. 2015, 17, 2494; (d) X.
Hu, X. Chen, Y. Shao, H. Xie, Y. Deng, Z. Ke, H. Jiang and W.
Zeng, ACS Catal. 2018, 8, 1308.
There are no conflicts to declare.
Notes and references
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