Cobalt-Catalyzed C—H Allylation of Arenes with Allylic Amines

Article abstract of DOI:10.1002/cjoc.202000680

[Cp*Co(CO)I₂] effectively catalyzes pyridyl-directed C—H allylation of arenes with allylic amines in the presence of AgOAc and CF₃COOAg. The reaction features ortho-position monoallylation of 2-pyridylarenes, giving the allylated are

Full text of DOI:10.1002/cjoc.202000680

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中
国 化 学
Cite this paper: Chin. J. Chem. 2021, 39, 1205—1210. DOI: 10.1002/cjoc.202000680
Cobalt-Catalyzed C—H Allylation of Arenes with Allylic Amines
a
a
,a,b
Rui Yan, Hang Yu, and Zhong-Xia Wang*
a
CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei,
Anhui 230026, China
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China
b
Keywords
C—H activation | C—N activation | Homogeneous catalysis | Cobalt catalysis | Allylation
Main observation and conclusion
[
Cp*Co(CO)I
CF COOAg. The reaction features ortho-position monoallylation of 2-pyridylarenes, giving the allylated arenes in moderate to high
yields. A range of functional groups including OMe, Me, Ph, F, Cl, Br, CF , C(O)Me, COOEt, and COOH groups are tolerated. Pyrim-
idyl-directed C—H allylation of arenes were also performed under the same conditions. Reaction of 2-phenylpyrimidine,
-(4-methoxyphenyl)pyrimidine, and 2-(3-fluorophenyl)pyrimidine leads to a mixture of ortho-position mono- and bisallylation prod-
2
] effectively catalyzes pyridyl-directed C—H allylation of arenes with allylic amines in the presence of AgOAc and
3
3
2
ucts. Reaction of other 2-(substituted aryl)pyrimidines resulted in ortho-position monoallylation products.
Comprehensive Graphic Content
*E-mail: zxwang@ustc.edu.cn
View HTML Article
Supporting Information
Chin. J. Chem. 2021, 39, 1205－1210
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Concise Report
Yan, Yu & Wang
a
Table 1 Optimization of reaction conditions
Background and Originality Content
Allyl compounds are important in organic synthesis because
the allyl moiety can be further converted into various functional
groups. The compounds containing an allyl moiety are also found
[1]
in a number of biologically active molecules. Therefore, synthe-
sis of allyl compounds have attracted much attention over the
[
1,2]
years.
In the known synthetic methods, transition-metal-cata-
lyzed allylation of inert C—H bonds is attractive in terms of atom-
and step-economy. Ruthenium, rhodium, iridium, palladium, co-
balt, iron, and manganese have been used as catalysts for allyla-
tion of aryl or alkenyl C—H bonds employing various allylating
b
Equiv of
Yield /%
Entry Additive 1 (equiv) Additive 2
Solvent
2a
3a (3a’)
1
2
AgOAc (0.5)
AgOAc (0.5)
AgOAc (0.2)
AgOTf (0.2)
–
2
CF
3
CF
3
CF
3
CF
3
CH
CH
CH
CH
2
OH
2
OH
2
OH
2
OH
50 (0)
[
3]
[4]
reagents such as allylic halides, allylic alcohols or their deriva-
AgSbF
AgSbF
AgSbF
6
6
6
2
2
66 (0)
81 (0)
34 (0)
64 (0)
52 (0)
57 (0)
22 (0)
60 (8)
88 (0)
80 (0)
80 (11)
[
5]
[6]
[7]
[8]
tives, allylic amines, allenes, and 1,3-dienes. Among the
allylating reagents, allylic amines have been rarely used because
of stability of the C—N bonds and poor leaving ability of the ami-
no groups. Clavier et al. reported cobalt(III)-catalyzed C—H allyla-
3
4
2
[6a]
5
AgPF (0.2)
AgSbF6
2
CF CH OH
6
3
3
3
3
3
2
2
2
2
2
tion of arenes with strained vinylaziridines (Scheme 1a).
We
and Gooßen’s group respectively performed ruthenium-catalyzed
6
CF
3
COOAg (0.2)
AgSbF
AgSbF
6
6
2
CF
CF
CF
CF
CH
CH
CH
CH
OH
OH
OH
OH
[
6b,c]
C—H allylation of arenes with allylic amines (Scheme 1b).
7
Ag
2
CO (0.2)
3
2
These ruthenium-catalyzed reactions lead to ortho-position bisal-
lylation products of arenes in the absence of ortho- or hindered
meta-substituents. In the further study, we found that cobalt can
catalyze similar reaction, which features ortho-monoallylation of
arenes (Scheme 1c). Herein, we report the results.
8
KOAc (0.2)
KOAc (0.2)
2
9
AgSbF
6
2
10
AgOAc (0.2)
AgOAc (0.2)
AgOAc (0.2)
AgOAc (0.2)
AgOAc (0.2)
AgOAc (0.2)
AgOAc (0.2)
AgOAc (0.2)
AgOAc (0.2)
AgOAc (0.2)
AgOAc (0.2)
CF COOAg
3
2
CF CH OH
3
3
3
3
3
2
2
2
2
2
1
1
2
CF
3
CF
3
CF
3
CF
3
CF
3
CF
3
CF
3
CF
3
CF
3
CF
3
COOAg
COOAg
COOAg
COOAg
COOAg
COOAg
COOAg
COOAg
COOAg
COOAg
1.5
3
CF
CF
CF
CF
CH
CH
CH
CH
OH
OH
OH
Scheme 1 C—H allylation of arenes with allylic amines
1
c
13
2
60 (0)
d
d
d
d
d
d
f
e
1
1
1
1
1
1
4
5
6
7
8
9
2
OH 86/85 (0)
2
EtOH
Trace
2
Toluene
DMF
THF
–
2
–
–
2
2
DCE
Trace
–
2
0
2
3 2
CF CH OH
a
Unless otherwise stated, reactions were run in 1.5 mL of solvent under
b
nitrogen atmosphere; 0.2 mmol of 2-phenylpyridine was employed. De-
termined by H NMR analysis of the crude mixture using 1,1,2,2-tetra-
1
c
chloroethane as an internal standard. 0.2 equiv CF
3
COOAg was employed.
d
e
f
5
mol% of [Cp*Co(CO)I
2 2
] was employed. Isolated yield. No [Cp*Co(CO)I ]
was employed.
Results and Discussion
AgSbF
Table 1, entries 8 and 9). Further tests showed that the additive
AgOAc-CF COOAg combination was more effective, which led to
8% products yields (Table 1, entry 10). Role of the silver salts may
be to react with the cobalt complex to produce an active cata-
6 6
were also less effective than AgOAc-AgSbF combination
(
Cp*Co(III) has been reported to catalyze C—H allylation of
[
3a,4b,4c,6a]
arenes using various allylating reagents.
Cp*Co(CO)I ] as catalyst and employed 2-phenylpyridine (1a) and
We chose
3
8
[
2
N-allyl-N-methylaniline (2a) as the model substrates to screen
[
4c]
lyst. The study on temperature effect showed that reaction at
0 °C gave lower product yield compared with that at 75 °C; and
reaction conditions. In an earlier study, we performed Ru-cata-
[
8b]
6
lyzed allylation of arenes with allylic amines. In present study,
we first used the same conditions to test the cobalt-catalyzed
reaction. Encouragingly, monoallylation product was obtained in
reaction at 100 °C gave close yield to that at 75 °C, but along with
small amount of bisallylation product (Table S1 in Supporting In-
formation). Examination of loading amount of 2a showed that
employing 2 equiv of 2a was suitable. Higher loading (3 equiv) led
to formation of small amount of bisallylation species besides
monoallylation product (Table 1, entries 10—12). Reducing load-
5
0% yield (Table 1, entry 1). It was reported that cobalt-catalyzed
allylation reaction often required other silver salt additive to im-
prove reaction results. 0.5 equiv of AgSbF additive did lead to
6
increase of product yield (Table 1, entry 2). Reducing loading of
AgOAc to 0.2 equiv gave rise to further increase of product yield
ing of CF
3
COOAg caused decrease of product yield (Table 1, entry
1
3). Reducing amount of catalyst to 5 mol% resulted in almost
(
Table 1, entry 3). However, reducing loading of AgOAc to 0.1
equiv caused markedly decrease of yield (Table S1 in Supporting
Information). The combination of other silver salts and AgSbF
same product yield as that employing 10 mol% of catalyst (Table 1,
entry 14). Next, reaction time was examined and 12 h was
demonstrated to be suitable (Table S1 in Supporting Information).
Screening of reaction solvents showed that EtOH, toluene, DMF,
6
was also tested and they were less effective than AgOAc (Table 1,
entries 5—7). KOAc and the combination of KOAc and
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Cobalt-Catalyzed C—H Allylation
Chin. J. Chem.
THF, and DCE were less effective than CF
3
CH
2
OH (Table 1, entries
2a (Table 3). A series of 2-(para-substituted phenyl)pyridines were
demonstrated to react smoothly with 2a to afford ortho-mono-
allylation products in 70%—82% yields (entries 1—10). From the
reaction results, it seems that reactivity of the substrates is not
regularly related to electron effect of the substituents. A range of
1
5—19). In addition, in the absence of AgOAc, the reaction gave
markedly lower product yield. In the absence of cobalt catalyst,
the reaction cannot occur at all (Table S1 in Supporting Informa-
tion and Table 1, entry 20).
Next, we examined scope of allylic amines via reaction with
-phenylpyridine under the above optimized conditions (Table 2).
3
functional groups including OMe, Ph, F, Cl, Br, CF , C(O)Me, COOEt,
2
and COOH were tolerated. Reaction of 4-(pyridin-2-yl)benzoic acid
is a little surprising. The presence of acidic COOH group did not
affect the reaction result. We speculated that excess 2a neutral-
ized the acid and the carboxylate salt participated in the following
coupling reaction. Reaction of 2-(p-tolyl)pyridine required higher
temperature (100 °C) and higher loading of catalyst (10 mol%) to
achieve good yield for unclear reasons (entry 1). Reaction of
2-([1,1'-biphenyl]-4-yl)pyridine and 2-(4-chlorophenyl)pyridine
required lower loading of 2a (1.5 equiv) to make sure of formation
of monoallylation products (entries 3 and 5). 2-(meta-Substituted
phenyl)pyridines also reacted smoothly with 2a to afford ortho-
monoallylation products in 69%—78% yields (entries 11—15). In
each case, the substitution took place on the side of less steric
hindrance. Reaction of 2-(m-tolyl)pyridine also required higher
temperature and higher loading of catalyst (entry 11). 1.5 equiv of
2a was employed in the reaction of 2-(3-fluorophenyl)pyridine to
guarantee monoallylation (entry 14). Reaction of 2-(3,4-dimethyl
phenyl)pyridine and 2-(naphthalen-2-yl)pyridine also gave mono-
allylation products. Reaction of the former proceeded at 100 °C in
the presence of 10 mol% of catalyst (entry 16). Several 2-(ortho-
substituted phenyl)pyridines including 2-(o-tolyl)pyridine,
Besides N-allyl-N-methylaniline, allylic amines including N-allyl-N-
phenylaniline, N-allyl-N-phenylhydroxylamine, N,O-diallyl-N-phe-
nylhydroxylamine, N,N-diallylaniline and N-allylaniline can react
with 2-phenylpyridine to afford monoallylation product 2-(2-allyl-
phenyl)pyridine in 32%—84% yields (entries 2—6). N-Allylaniline
exhibited similar reactivity to N-allyl-N-methylaniline. Other allylic
amines showed lower reactivity than N-allylaniline and N-allyl-N-
methylaniline. Among them, N,O-diallyl-N-phenylhydroxylamine
exhibited the lowest reactivity. Its reaction with 2-phenylpyridine
gave the desired product in 32% yield (entry 4). Prop-2-en-1-
amine cannot react with 2-phenylpyridine under the standard
conditions (entry 7). Several N-(methylallyl)-N-methylanilines
including
N-(but-3-en-2-yl)-N-methylaniline,
N-methyl-N-(2-
methylallyl)aniline, and N-methyl-N-(2-methylallyl)aniline were
also tested. The reaction of each of them with 2-phenylpyridine
cannot form the desired product (entries 8—10).
a
Table 2 Scope of allylic amines
2
=
-(2-methoxyphenyl)pyridine, and 2-(2-halophenyl)pyridine (halo
F, Cl, and Br) were tested and each of them reacted with 2a to
give the desired ortho-monoallylation product (entries 18—22).
Reaction of 2-(o-tolyl)pyridine and 2-(2-bromophenyl)pyridine
with 2a can achieve higher yields when the reactions were per-
2
formed at 100 °C in the presence of 10 mol% of [Cp*Co(CO)I ].
The reaction of 2-(2,4-difluorophenyl)pyridine with 2a under the
standard conditions gave 2-(2-allyl-4,6-difluorophenyl)pyridine in
71% yield (entry 23).
b
Entry
1
Allylic amine
Product
Yield /%
The effect of substituent on the directing group was also
tested (Scheme 2). Reaction of 5-methyl-2-phenylpyridine with 2a
was first examined under the standard conditions. The desired
product was obtained in 88% yield. This result is very close to that
of reaction of 2-phenylpyridine with 2a. Surprisingly, reaction of
2-methyl-6-phenylpyridine with 2a did not give any desired prod-
uct. This is ascribed to steric effect of the methyl group. Thus, the
methyl group adjoining the pyridyl nitrogen atom blocks coordina-
tion of the nitrogen atom to the cobalt center.
85
2
3
3a
3a
55
57
Pyrimidyl group also directed allylation of arenes with 2a.
However, respective reaction of 2-phenylpyrimidine and
4
3a
32
2
-(4-methoxyphenyl)pyrimidine with 2a under the standard con-
ditions formed a mixture of mono- and bisallylation products
Scheme 3). Reducing loading amount of 2a and shortening reac-
5
6
7
8
PhN(CH
2
CH=CH
2
)
2
3a
3a
75
84
–
(
tion time cannot lead to formation of single product. For example,
reaction of 2-phenylpyrimidine with 1.5 equiv of 2a for 4 h af-
forded a about 7.4 : 1 mixture of 4a and 4a’ in 67% overall yield.
Reaction of 2-(meta-substituted phenyl)pyrimidine with 2a
under the standard conditions exhibited good selectivity. Reaction
of each of 2-(m-tolyl)pyrimidine, 2-(3-methoxyphenyl)pyrimidine,
2-([1,1'-biphenyl]-3-yl)pyrimidine, and 2-(3-(trifluoromethyl)phe-
nyl)pyrimidine with 2a gave the corresponding ortho-monoallyla-
tion product in good yield (Table 4, entries 1—4). Exceptionally,
reaction of 2-(3-fluorophenyl)pyrimidine under the same condi-
tions gave a mixture of mono- and bisallylation products (Table 4,
entry 5). This is attributable to small steric hindrance of the fluo-
rine atom. For comparison, we examined reaction of 2-(3,5-difluo-
rophenyl)pyrimidine and 2-(3,5-dimethylphenyl)pyrimidine, re-
spectively. Reaction of the former gave ortho-monoallylation prod-
uct in 47% yield. No bisallylation product was observed. Reaction
of the latter cannot occur (Table 4, entries 6 and 7). Reaction of
3a
none
–
9
none
none
–
–
10
a
Unless otherwise specified, the reactions were carried out on a 0.2 mmol
scale according to the conditions indicated by the above equation, 2 equiv
of allylic amines were employed. Isolated yield.
b
Next we examined scope of 2-arylpyridines via reaction with
Chin. J. Chem. 2021, 39, 1205－1210
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Yan, Yu & Wang
a
Table 3 Scope of 2-arylpyridines
Scheme 2 Reaction of 2-methyl-6-phenylpyridine and 5-methyl-2-phe-
nylpyridine with 2a
b
Entry
2-Arylpyridine
Product
Yield /%
c,d
1
2
3
4
5
6
7
8
9
X = Me (3b)
70
X = OMe (3c)
X = Ph (3d)
X = F (3e)
X = Cl (3f)
X = Br (3g)
82
e
80
Scheme
3
Cobalt-catalyzed reaction of 2-phenylpyrimidine and
75
2-(4-methoxyphenyl)pyrimidine with 2a
e
80
73
72
72
82
71
3
X = CF (3h)
X = C(O)Me (3i)
X = COOEt (3j)
X = COOH (3k)
10
c,d
11
12
13
14
15
X = Me (3l)
X = OMe (3m)
X = Ph (3n)
X = F (3o)
69
2-(o-tolyl)pyrimidine and 2-(2,3-difluorophenyl)pyrimidine under
the standard conditions afforded the desired products in relatively
low yields. The reaction can be improved by employing 10 mol%
of catalyst (Table 4, entries 8 and 9). Finally, reaction of 1-(pyri-
midin-2-yl)-1H-indole with 2a was tested, which gave 2-allyl-1-
71
78
e
73
X = Cl (3p)
77
(
pyrimidin-2-yl)-1H-indole in 76% yield (Table 4, entry 10).
Preliminary mechanistic studies were performed. Firstly, in the
c,d
2
absence of an allylic amine, reaction of 1a with D O was run un-
der the standard conditions for 2 h and the resulting product 1aa
contained 45% of ortho-D content (Scheme 4a). Next, in the ab-
16
62
(3q)
sence of an allylic amine, treatment of 2-(phenyl-d
for 2 h resulted in 1ac, which contained 18% of ortho-D content
Scheme 4b). These facts showed that a reversible H/D exchange
5
)pyridine 1ab
(
can occur under the experimental conditions. Finally, we meas-
ured the kinetic isotopic effect via the reaction of 1a and 1ab with
17
60
2
a under the standard conditions. A k
H
/k
tained by analyzing the H NMR spectrum of the product (Scheme
c). This result suggests that the C—H bond cleavage may not be
the rate-limiting step. Based on the experimental facts and litera-
D
value of 1.1 was ob-
(3r)
1
4
[
4c,9]
ture reports,
in Scheme 5. [Cp*Co(CO)I
CF COOAg to form active catalyst [Cp*Co (OAc)] (A). Next, C—H
bond metalation takes place to produce cobaltacycle B. C—C
double bond insertion of the allylic amine leads to intermediate C.
β-Amino elimination generates the allylated product and amino
cobalt complex D, which further converts to active catalyst A via
reaction with AcOH. In the step of β-amino elimination, the protic
solvent might promote the C—N bond cleavage of allylic amines
we proposed a plausible catalytic cycle as shown
] reacts with AgOAc in the presence of
2
III
+
c,d
3
18
19
20
21
22
X = Me (3s)
X = OMe (3t)
X = F (3u)
X = Cl (3v)
X = Br (3w)
50 (65
81
)
82
69
c,d
56 (67
)
[
10]
via a hydrogen-bond activation.
23
71
Conclusions
(3x)
a
Unless otherwise specified, the reactions were carried out on a 0.2 mmol
In summary, we developed a cobalt-catalyzed method for the
allylation of arenes via pyridyl- or pyrimidyl-directed aryl C—H
bond activation and cleavage of the C—N bond of allylic amines.
The reaction proceeded under mild conditions and afforded the
scale according to the conditions indicated by the above equation, 2 equiv
of 2a was employed. Isolated yield. Reaction was run at 100 °C. 10 mol%
of [Cp*Co(CO)I
b
c
d
e
2
] was employed. 1.5 equiv of 2a was employed.
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Cobalt-Catalyzed C—H Allylation
Chin. J. Chem.
a
Table 4 Cobalt-catalyzed reaction of 2-arylpyrimidines with 2a
Scheme 4 Mechanistic studies
b
Entry
2-Arylpyrimidine
Product
Yield /%
1
2
3
4
5
X = Me (4c)
X = OMe (4d)
X = Ph (4e)
84
76
82
X = CF
3
(4f)
86 c
X = F (4g)
40 (51 )
6
7
X = F (4h)
X = Me (4i)
47
0
d
8
53 (70 )
(4j)
d
9
34 (57 )
Scheme 5 Plausible mechanism
(4k)
10
76
(
4l)
a
Unless otherwise specified, the reactions were carried out on a 0.2 mmol
scale according to the conditions indicated by the above equation. Iso-
b
c
d
lated yield. Yield of 2-(2,6-diallyl-3-fluorophenyl)pyrimidine. Yield of
monoallylation product when 10 mol% of [Cp*Co(CO)I ] was employed.
2
allylation products in moderate to high yields. Pyridyl-directed
reactions exhibited higher selectivity. ortho-Position monoallyla-
tion products of the phenyl groups were obtained whether it is
ortho-, meta- or para-substituted phenyl substrates to be used. A
range of functional groups including electron-donating and elec-
tron-withdrawing groups such as OMe, Me, Ph, F, Cl, Br, CF ,
3
C(O)Me, COOEt, and COOH on the phenyl rings can be tolerated.
This protocol is complementary with Ru-catalyzed allylation of
2
-arylpyridines with allylation amines, which led to bisallylation
products of 2-(para-substituted phenyl)pyridines and less steri-
cally hindered 2-(meta-substituted phenyl)pyridines.
Experimental
Supporting Information
2
-Arylpyridines (0.2 mmol), allylic amines (0.4 mmol), AgOAc
0.04 mmol), CF COOAg (0.1 mmol), [Cp*Co(CO)I ] (0.01 mmol),
and CF CH OH (1.5 mL) were successively added into a Schlenk
tube. The mixture was stirred at 75 °C for 12 h. Upon cooling to
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.202000680.
(
3
2
3
2
room temperature, the resulting mixture was diluted with EtOAc Acknowledgement
and filtered through a short pad of silica gel. The filtrate was con-
centrated under reduced pressure and the residue was purified by
column chromatography to afford the desired product.
Financial support from the National Natural Science Founda-
tion of China (No. 21372212) and the National Basic Research
Chin. J. Chem. 2021, 39, 1205－1210
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Concise Report
Yan,ꢀYuꢀ&ꢀWang
Program of China (No. 2015CB856600) is greatly acknowledged.
Wang, H.; Schroder, N.; Glorius, F. Mild Rhodium(III)‐Catalyzed Direct
C‐H Allylation of Arenes with Allyl Carbonates. Angew. Chem. Int. Ed.
2
013, 52, 5386–5389; (d) Cajaraville, A.; Lopez, S.; Varela, J. A.; Saá, C.
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Manuscript received: December 14, 2020
Manuscript revised: January 25, 2021
Manuscript accepted: January 26, 2021
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