Directing-Group-Controlled Ring-Opening Addition and Hydroarylation of Oxa/azabenzonorbornadienes with Arenes via C-H Activation

Article abstract of DOI:10.1021/acs.orglett.0c00765

An efficient method for the directing group controlled rhodium-catalyzed addition reaction of oxa/azabicylic alkenes with aromatic ketones and benzoic acids has been developed. The ketones and benzoic acids afforded different addition products when reacte

Full text of DOI:10.1021/acs.orglett.0c00765

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Letter
Directing-Group-Controlled Ring-Opening Addition and
Hydroarylation of Oxa/azabenzonorbornadienes with Arenes via
C−H Activation
∇
∇
Keyang Zhang, Ruhima Khan, Jingchao Chen, Xuexin Zhang, Yang Gao, Yongyun Zhou,* Kangkui Li,
Youxian Tian, and Baomin Fan*
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sı Supporting Information
ABSTRACT: An efficient method for the directing group controlled rhodium-catalyzed addition reaction of oxa/azabicylic alkenes
with aromatic ketones and benzoic acids has been developed. The ketones and benzoic acids afforded different addition products
when reacted with oxa/azabicyclic alkenes. The reaction between ketones and azabenzonorbornadienes furnished the ring-opening
addition products. The reaction between benzoic acids and aza/oxabicyclic alkenes proceeded in the absence of silver salt, giving the
1
:2 hydroarylation products in yields up to 96%.
7
he direct functionalization of C−H bonds has become a
work by Miura et al., there have been various reports on the
T
prominent method for the construction of new C−C
carboxylate-directed ortho-C−H bond functionalization of
1
8
bonds in organic synthesis. The regioselectivity in C−H bond
functionalization controlled by various directing groups (DG)
is now regarded as an atom- and step-economical synthetic
tool, since such transformations do not require prefunction-
arenes.
The transition-metal-catalyzed addition and ring-opening
reaction of strained 7-oxa/azabenzonorbornadienes provide
significant pathways for the introduction of new functionalities
into the framework of organic compounds. Hence, it has
emerged as an important transformation and has been
employed in the preparation of a variety of organic products
2
alization. Since the pioneering work by Murai and co-workers
3
on Ru-catalyzed addition of C−H bonds to olefins, the
transition-metal-catalyzed C−H bond functionalization with
various directing groups has provided a straightforward
method for the regioselective construction of C−C and C-
9
of biological interest featuring diverse functional groups. Since
10
the first work reported by the Li group, the transition-metal-
catalyzed addition of C−H bond to strained oxa/azanorborna-
dienes has become an interesting approach for the synthesis of
polyaromatic compounds. In this context, Miura et al.
demonstrated the rhodium-catalyzed direct coupling of arenes
with heterobicyclic alkenes to form ortho-naphthylated
4
heteroatom bonds. Among the various directing groups, the
weakly coordinating ketone-directed ortho-C−H bond func-
tionalization reactions offer an efficient and straightforward
method for the synthesis of highly functionalized ketones.
These reactions are catalyzed by transition metals such as Ru,
11a
5
products. There have been reports on the coupling reactions
Rh, Pd, Ir, Mn, Co, etc. Recently, low coordinating
carboxylates have also been successfully used as directing
groups for ortho-C−H bond functionalization for the
construction of C−C, C−O, C−N, C−S, C−P, C−halogen
bonds in synthetic chemistry. The growing interest in the
application of carboxylate as DG is because they are broadly
abundant and they can be removed tracelessly or used for
Received: February 28, 2020
6
further functionalization/derivatization. After the pioneering
©
XXXX American Chemical Society
https://dx.doi.org/10.1021/acs.orglett.0c00765
A
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of oxa/azanorbornadienes with arenes via C−H bond
Gratifyingly, the yield was enhanced to 61% in 24 h when
12
11,13
14
activation under the catalysis of Ru, Rh,
Co, etc.
AgNTf was used (Table 1, entry 5). The reaction did not
2
Despite these achievements, it is still interesting to explore new
C−H functionalization reactions with oxa/azanorbornadienes.
Very recently, Li and co-workers demonstrated the first
application of 7-azabenzonorbornadienes in Rh-catalyzed
enantioselective desymmetrizative coupling reaction with N-
occur when AgNTf2 was used as the sole additive,
demonstrating the indispensable role of NaOAc in the present
reaction (Table 1, entry 7). To our delight, the desired product
3aa was obtained in increased yield of 66% in just 12 h when
0.5 equiv of NaOAc was used (Table 1, entry 9). So, the
following investigation was continued using 0.5 equiv of
NaOAc (Table 1, entry 12) (see the Supporting Information
for details).
15a
pyrimidylindoles via C−H activation.
The same group
reported the Rh-catalyzed chemo-divergent coupling reaction
1
5b
of oxa/azabicyclic olefins with sulfoxonium ylides. We have
been paying interest in the asymmetric ring-opening reactions
The efficiency of [RhCp*Cl ] in the carboxylate-group-
2 2
16
(
ARO) of oxa/azanorbornadienes. As a part of our study, we
directed C−H activation reaction has been reported by many
18
have demonstrated the Rh(III)-catalyzed ring-opening addi-
groups. We extended our study by using carboxylates as
directing groups instead of ketones (see Table 2). Initially,
tion of azabenzonorbornadienes with cyclic N-sulfonyl
17
ketimines through C−H bond functionalization. In con-
tinuation of our interest in the C−H bond functionalization
reaction of oxa/azabenzonorbornadienes, we herein report the
Rh-catalyzed ring-opening addition and hydroarylation of
bicyclic alkenes through ortho C−H activation controlled by
weakly coordinating directing groups ketone and carboxylate
groups. The methodology provides a mild pathway for the
synthesis of highly substituted aromatic compounds.
Table 2. Optimization of Reaction Conditions for
Carboxylate Directed C−H Functionalization Reaction
a
b
entry
additive 1
additive 2
solvent
time (h)
yield (%)
Considering the efficiency of [RhCp*Cl ] in the ketone
2
2
directed C−H bond functionalization of arenes, at the onset of
our investigation, the reaction between acetophenone 1a and
azabenzonorbornadiene 2a was performed using [RhCp*Cl2]2
1
2
3
4
5
6
7
AgSbF
AgSbF
6
6
NaOAc
NaOAc
NaOAc
−
DCE
THF
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
3
24
8
36
15
13
11
8
95
29
93
−
−
−
−
−
−
−
−
c
NR
(
5 mol %) as the metal catalyst in the presence of additives
KOAc
85
AgSbF (15 mol %) and NaOAc (1 equiv) in 1,4-dioxane at
6
2
K CO3
trace
1
00 °C for 48 h. The regioselective ring-opening addition of 2a
c
PivOH
NR
occurred at the ortho-position of ketone and the desired
product 3aa was observed only in trace amounts (see Table 1,
entry 1). The reaction was stereoselective as the cis-isomer was
obtained as the only product. Screening of various solvents
indicated that DCE was the most appropriate solvent (Table 1,
entry 3). No reaction occurred in the absence of silver salt,
showing that the additive is important for the present reaction
d
8
NaOAc
NaOAc
NaOAc
96
92
93
e
9
f
4
18
1
0
a
Reaction conditions: 4a (0.2 mmol), 2a (0.2 mmol), [RhCp*Cl
]
2 2
(
5 mol %), additive 1 (15 mol %), additive 2 (1 equiv), solvent (2
b
c
d
mL). Isolated yield. NR = No reaction. NaOAc (2 equiv) was
e
f
used. Reaction temperature was 100 °C. [RhCp*Cl2]2 (2.5
mmol %) was used.
(Table 1, entry 4). Next, a series of additives were screened.
Table 1. Optimization Table for Ring-Opening Addition
Reaction
a
commercially available benzoic acid 4a was treated with
azabenzonorbornadiene 2a in the presence of [RhCp*Cl ] (5
2
2
mol %), AgSbF (15 mol %), and NaOAc (1 equiv) in DCE at
6
80 °C. The reaction proceeded smoothly in 3 h, giving the 1:2
addition product 5aa at both ortho-positions in excellent yield
of 95% (Table 2, entry 1). Screening of other solvents gave
inferior results. Surprisingly, the addition product 5aa was
obtained in 93% in 8 h when the reaction was performed
without any silver salt, indicating that the addition reaction
could be performed without using the expensive silver salts
b
entry additive 1 additive 2
solvent
time (h) yield (%)
1
2
3
4
5
6
7
8
9
0
1
2
AgSbF6
AgSbF6
AgSbF6
−
AgNTf2
ScOTf3
AgNTf2
AgNTf2
AgNTf2
AgNTf2
AgNTf2
AgNTf2
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
−
LiOAc
NaOAc
NaOAc
NaOAc
NaOAc
1,4-dioxane
48
48
48
48
24
56
24
36
12
17
76
24
trace
NR
25
NR
61
trace
NR
55
66
51
61
53
c
CH CN
3
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
c
(
Table 2, entry 3). Hence, the following studies were
performed without using silver salts. No reaction occurred in
the absence of the additional additive (Table 2, entry 4). Upon
using a strong base (K CO ), the addition product 5aa was
c
2
3
obtained in 82% after 6 h. However, upon extending the
d
e
f
reaction time to 13 h, 5aa reacted with the solvent DCE, giving
1
1
1
8s
the corresponding ester in 69% (Table 2, entry 6) (see the
Supporting Information for details).
g
Having obtained the optimized reaction conditions, the
scope of this interesting transformation was investigated. The
reaction was compatible for a wide range of aromatic ketones
a
Reaction conditions: 1a (0.6 mmol), 2a (0.2 mmol), [RhCp*Cl2]2
5 mol %), additive 1 (15 mol %), additive 2 (1 equiv), solvent (2
mL). Isolated yield. NR = No reaction. NaOAc (0.5 equiv) was
(
b
c
d
(
Scheme 1). Acetophenones bearing electron-withdrawing as
e
f
used. NaOAc (0.25 equiv) was used. Reaction temperature was 80
well as electron-donating substituents at para-position (1a−1f)
reacted smoothly with azabenzonorbornadiene 2a to furnish
g
°
C. [RhCp*Cl ] (2.5 mol %) was used.
2 2
B
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Letter
a
,
b
Scheme 1. Substrate Scope of Ring-Opening Addition
Reaction
Scheme 2. Substrate Scope with Respect to Benzoic Acids
,
a b
a
Reaction conditions: 2 (0.2 mmol), 4 (0.2 mmol), [RhCp*Cl ] (5
2
2
b
mol %), NaOAc (2 equiv), DCE (2 mL) at 80 °C. Isolated yield.
a
Reaction conditions: 1 (0.6 mmol), 2 (0.2 mmol), [RhCp*Cl ] (5
2
2
reaction was incomplete, even after extending the reaction time
to 61 h, and gave the 1:2 addition product 5la only in trace
amounts.
mol %), AgNTf (15 mol %), NaOAc (0.5 equiv), DCE (2 mL) at
1
2
b
00 °C. Isolated yield.
The applicability of the present methodology was further
illustrated with respect to different substituted bicyclic alkenes
2 in reaction with benzoic acid 4a (Scheme 3). Azabenzo-
norbornadienes with both electron-donating and electron-
withdrawing groups on the benzene ring were found to be
suitable reaction partners under the optimized reaction
conditions and furnished the corresponding 1:2 addition
products 5ab−5af in 82%−94% yields. N-tosyl-protected
azabenzonorbornadiene 2g also reacted smoothly with benzoic
acid to give the corresponding product 5ag in 93% yield. Next,
the substrate scope was extended to oxabenzonorbornadienes.
In the case of oxabicyclic alkenes, the reaction between
oxabenzonorbornadiene 2h and 4a was incomplete under the
optimized reaction condition used for azabenzonorborna-
dienes. Gratifyingly, upon using 2 equiv of KOAc instead of
NaOAc, the reactants were consumed in 5 h and the desired
1:2 addition product 5ah was obtained in 92% yield. 7-
Oxabenzonorbornadienes with different substituents on the
benzene ring reacted smoothly to give the desired products
5ai−5al in good to excellent yields. The present methodology
was found to be unsuitable for oxabenzonorbornadienes with
electron-withdrawing substituents as a complex mixture was
formed and the desired addition products could not be
isolated.
the corresponding ring-opening addition products (3ba−3fa)
in moderate to good yields. The electron-donating −OCH
3
group at both meta- and ortho-positions participated in the
reaction and afforded the addition products 3ga and 3ha in
6
0% and 82% yields, respectively.
The methodology was also suitable for naphthylene
derivative (1i) and heterocyclic compound 1-(thiophen-2-
yl)ethan-1-one (1j). The methodology worked for the ketone
with a longer aliphatic chain and gave the product 3ka in 43%
yield. The applicability of the catalytic system was evaluated
with respect to bicyclic alkenes. N-Boc protected azabicylic
alkenes with both electron-donating and electron-withdrawing
substituents participated under the optimized reaction
conditions to give the addition products (3ab, 3ac, 3ad) in
low to good yields. N-tosyl-protected azabenzonorbornadiene
also reacted smoothly.
Next, the substrate scope of the hydroarylation reaction via
carboxylate-group-directed C−H activation reaction between
different substituted benzoic acids and bicyclic alkenes was
examined (see Scheme 2). The electronic nature of
substituents at para-position of benzoic acid did not have a
remarkable effect on the efficiency of the reaction. Benzoic
acids with electron-withdrawing and electron-donating groups
at the para-position participated in the addition reaction and
the corresponding 1:2 addition products (5ba−5ia) were
obtained in moderate to excellent yields. In the case of methyl
group at meta- and ortho-positions, the 1:1 addition products
The synthetic application of the present methodology was
further demonstrated by reacting the addition product 5ah
15b
with p-TSA in DCE at 80 °C for 36 h (see Scheme 4). The
hindered 2,6-diaryl benzoic acid 6ah was obtained in 74%
yield.
(5ja, 5ka) were obtained as the only products in 90% and 93%
yields. This selectivity could be attributed to the steric
interaction between the substituent and the incoming bicyclic
alkene. Unfortunately, methyl benzoate was sluggish and the
To obtain a mechanistic insight of the present trans-
formation, control experiments were performed (Scheme 5).
Significant incorporation of deuterium (45%) at both the
1
9a
C
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Scheme 3. Substrate Scope of Oxa/Azabicyclic Alkenes ,
a b
Scheme 5. Control Experiments
H addition products were obtained in 34%−82% yields.
Interestingly, for the carboxylate-directed C−H bond
functionalization reaction, the expensive silver salt was not
required. Both oxa- and aza-bicylic alkenes with different
substituents participated under the developed reaction
conditions and the 1:2 addition products were obtained in
good to excellent yields. The present protocol showed a wide
range of functional group tolerance and offered a synthetic
method for the construction of highly substituted polycyclic
organic compounds.
a
Reaction conditions: 2 (0.2 mmol), 4 (0.2 mmol), [RhCp*Cl ] (5
2
2
b
mol %), NaOAc (2 equiv), DCE (2 mL) at 80 °C. Isolated yield.
Scheme 4. Derivatization of 5ah
ASSOCIATED CONTENT
■
ortho-positions was observed when benzoic acid 4a was
subjected to the standard reaction conditions with 5 equiv of
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c00765.
D O (see Scheme 5a). This indicates the reversibility of the
2
19a
C−H bond cleavage step. Next, parallel experiments using
benzoic acid 4a or 4a-d with azabenzonorbornadiene resulted
5
Experimental procedures and compounds character-
ization data, including the NMR spectra (PDF)
into a kinetic isotope effect (KIE) value of 1.1 (see Scheme
5
b). Finally, when a competitive reaction was performed
between 4a and 4a-d with 2a under the standard reaction
5
conditions, a KIE value of 4.5 was observed (see Scheme 5c).
These results indicate that the rate-determining step involves
AUTHOR INFORMATION
■
12b,17,19b
Corresponding Authors
cleavage of the C−H bond.
experiments and the literature reports,
Based on the control
5
c,d,11,13,17,18a,19
we have
Baomin Fan − Key Laboratory of Chemistry in Ethnic Medicinal
Resources, Yunnan Minzu University, Kunming 650500, China;
School of Chemistry and Environment, Institution Yunnan
Minzu University, Kunming 650500, China; orcid.org/
0000-0003-1789-3741; Email: FanBM@ynni.edu.cn
Yongyun Zhou − Key Laboratory of Chemistry in Ethnic
Medicinal Resources, Yunnan Minzu University, Kunming
650500, China; School of Chemistry and Environment,
Institution Yunnan Minzu University, Kunming 650500,
China; Email: zhouyy@ynni.edu.cn
speculated possible reaction pathways for the present addition
reactions in the Supporting Information.
In summary, we have successfully developed an efficient
regioselective Rh-catalyzed addition reaction between arenes
and oxa/azabicyclic alkenes. The reaction was controlled by
weakly coordinating directing groups ketone and carboxylate
groups. The reaction proceeded via C−H bond functionaliza-
tion at the ortho-position of the arenes. In the case of ketone-
directed addition reaction, the stereoselective ring-opening C−
D
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Authors
pubs.acs.org/OrgLett
Letter
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Complete contact information is available at:
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Author Contributions
∇
These authors contributed equally.
Notes
(
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The authors declare no competing financial interest.
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Applied Basic Research Project of Yunnan Province (Nos.
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017FA004 and 2018FB021), the Department of Education of
Yunnan Province (No. 2019Y0198), National Innovation and
Entrepreneurship Training Program for College Students, and
Yunnan Provincial Key Laboratory Construction Plan Funding
of Universities for their financial support.
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