Cobalt-catalyzed ring-opening addition of azabenzonorbornadienes: Via C(sp3)-H bond activation of 8-methylquinoline

Article abstract of DOI:10.1039/d0cc05374k

The first ring-opening addition of a benzylic C(sp3)-H bond to azabenzonorbornadienes is demonstrated. The reaction proceeded under the catalytic system of [Cp?CoI2(CO)], AgSbF6 and Fe(OAc)2 in PhOMe. The methodology showed a good substrate scope with up to 96 yield. The relative configuration of the product was determined as cis-configuration by X-ray crystallography.

Full text of DOI:10.1039/d0cc05374k

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Cobalt-Catalyzed Ring-opening Addition of
Azabenzonorbornadienes via C(sp3)-H Bond Activation of 8-
Methylquinoline
Received 00th January 20xx,
Accepted 00th January 20xx
Heng Tan,a‡ Ruhima Khan,a‡ Dandan Xu,a Yongyun Zhou,*a,b Xuexin Zhang,a Guangrui Shi,a and
DOI: 10.1039/x0xx00000x
Baomin Fan*a,b
The first ring-opening addition of benzylic C(sp3)-H bond to workers demonstrated the participation of oxa/azabicyclic
azabenzonorbornadienes is demonstrated. The reaction alkenes in the C-H activation reaction for the first time.13
proceeded under the catalytic system of [Cp*CoI2(CO)] , AgSbF6 Following this pioneering work, many groups have reported
and Fe(OAc)2 in PhOMe. The methodology showed good substrate the C-H activation reaction using oxa/azabicyclic alkenes as the
scope with up to 96% yield. The relative configuration of the coupling partners (Scheme 1).14 Li’s group reported the first
product was determined as cis-configuration by X-ray CpXRh(III)/AgSbF6-catalyzed asymmetric ring-opening reaction
crystallography.
of azabenzonorbornadienes with indoles via C-H activation
pathway.15 As a part of our interest in the C-H functionalization
reaction,16 we have developed an efficient Rh-catalyzed
addition reaction between oxa/azabicyclic alkenes and arenes
via C-H activation. The reaction was controlled by directing
groups - ketone-directed reaction provided the stereoselective
ring-opening C − H addition products whereas carboxylate-
directed C − H functionalization reaction furnished the 1:2
addition products.16c However, the studies so far are limited to
the functionalization of C(sp2)-H bonds. To the best of our
knowledge, there has been no reports on the involvement of
oxa/azabicyclic alkenes in the C(sp3)-H activation reactions. In
this work, we report the first C(sp3)-H ring-opening addition
reaction of 8-methylquinolines with azabenzonorbornadienes
catalyzed by earth abundant cobalt catalyst.
In the last few decades, transition-metal-catalyzed
functionalization of C-H bonds has emerged as one of the most
important and efficient synthetic strategy for the construction
of complex structures in organic chemistry.1 The method
provides many useful compounds in shorter reaction pathways
by avoiding prefunctionalization of substrates in high atom
economy. The transition metals involved in the C-H
functionalization reaction includes Rh,2 Ru,3 Co,4 Pd,5 Ir,6 etc.
Recently, chemists have been paying attention on the
functionalization of C(sp3)-H bonds.8 However, this kind of
reaction is still challenging due to the poor reactivity of C(sp3)-
H bond in the bond cleavage stage and the subsequent
coupling step. Among the various C(sp3)-H bond substrates, 8-
methylquinolines have been proved to be good substrates for
(a) Previous work: Coupling of arenes with oxa/azabicyclic alkenes via C(sp2)-H
the transition-metal-catalyzed C(sp3)-H
functionalization
XH
functionalization
X
Ar
reactions.9 They can overcome the difficulty in the formation
of cyclometallated complexes. Since the first work by
Sundararaju et al.,10 there are other reports on the application
of the environmentally friendly, inexpensive, and earth
abundant first-row transition metal cobalt in the C(sp3)-H
activation reactions of 8-methylquinoline.11
Rh, Ru, Co, Pd
+
Arenes
C(sp2)-H functionalization
X= O, NR
(b) Present work: Coupling of 8-methylquinoline with azabicyclic alkenes via C(sp3)-H
functionalization
X
CH3
X
N
Co
On the other hand, there have been extensive studies on the
transition-metal-catalyzed
oxa/azabicyclic alkenes with various nucleophiles.12 Li and co-
+
C(sp3)-H functionalization
N
ring-opening
reaction
of
X = NBoc, NCbz, NTs
Scheme 1. Transition-metal-Catalyzed C−H Bond Activation of Arenes
with Oxa/Azabicyclic Alkenes
a. Key Laboratory of Chemistry in Ethnic Medicinal Resources, Yunnan Minzu
University, Yuehua Street, Kunming, 650500, China
E-mail: zhouyy@ynni.edu.cn (Yongyun Zhou), FanBM@ynni.edu.cn (Baomin Fan)
b. School of Chemistry and Environment, Yunnan Minzu University, Yuehua Street,
Kunming, 650500, China
Recently, the Cp*CoIII-catalyst has emerged as an efficient and
versatile catalyst in C-H activation reactions because it is easily
available, cost effective and exhibits excellent reactivity, good
nucleophilicity and selectivity.4a,17 Our investigation began
with the reaction between 8-methylquinoline 1a and
azabenzonorbornadiene 2a under the catalysis of
‡ These authors contributed equally.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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[Cp*CoI2(CO)], AgSbF6 and NaOAc in DCE (dichloroethane) at
80 oC for 48 h. The ring-opening C-H addition product 3aa was
obtained in 44% yield (Table 1, entry 1). Other silver salts such
as AgPF6, AgBF4, AgOTf and AgNTf2 failed to improve the yield.
No reaction occurred in the absence of the silver salt (entry 2).
Next, the screening of various additives revealed that Fe(OAc)2
was the most suitable additive (entry 3). A further increase in
the yield (57%) was obtained when 10 mol% Fe(OAc)2 was
6e
PhOMe
70
18
87
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DOI: 10.1039/D0CC05374K
aReaction conditions: 1a (0.4 mmol), 2a (0.2 mmol), [Cp*CoI2(CO)] (5
mol%), AgSbF6 (30 mol%), Fe(OAc)2 (10 mol%), Solvent (2mL) at 80 °C
under argon atmosphere. bIsolated yields. c[Cp*CoI2(CO)] (10 mol%).
dAgSbF6 (20 mol%). e1a (0.6 mmol).
After obtaining the optimized reaction conditions, the scope
and limitation of the present protocol was investigated with
respect to various substituted 8-methylquinolines (Scheme 2).
The 8-methylquinolines with electron donating substituents
(CH3, OMe) at C5-position gave the desired ring-opening C-H
addition products (3ba, 3ca) in 93% and 87% yields
respectively. Halogen (F, Cl, Br, I) group substituted 8-
methylquinolines also participated in the reaction with the
halogens remaining intact in the product which could be used
for further functionalization reactions (3da-3ga). No reaction
occurred in the cases of heterocyclic 4-methyl-1H-
benzotriazole (1r) and quinoline-8-carbaldehyde (1s).
used (entry 6) (See supporting information for details).
Table 1. Optimization table for the formation of 3aaa
CH3
Boc
[Cp*CoI2(CO)] (5 mol%)
Lewis acid (30 mol%)
N
N
N
NHBoc
+
Additive (0.2 mmol)
DCE, 48 h, 80 °C
1a
2a
3aa
Entry
Ag
Additive
Yieldb
1
2
AgSbF6
-
NaOAc
NaOAc
Fe(OAc)2
-
44
NRc
54
9
BocHN
3
AgSbF6
AgSbF6
AgSbF6
AgSbF6
CH3
Boc
[Cp*CoI2(CO)] (10 mol%)
AgSbF6 (30 mol%)
N
N
N
4
R
Fe(OAc)2 (10 mol%)
PhOMe, 70 C
R1
R
R1
5d
6e
Fe(OAc)2
Fe(OAc)2
50
57
2a
1
3
BocHN
BocHN
BocHN
BocHN
BocHN
aReaction conditions: 1a (0.4 mmol), 2a (0.2 mmol), [Cp*CoI2(CO)] (5
mol%), Ag (30 mol%), Additive (0.2 mmol), DCE (2 mL) at 80 °C under
N
N
N
N
N
c
argon atmosphere. bIsolated yield. NR = No Reaction. dFe(OAc)2 (2
equiv). eFe(OAc)2 (10 mol%).
OMe
Cl
F
3ea,
3da,
16h, 69%
3aa,
3ba,
24h, 66%
18h, 87%
24h, 93%
3ca,
16h, 87%
The optimization study was further continued by screening
different solvents (Table 2). Gratifyingly, the ring-opening C-H
addition product 3aa was furnished in highest yield of 64%
when anisole (PhOMe) was used as the solvent (entry 2). On
increasing the amount of [Cp*CoI2(CO)] to 10 mol%, an
improvement in the yield to 70% was observed in 16 h (entry
3). So, further studies were performed by using 10 mol% of
[Cp*CoI2(CO)]. The analysis of different temperatures showed
that the most ideal temperature is 70 oC (entry 4). To our
delight, a remarkable enhancement in the reaction yield (87%)
was observed on using 0.6 mmol of 1a (entry 6) (See
supporting information for details).
BocHN
BocHN
BocHN
BocHN
BocHN
N
N
N
N
N
CF3
I
NO2
Br
3ja,
48h, 25%
3ga,
16h, 67%
3ha,
24h, 67%
3fa,
16h, 68%
3ia,
48h, 45%
BocHN
BocHN
BocHN
BocHN
N
N
R
N
N
R
Table 2. Further optimization of reaction conditionsa
R = CH3, 48h, 38%
R = Br, 24h, 62%
3ka,
3la,
3ma,
R = CH3, 24h, 92%
R = OMe, 12h, 96%
3na,
3oa,
3qa
, 24h, 69%
3pa
, 24h, 56%
R = Br, 24h, 72%
NHBoc
O
Boc
N
NH
NHBoc
N
CH3
[Cp*CoI2(CO)] (5 mol%)
AgSbF6 (30 mol%)
N
N
N
NHBoc
+
Fe(OAc)2 (10 mol%)
Solvent
N
3ra
3sa
, 48h, NR
, 48h, NR
1a
2a
3aa
aReaction conditions: 1 (0.6 mmol), 2a (0.2 mmol), [Cp*CoI2(CO)] (10 mol%),
AgSbF6 (30 mol%), Fe(OAc)2 (10 mol%), PhOMe (2 mL) at 70 °C under argon
atmosphere for indicated time. bIsolated yields.
Entry
Solvent
Toluene
PhOMe
PhOMe
PhOMe
PhOMe
Temp (oC)
Time (h)
48
Yieldb
1
2
80
80
80
70
70
55
64
70
78
30
Scheme 2. Substrate Scope with respect to 8-methylquinolinesa,b
Other electron withdrawing groups such as CF3, NO2 at C5-
position also performed well under the present reaction
conditions. Gratifyingly, 8-methylquinolines with electron
donating groups (CH3, OMe) at C6-position furnished the
desired products (3la, 3ma) in excellent yields. 6-Bromo-8-
methylquinoline 1n also gave the C-H addition products in 72%
48
3c
4
16
24
5d
24
2 | J. Name., 2012, 00, 1-3
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yield. Lowering in the reaction yields was observed in the case were conducted (Scheme 4b) (See supporting information for
View Article Online
DOI: 10.1039/D0CC05374K
of electron donating substituents at C7-position. The more details). The results indicate that the C-H cleavage is probably
hindered 3-ethyl-5,8-dimethylquinoline 1p and 3-ethyl-6,8- involved in the rate-limiting step.
dimethylquinoline 1q also performed well in the reaction.
The evaluation of substrate scope for the present C(sp3)-H
(a) H/D Exchange reaction
H/D
addition reaction was further extended with different
CH3
substituted
azabenzonorbornadienes
(Scheme
3).
N
N
Standard Conditions
CD3OD (10 equiv)
13% D
Azabenzonorbornadienes with both electron donating and
electron withdrawing substituents participated in the reaction
giving the addition products (4ab, 4ac, 4ad) in poor to
1a
d3-1a
(b) Competitive Experiment
moderate yields.
Azabenzonorbornadienes with other
BocHN
protecting groups such as tosyl and benzyl carbamate also
afforded the desired ring-opening addition products 4ae and
4af in 60% and 62% yields respectively. The desired products
were not obtained on using oxabenzonorbornadiene (2g) and
benzonorbornadiene (2h).
CH3
N
N
3aa
[Cp*CoI2(CO)] (10 mol%)
AgSbF6 (30 mol%)
Boc
1a
0.3 mmol
N
BocHN
CD3
N
Fe(OAc)2 (0.02 mmol)
PhOMe, 70 C
D
D
R
2a
0.2 mmol
X
3 h
H
CH3
N
KIE = PH/PD = 5.7
[Cp*CoI2CO] (10 mol%)
AgSbF6 (30 mol%)
d2-3aa
N
X
d3-1a 0.3 mmol
N
Fe(OAc)2 (10 mol%)
PhOMe, 70 C
R
Scheme 4. Mechanistic experiments
2
1
Based on our control experiments and precedent literature
reports,10,11a,14g,17a,18 we have proposed a possible reaction
mechanism for the present addition reaction (Scheme 5).
4
X = NBoc, NTs, NCbz, O, CH2
F
Br
Br
TsHN
F
Boc
BocHN
BocHN
BocHN
HN
Me
[Cp*CoI2(CO)]
N
N
N
N
N
N
AgSbF6
Fe(OAc)2
1a
Cp*CoX2
X = SbF6 or OAc
n
4ad
, 48h,35%
H3C
3aa
4ab
4ac,
48h, 45%
48h, 51%
4ae
Co
X
, 48h, 60%
C-H activation
N
Cp*
-HX
HX
CbzHN
Boc
N
HO
I
protonatio
alkene
coordination
Boc
N
*Cp
N
N
2a
N
Co
X
N
4af
, 48h, 62%
4ag
4ah
, 21h, NR
, 48h, ND
aReaction conditions: 1 (0.6 mmol), 2 (0.2 mmol), [Cp*CoI2(CO)] (10 mol%),
AgSbF6 (30 mol%), Fe(OAc)2 (10 mol%), PhOMe (2 mL) at 70 °C under argon
atmosphere for indicated time. bIsolated yields. ND = Not determined.
Scheme 3. Substrate Scope with respect of Azabenzonorbornadienesa,b
Based on the single crystal structure of the product 4ae, the
relative configuration of the product was assigned as Cis-
configuration (Figure 1).
X
N
NBoc
Co
Co Cp*
IV
X
II
NBoc
Cp*
N
-N elimination

coordinative
insertion
III
Scheme 5. Plausible Reaction mechanism
Initially, the reaction of [Cp*CoI2CO] with AgSbF6 and Fe(OAc)2
will form the intermediate Cp*CoX2 (X = OAc or SbF6) which
probably initiates the C(sp3)-H activation of 8-methylquinoline
1a by forming a five-membered metallacycle I with formation
of HX. Then, coordination of azabenzonorbornadiene 2a with I
affords the complex II which undergoes Co-C bond migratory
insertion to give the seven-membered intermediate III. Then,
complex III undergoes β-nitrogen elimination to afford ring-
opening product IV which on protonation gives the final
product 3aa with regeneration of the active cobalt species.
In summary, an efficient and cost effective Cobalt-catalyzed
method for the addition of C(sp3)-H bond to
azabenzonorbornadienes was developed for the first time. The
quinolines which are important skeletons present in bioactive
compounds and natural products were successfully added to
azabenzonorbornadienes. The ring-opening addition products
TsHN
N
Figure 1. X-ray Single Crystal Structure of 4ae
To further understand the reaction pathway, some control
experiments were performed (Scheme 4). The H/D exchange
reaction of 1a by using CD3OD (10 equiv) under the standard
reaction conditions showed 13% deuterium incorporation
indicating that the C-H cleavage step is reversible. No
deuterium incorporation occurred in the presence of 2a
(Scheme 4a). To further investigate the kinetic isotopic effect
(KIE) of the reaction, parallel experiments of 1a and d3-1a with
2a and competitive experiment between 1a and d3-1a with 2a
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J. Name., 2013, 00, 1-3 | 3
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10, 3987; (c) B.-X. Liu, T. Zhou, B. Li, S.-S. Xu, HV.-ieBw.ASrtoicnlegOanlninde
were furnished in average to excellent yields. The reaction
exhibited broad substrate scope with good functional group
tolerance.
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DOI: 10.1039/D0CC05374K
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The authors are thankful to the National Natural Science
Foundation of China (21961045), the Applied Basic Research
Project of Yunnan Province (2017FA004, 2018FB021), the
Department of Education of Yunnan Province (2019J0683),
Yunnan Provincial Key Laboratory Construction Plan Funding of
Universities and Yunnan Provincial Engineering Research
Center Construction Plan Funding of Universities for their
financial support.
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There are no conflicts to declare.
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