Ru(ii)-catalyzed amidation reactions of 8-methylquinolines with azides via C(sp3)-H activation

Article abstract of DOI:10.1039/c5cc06230f

Ru(ii)-catalyzed amidation reactions of 8-methylquinolines with azides have been developed. They are the first examples of [(p-cymene)RuCl₂]₂-catalyzed C(sp³)-H bond intermolecular amidation reactions which give quinolin-8-ylmethanamines under mild reaction conditions in good yields.

Full text of DOI:10.1039/c5cc06230f

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COMMUNICATION
Ru(II)-Catalyzed Amidation Reactions of 8-Methylquinolines with Azides via
C(sp3)−H Activation†
Bingxian Liu,a Bin Li,a and Baiquan Wang*,a,b,c
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
The Ru(II)-catalyzed amidation reactions of 8-methylquinolines with azides have been developed. It
is the first example of [(p-cymene)RuCl2]2-catalyzed C(sp3)−H bond intermolecular amidation
reaction which give quinolin-8-ylmethanamines under mild reaction conditions in good yields.
Nitrogen widely exists in natural products, bioactive
10 compounds and materials.1 In the context of synthesis of the 50 higher reactivity and broader substrate scope than the rhodium
C(sp3)−N bond formation reactions of 8-methylquinolines, and
compounds with nitrogen atom, much attention has been paid to
the exploration of efficient and selective C–N bond forming
procedures. In the last decade, with the development of
transition-metal catalysis, great efforts have been made to
15 construct C–N bond via transition-metal catalyzed direct C–H
amination as it alleviates the need for prefunctionalization and is
environmental friendly. A variety of transition-metals,2 such as
palladium,3 rhodium,4 iridium,5 and ruthenium6−8 have been used
to catalyze this kind of reactions. During the last decade,
20 following the pioneering works of Oi and Inoue, Ackermann,
Darses and Genet, Maseras and Dixneuf, and Li,9 easy to prepare
[(arene)RuCl2]2 catalysts became one of the most hot catalysts in
C−H bond functionalizations.10 Despite many significant
achievements include C−C, C−O, and C−X (X = halogen) bond
25 formation have been made, there are only a few works focused on
[(p-cymene)RuCl2]2-catalyzed direct C–H amination reactions.6−8
Sahoo, Chang, Jiao, and Ackermann et al have reported some
important [(p-cymene)RuCl2]2-catalyzed C−H/C−N coupling
reactions, in which azides were used as N atom sources for no
30 oxidant would be required and the only byproduct would be
environmentally benign N2 (Scheme 1).7 However, all the
reported examples are limited to C(sp2)–H bond activation. To
the best of our knowledge, there no C−H amination reaction via
C(sp3)−H bond activation catalyzed by [(p-cymene)RuCl2]2 has
35 been reported up to now. Herein we report the first [(p-
cymene)RuCl2]2-catalyzed C(sp3)−H amidation reaction of 8-
methylquinolines with azides (Scheme 1).
8-Methylquinolines have been proved to have good
cyclometallation ability,11 many transition-metal catalyzed
40 C(sp3)−H bond activation of 8-methylquinoline has been
reported.12 But most of these reactions are catalyzed by palladium,
little work catalyzed by other metals was reported, and even no
report on the use of Ru(II). Our group is continuously interested
in Ru(II)-catalyzed C−H bond activation.13 Meanwhile, we also
45 developed Rh(III)-catalyzed alkenylation and amidation reactions
of 8-methylquinolines.12u,v Ruthenium is not only much cheaper
than rhodium, but also often shows different reactivities from
rhodium.6,10 In this work we have achieved the Ru(II)-catalyzed
catalyst were observed.
Privious works via C(sp2)-H activation
DG
DG
[(p-cymene)RuCl2]2
+
R N3
additive
-N2
NHR
H
By Sahoo, Chang, Jiao, Ackermann, Zhu, Liang, Luo and Ding, Kim
Our present work via C(sp3)-H activation
H
RSO2HN
[(p-cymene)RuCl2]2
N
N
+
RSO2 N3
additive
Mild reaction condition
Single by-product: N2
Up to 89% yield
Scheme 1. [(p-Cymene)RuCl2]2-catalyzed C−H bond amidation reactions
using azides as N atom sources.
55
At the outset of our study, 8-methylquinoline (1a) was chosen
as the model substrate. As shown in Table 1, by treating 1a (0.3
mmol) with 4-(trifluoromethyl)benzenesulfonylazide (2a) (0.6
mmol) in the presence of [(p-cymene)RuCl2]2 (0.015 mmol, 5
mol %) and AgSbF6 (0.06 mmol) in DCE (2 mL) at 80 °C for 12
60 h, no desired product was detected (entry 1). Catalytic amount of
acetate additive always provided
a dramatic improvement
inreaction efficiency.5d,7a−c Thus various acetate ions were
.
screened (entries 3−6), among which Zn(OAc)2 2H2O was most
efficient in leading to good product yield (entry 5). Other solvents
65 were tested in this system giving deficient or negative results
(entries 7−9). Raising the reaction temperature was not effective
in increasing the product yield (entry 10). The less amount of
.
Zn(OAc)2 2H2O (25 mol%) yielded a poor amount of 3aa (entry
11). By changing the ratio of 1a:2a, we were pleased to observe
70 that higher yield was obtained with two equivalents of 1a being
used (entries 16−18). Finally, we chose the reaction condition of
entry 18 as the standard conditions.
With the optimal reaction conditions in hand, various
substituted 8-methylquinolines (1a−p) were treated with an azide
75 (2a) and the corresponding C(sp3)-amidated products (3aa−na)
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

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Page 2 of 4
Table 2 Substrate Scope of 8-Methylquinolinesa
Table 1 Optimization of Reaction Conditionsa
H
View Article Online
DOI: 10.1039/C5CC06230F
[(p-cymene)RuCl2]2
O
S
N
AgSbF6
Ar SO2N3
HN
Ar
additive
solvent, temp
N
O
Ar = 4-CF3C6H4
1a
2a
3aa
Entry
Additive (50%)
Solvent 1a:2a
Yield (%)
1
2
3
4
5
6
7
8
no additive
no [Ag] and additive
AgOAc
Cu(OAc)2⋅H2O
Zn(OAc)2⋅2H2O
Zn(CF3SO3)2
Zn(OAc)2⋅2H2O
Zn(OAc)2⋅2H2O
DCE
DCE
DCE
DCE
DCE
DCE
CH2Cl2 1:1
THF
t-
AmOH
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
1:1
1:1
1:1
1:1
1:1
1:1
n.r.
n.r.
16
16
51
n.r.
22
23
1:1
9
1:1
n.r.
Zn(OAc)2⋅2H2O
10b
11
1:1
1:1
1:1
1:1
1:1
1:1
1:2
1.5:1
2:1
3:1
44
40
49
44
46
51
41
59
61
61
Zn(OAc)2⋅2H2O
Zn(OAc)2⋅2H2O 25%
Zn(OAc)2⋅2H2O 75%
Zn(OAc)2⋅2H2O
Zn(OAc)2⋅2H2O
Zn(OAc)2⋅2H2O
Zn(OAc)2⋅2H2O
Zn(OAc)2⋅2H2O
Zn(OAc)2⋅2H2O
Zn(OAc)2⋅2H2O
12
13c
14d
15e
16
17
18
19
aConditions: 1 (0.6 mmol), 2a (0.3 mmol), [(p-cymene)RuCl2]2 5 mol %,
AgSbF6 20 mol %, Zn(OAc)2⋅2H2O 50 mol %, DCE 2 mL, at 80 °C for 12
h, under Ar, isolated yield.
aConditions: 1a or 2a (0.3 mmol), [(p-cymene)RuCl2]2 5 mol %,
AgSbF6 20 mol %, additive 50 mol %, solvent 2 mL, at 80 °C for 12 h,
under Ar, isolated yield. bTemp 120 °C. c6 h. d24 h. eSolvent 3 mL.
35
Table 3 Sulfonyl Azide Scope a
were obtained in moderate to good yields (Table 2). When 5-
substituted or 7-substituted substrates reacted with 2a, higher
yields were obtained with electron-withdrawing groups (3ea, 3ka,
and 3na) than that with electron-donating groups (3ba and 3la).
When the substituent groups were located at the 6-position, the
electronic effect is not obvious. Both of electron-rich and
5
10 electron-deficient substrates (1f−j) gave moderate to good yields
(55−82%). It is noteworthy that 6-OMe substrate (1g) and 7-OMe
substrate (1l) with strong electron-rich group both can give the
desired products which are not effective in the Rh(III) system.12v
The effect of steric hindrance was also investigated. When 8-
15 methylquinoline was replaced by 8-ethylquinoline (1o) or
quinolin-8-ylmethyl acetate (1p), no product was detected
probably due to the steric effect of the substrate.
In addition to 2a, different sulfonyl azides were also tested
under the standard reaction conditions (Table 3). All the para-,
20 ortho-, and meta-substituted arenesulfonylazide substrates with
electron-withdrawing groups provided good yields (3ea, 3ee, 3ef,
and 3eg). Compared with the substrates of 8-methylquinolines,
azides bearing electron-donating groups also afforded the
corresponding products in high yields (3eb and 3ec). Besides the
25 arenesulfonylazides, aliphatic sulfonyl azides (2h and 2i) were
also viable to give the desired products in moderate to good
yields.
aConditions: 1e (0.6 mmol), 2 (0.3 mmol), [(p-cymene)RuCl2]2 5 mol %,
AgSbF6 20 mol %, Zn(OAc)2⋅2H2O 50 mol %, DCE 2 mL, at 80 °C for 12
h, under Ar, isolated yield.
To gain more insight to the mechanism of this reaction, KIE
(kinetic isotope effect) experiments were performed in two
30 independent reactions (Scheme 2). The KIE was found to be
kH/kD = 1.9, indicated that the cleavage of the methyl C−H bond
may be involved in the rate-determining step.
Based on the known Ru(II)-catalyzed C(sp2)−H bond
40 amidation reactions,7 a possible mechanism is proposed for the
present catalytic reaction (Scheme 3). The first step is likely to be
a C(sp3)−H activation process affording a five-membered
2
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 3 of 4
ChemComm
CH3
CF3
H
H
D
Standard
condition
N
N
O
S
+
HN
CF3
View Article Online
N
N
O
DOI: 10.1039/C5CC06230F
SO2N3
CF3
CD3
D
Standard
condition
O
S
+
DN
CF3
O
SO2N3
kH/kD = 1.9 (1H NMR)
Scheme 2. The KIE experiments.
1/2 [(p-cymene)RuCl2]2
Scheme 4. Utility and derivatization reactions of 3.
(p-cymene)RuCl2
NHR
N
OAc− AgSbF6
N
[(p-cymene)Ru(OAc)]+[SbF6]−
35
The authors wish to thank the National Natural Science
Foundation of China (Grant Nos. 21372122, 21372121, and
21421062) for financial support.
A
−
HOAc
HOAc
(p-cymene)
(p-cymene)
Ru
Ru
−
−
Notes and references
SbF6
R
SbF6
N
N
N
[a] State Key Laboratory of Elemento-Organic Chemistry, College of
40 Chemistry, Nankai University, Tianjin 300071, P. R. China. Phone/Fax:
+86 (22) 23504781, E-mail: bqwang@nankai.edu.cn.
[b] Collaborative Innovation Center of Chemical Science and
Engineering, Tianjin 300071, P. R. China
[c] State Key Laboratory of Organometallic Chemistry, Shanghai
45 Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai
200032, P. R. China
† Electronic Supplementary Information (ESI) available: Full
experimental details, characterization and NMR spectra of the target
products are provided. See DOI: 10.1039/b000000x/
50
B
E
(p-cymene)
SbF6
R
−
(p-cymene)
Ru
N
Ru
R
N
N2
N
N
R
−
N
N2
SbF6
N2
C
D
5 Scheme 3. Proposed mechanistic pathway of the amidation reaction.
1
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intermediate C. The sulfonamido moiety of intermediate C
subsequently inserts into the Ru−C bond directly or involving a
Ru(IV)−nitrenoid intermediate D to form intermediate E. Finally,
10 protonolysis of E delivers the desired product.
55
Quinolin-8-ylmethanamine was reported to be a building
block in enormous areas involved in medicinal chemistry, organic
synthesis, and analytical chemistry.14 Its derivatives have been
studied for their medicinal properties, as exemplified by the
15 potent and selective melanin concentrating hormone (MCH)
antagonists.14a They are also building blocks in inorganic
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NaBH4/NiCl2⋅6H2O, giving the product with exposed amino
group (Scheme 4).15,12v
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25
In conclusion, we have developed a Ru(II)-catalyzed
amidation reaction of 8-methylquionlines with azides to achieve
quinolin-8-ylmethanamine derivatives in good yields. This is the
first [(p-cymene)RuCl2]2-catalyzed amidation reaction of
C(sp3)−H bond with azides. Further applications of this method in
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