Halogenations of substituted 2-alkylquinoline with iodine and halide exchange with AgF2

Article abstract of DOI:10.1039/c6ra17410h

Halogenations of substituted 2-alkylquinoline with iodine and halide exchange with AgF₂ have been developed. These processes provide facile strategies to construct C-I/F bonds, and expand the methods of fluorination of 2-alkylquinolines. These transformations exhibit good tolerance of functional groups and generate the desired products in moderate to good yields.

Full text of DOI:10.1039/c6ra17410h

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DOI: 10.1039/C6RA17410H
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Halogenations of Substituted 2-Alkylquinoline with iodine and
Halide Exchange with AgF2
Received 00th January 20xx,
Accepted 00th January 20xx
Xiaobo Pang, Likui Xiang, Jianxin Ma, Xiaodong Yang, and Rulong Yan*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Halogenations of substituted 2-alkylquinoline with iodine and
halide exchange with AgF2 have been developed. These
processes provide facile strategies to construct C-I/F bond,
and expand the methods of fluorination of 2-alkylquinolines.
These transformations exhibit well tolerance of functional
groups and generate the desired products in moderate to
good yields.
Organic molecules containing halogenated functional groups
are recognized as crucial class of scaffolds, which are widely
appilied in pharmaceutical chemistry, agrochemistry and
functional material science.1-2 In addition, organohalogen
compounds are also used as synthetic precursors for organic
synthesis.3 In view of these benefits, the development of
carbon-halogen bonds formation have attracted substantial
interests and received enormous progresses during the past
several years.4-5 Particularly, organic molecules containing
fluorine atoms have emerged as star products in many fields
Scheme 1. C-I/F bonds formation
6
due to the unique characteristics of carbon-fluorine bond,
such as steric size effect, strong bond energy, change of
lipophilicity, hydrogen bond acceptor, biological activity and
22
Buchwald,20 Nguyen,21 Gouverneur
et al. have
contributed greatly to the transition-metal-catalyzed C-F bond
high electronegativity. As consequence, continuous efforts formation. Another important progress has also been
have been devoted for the fluorination in the past several
decades, as a rule, there are three general strategies for the
investigated in the formation of C-F bonds based on the direct
halide exchange. For instance, in 2012, Hartwig’s group
reported a new strategy of copper-mediated fluorination of
7
construction of carbon-fluorine bond: nucleophilic,
9
electrophilic, 8 and radical fluorination. And more recently,
23
25
aryl iodides
respectively reported the fluorination of alallylic halides by
using Et3N HF and (Ph3P)3CuF as the fluorine sources in the
(Scheme 1, entry A). Liu24 a a
success in this area can be attributed to the development of
various efficient transition-metal catalysts, such as Pd,10 Cu,11
Ag,12 Au,13 which have been employed widely in the
construction of C-F bond processes. Li,14 sanford,15 Furuya,16
·
same year (Scheme 1, entry B). In contrast to recent
conspicuous progress in formation of aromatic C(sp2)-F bond,26
the strategies of benzylic C(sp3)-F bond construction of 2-
alkylquinolines are relatively limited.27 Therefore, the
development of briefness methods to construction of C(sp3)-F
bond of 2-alkylquinolines are very desirable and useful.
Hu,17
Ribas,18
Doyle,19
State Key Laboratory of Applied Organic Chemistry, Key laboratory of Nonferrous
Metal Chemistry and Resources Utilization of Gansu Province, Department of
Chemistry, Lanzhou University, Lanzhou, China.
Fax: 0931-8912596 E-mail: yanrl@lzu.edu.cn
Electronic Supplementary Information (ESI) available: Experimental procedures,
spectroscopic data. See DOI: 10.1039/c000000x/
To our best knowledge, we found there was very few
available literature concerning the methods of C(sp3)-I/F bonds
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Table 1. Screening of Reaction Conditions for the Iodination of Table 2. Iodination of Substituted 2-Alkylquinolines a
View Article Online
DOI: 10.1039/C6RA17410H
2-Methylquinoline a
Entry
Iodination
reagent
Additive
(10 mol%)
Base
Solvent Yield
(%)b
1
2
3
I2
I2
I2
-
NaHCO3
NaHCO3
NaHCO3
THF
THF
THF
33 c
51 c
n.r.c
PPh3
1.10-
Phenanthr
oline
4
I2
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
K2CO3
THF
THF
THF
THF
THF
THF
THF
DCE
77
34 d
5
I2
e
6
TBAI/TBHP
-
7
NIS
I2
trace
8
-
9
I2
Na2CO3
NaOH
-
10
11
12
I2
48
65
I2
NaHCO3
NaHCO3
NaHCO3
I2
toluene 51
THF
72 f
13
I2
a
Reaction conditions: 1a (0.30 mmol), Iodination reagent (1.5
o
equiv.), NaHCO3 (1.5 equiv.), PPh3 (10 mol%), THF (2 mL), 120 C,
under N2. b Isolated yields. c Reaction temperature was 100 oC.
d
Reaction temperature was 140 oC. TBHP (1.5 equiv). The
e
f
amount of I2 and NaHCO3 was increased to 2.0 equiv.
construction of 2-alkylquinolines and their derivatives.28
Inspired by the previous works, herein, we had developed
facile methods for C(sp3)-I/F bonds formation of substituted 2-
alkylquinolines with iodine and halide exchanging by AgF2
(Scheme 1).
Firstly, 2-methylquinoline 1a was used as the model
substrate to start our research. The expected product 2-
(iodomethyl)quinoline 2a was isolated in 33% yield when the
reaction was conducted with I2 (1.5 equiv.) and NaHCO3 (1.5
o
equiv.) in THF at 100 C under N2 for 1.5 h (entry 1, Table 1).
a Reaction conditions: 1 (0.30 mmol), I2 (1.5 equiv.), NaHCO3 (1.5 equiv.), PPh3
(10 mol%), THF (2 mL), 120 oC, under N2, 1.5 h. b Reaction conditions: 1 (0.3 0
Encouraged by this initial result, we subsequently assessed
Lewis bases as additives to improved the yield of this reaction
(entry 2-3, Table1), PPh3 promoted this reaction efficiently and
the yield increased to 51%. The reaction temperature was also
screened, 120 oC had been proven to be the efficient
temperature in this process (entry 4-5, Table1). Then several
iodination reagents, such as tetrabutylammonium iodide (TBAI)
and N-iodosuccinimide (NIS), were evaluated and only trace 2a
were detected (entry 6-7, Table1). Other bases were also
examined, lower yields of 2a were obtained (entry 8-10,
Table1). Changing the solvent and the equivalent of I2 did not
improve the yields (entry 11-13, Table 1). Consequently, the
optimized reaction conditions should be proceeded with I2 (1.5
equiv.), NaHCO3 (1.5 equiv.) and PPh3 (10 mol%) in THF at 120
oC .
.
mmol), I2 (1.2 equiv.), TBHP (2.0 equiv.) and THF (2 mL), 120 oC, under N2
With the optimized reaction conditions in hand, the scope of
substituted 2-alkylquinolines was examined and the results
were summarized in Table 2. A wide series of substrates were
tolerated in this transformation and gave desired products in
moderate yields. Obviously, substituted 2-alkylquinolines with
electron-donating groups, such as methyl and alkoxy groups,
generated the iodination products in moderate yields.
Nevertheless, the substrates with electron-withdrawing groups
of fluorine, chlorine and bromine needed longer reaction time
and failed to give ideal yields except these groups at C7
2 | J. Name., 2012, 00, 1-3
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Table 3. Reaction Conditions for the Fluorination of 2- Table 4. Fluorination of Substituted 2-Methylquinoline a
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DOI: 10.1039/C6RA17410H
Methylquinoline a
Entry
Fluorination reagent.
Solvent
DMF
Yield(%)b
1c
2
AgF
AgF2
AgF2
AgF2
AgF2
AgF2
AgF2
AgF2
AgF2
31
54
43
51
51
65
-
DMF
3d
4
DMF
DMF
5
CH3CN
DCE
6
7
THF
8
toluene
DMSO
89
trace
9
a
Reaction conditions: 2a (0.30 mmol), AgF2 (1.2 equiv.), toluene
(1.5 mL) at 80 oC under N2, 16 h. Isolated yields. Reaction
b
c
temperature was 120 oC. d Reaction temperature was 40 oC.
position (2j, 2l). 3-Methylbenzo[f]quinoline 1o was employed
for this process under the standard conditions and product 2o
was isolated in 68% yield. In addition, substrates 1p, 1q and 1r
displayed better compatibility and gave desired products in
moderate yields. Unfortunately, the benzylic C(sp3)-H of 1s and
1t could not be activated and give the unexpected products 2s
and 2t. 2-methylpyridine 1u and substrate 2v were also failed
to give the desired product.
a Reaction conditions: 2a (0.30 mmol), AgF2 (1.2 equiv.), toluene (1.5 mL) at
80 oC under N2, 16 h.
In view of the importance of fluorination, we expected that
the halide exchange of 2a would be an ideal method for
specific position C-F bond formation. To probe the viability of
this approach, we started our research with the reaction of 2a
As shown in Table 4, substrate 2o was also tolerated in this
process and the target compound 3o was obtained in excellent
yield. When 2-(1-iodoethyl)quinoline 2p and 4-iodo-1,2,3,4-
tetrahydroacridine 2r reacted with AgF2 under the optimized
conditions, the desired products 3p and 3r were afforded in
moderate yields. Additionally, Substrate 2q failed to give
o
and AgF in DMF at 120 C. To our delight, the desired product
2- (fluoromethyl)quinoline 3a was obtained in 31% yield (entry
1, Table 3). The yield was increased to 54% when AgF2 was
used as fluoride reagent (entry 2, Table 3). Further
optimization of solvents demonstrated that toluene was the
target product 3q
.
In order to gain further information about the reaction
efficient solvent (entry 4-9, Table 3). After screening other mechanism, several control experiments were set up. First, to
parameters such as reaction temperature and time, the determine whether 2-methylquinoline 1a rendered into 2-
optimized reaction conditions should be performed in the (iodomethyl)quinoline 2a through a sequence of radical
presence of AgF2 in toluene at 80 oC for 16 h.
Under the optimized reaction conditions, we then
proceeded to investigate the scope of 2-(iodoalkyl)quinolines
pathway in this transformation, radical scavengers 2,2,6,6,-
tetramethylpiperidyl-1-oxyl (TEMPO) and 2,6-di-tert-butyl-4-
methylphenol (BHT) were respectively performed with 2-
methylquinoine 1a under the standard conditions (Scheme 2,
entry A), the corresponding product 2a were separately
isolated in 71% and 53% yields, which ruled out that the
iodination process might proceed through a radical pathway.
Then, further experimental study was carried out to confirm
the mechanism for fluorination of 2a. TEMPO was added into
(Table
4).
To
our
delight,
various
substituted
iodoalkylquinolines reacted with AgF2 well and generated the
desired products in moderate to high yields. In this process,
the presence of electron-donating and electron-withdrawing
groups had very little influence on this transformation (3a-3n).
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the reaction system of (iodomethyl)quinoline 2a and AgF2 in Acknowledgment This work was supported by National
toluene at 80 oC under N2, and gave the corresponding product Natural Science Foundation of China (2D1O6I7:2100.81063V,9ie/2wC1A62rRt0iAc2l1e70O46n17l0inH)e,
3a in 85% yield (Scheme 2B), which indicated that the Gansu Province Science Foundation for Youths (1606RJYA260)
(iodomethyl)quinoline 2a transformed to the target product 3a and the Fundamental Research Funds for the Central
without a radical procedure. Based on the above experiment Universities (lzujbky-2016-39).
Notes and references
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.
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C
D
went through a
, afforded the
consecutive state of intermediate
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Scheme 3. Proposed Mechanism
In summary, we have developed simple methods of
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DOI: 10.1039/C6RA17410H