Copper(II)-Catalysed Aerobic Oxidative Coupling of Arylamines with Hexafluoroisopropanol: An Alternative Methodology for Constructing Fluorinated Compounds

Article abstract of DOI:10.1002/adsc.202001048

The selective functionalisation of arylamine derivatives with hexafluoroisopropanol through copper(II)-catalysed aerobic oxidative coupling was developed to generate various fluoroalkylated arylamines under mild conditions. This method has a wide substrat

Full text of DOI:10.1002/adsc.202001048

Title: Copper(II)-Catalysed Aerobic Oxidative Coupling of Arylamines
with Hexafluoroisopropanol: An Alternative Methodology for
Constructing Fluorinated Compounds
Authors: Liangying Wu, Yang Song, Zhanchong LI, Jiabao Guo, and
Xiaoquan Yao
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202001048
Link to VoR: https://doi.org/10.1002/adsc.202001048

10.1002/adsc.202001048
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Copper(II)-Catalysed Aerobic Oxidative Coupling of
Arylamines with Hexafluoroisopropanol: An Alternative
Methodology for Constructing Fluorinated Compounds
Liangying Wua, Yang Songa, Zhanchong Lia, Jiabao Guoa, and Xiaoquan Yaoa*
a
Department of Applied Chemistry, College of Material Science and Technology, Nanjing University of Aeronautics
and Astronautics, Nanjing 210016, PR China
Fax: +86-25-52112626; E-mail: yaoxq@nuaa.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201
oxidant (Scheme 1a).[13] Even more recently, the
Abstract. The selective functionalisation of arylamine
derivatives with hexafluoroisopropanol through copper(II)- copper-catalysed coupling of HFIP with indole
catalysed aerobic oxidative coupling was developed to
generate various fluoroalkylated arylamines under mild
conditions. This method has a wide substrate scope with
excellent functional group tolerance and provides the
fluorinated products in good to excellent yields.
Furthermore, preliminary studies indicate that this reaction
occur via a radical mechanism. This protocol, which uses
atmospheric O2 as an oxidant, provides an alternative green
route for constructing fluorinated compounds.
derivatives was reported (Scheme 1b), which was
proposed to proceed via the formation of
hexafluoroacetone and a subsequent Friedel–Crafts
reaction.[14]
Keywords: Copper(II) catalysis; Fluorination; Aerobic
oxidative coupling; Arylamines; Hexafluoroisopropanol
The introduction of a fluorine atom into organic
molecules can greatly change their physical and
chemical properties and even their biological
activities.[1] In particular, many clinical drugs are
organofluorine compounds because of their specific
physiological activities.[2] Furthermore, fluorinated
compounds could also be utilised for the development
of new materials.[3–5]
Metal-catalysed C–X bond fracture is an efficient
strategy for generating free radicals. Over the past
decade, a considerable number of fluorine reagents
have been reported for constructing fluorinated
compounds via such a radical process.[6–11] However,
producing carbon radicals by breaking a C–H bond
would provide a green alternative for synthesising
fluorinated compounds.
Currently, only a few fluorine sources are known to
proceed through C–H bond fracture to generate a
carbon radical. Therefore, it is necessary to discover
new fluorine sources. Hexafluoroisopropanol (HFIP),
which is typically utilised as a polar solvent, also
shows promise as a fluorinated substrate.[12] Recently,
Zhang and co-workers reported the cobalt-catalysed
selective functionalisation of aniline derivatives with
HFIP as fluorinated reagent in the presence of
stoichiometric O-(benzoyloxy)piperidine as an
Scheme 1. Methods for synthesising hydroxyhexafluoro-
isopropyl arylamines.
Herein, we report a novel strategy for the coupling
reaction with HFIP. Using Cu(OTf)2–2,2′-bipyridine
(bpy) as a catalyst, the aerobic oxidative coupling of
arylamines with HFIP was realized under atmospheric
oxygen at 50 °C. Under these mild conditions,
excellent regioselectivity and functional group
tolerance were observed and good to excellent yields
were achieved (Scheme 1c).
The coupling reaction of N-isopropylaniline (1d)
and HFIP was selected as a prototype optimise the
reaction conditions, as summarised in Table 1.
According to previous reports, a single-electron
oxidation (SEO) process, which was proposed as the
key step in the reaction of Zhang and co-workers,[13]
can also be initialised using a copper catalyst and an
1
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10.1002/adsc.202001048
Advanced Synthesis & Catalysis
oxidant.[15] Thus, various copper salts were scanned such as Li2CO3 and K2CO3, were screened, but they
under atmospheric oxygen with Na2CO3 as an were inferior to Na2CO3 (entries 14–18). Base-free
additive (entries 1–10, Table 1).
conditions were also tested, but the yield of 3d was
only 28% (entry 19). In addition, the reaction was
carried out in air, but only a trace amount of coupling
product was observed (entry 20). When the
concentration of N-isopropylaniline was decreased
from 0.1 to 0.08 M by dilution with HFIP, the yield of
3d increased to 87% (entry 21).
Table 1. Optimisation of reaction conditionsa)
To further improve the reaction, a ligand was
introduced. Surprisingly, the combination of
Cu(OTf)2 (5 mol%) and bpy (2.5 mol%) gave the best
result, with a yield of 95% at a slightly prolonged
reaction time of 3.5 h, whereas the conventional ratio
between a copper salt and a bidentate ligand (1:1)
gave a much worse result (entry 22 vs. entry 23).
Furthermore, with 1,10-phenanthroline as the ligand,
the yield of 3d was only 78% (entry 24). Moreover,
various N-monodentate ligands, such as pyridine,
lutidine, and their derivatives were screened (Table
S1), but their catalytic activities were inferior to that
obtained with the combination of Cu(OTf)2 and bpy.
Thus, the optimal conditions were determined to be 5
mol% Cu(OTf)2, 2.5 mol% bpy, 0.3 equiv of Na2CO3,
and 0.2 mmol of arylamine in 2.5 mL of HFIP at
50 °C under an oxygen atmosphere.
Entry Catalyst
Base
Time Yield
(h)
3
(%)b)
45
1
CuSO4·5H2O
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
2
Cu(NO3)2·3H2O
Cu(acac)2
CuCl2·H2O
CuBr2
3
32
3
3
3
3
3
3
3
3
3
3
21
4
5
59
N.D.
53
6
7
Cu(CF3COO)2
Cu(OTf)2
CuCl
66
8
50
50
9
CuBr
10
11c)
12
13
14
15
16
17
18
19
20d)
21e)
22f)
CuI
Trace
Trace
79
Cu/C3N4
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2/bpy
(1:1)
Cu(OTf)2/bpy
(2:1)
Cu(OTf)2/1,10-
Phen
Na2CO3 2.5
Na2CO3
Li2CO3
K2CO3
NaOH
2
68
Subsequently, a series of secondary arylamines
were explored under the optimised reaction conditions
(Table 2). For N-alkyl anilines (3a–3e), bulky
substituents on nitrogen seemed to favour the reaction,
and 3d was obtained in 95% yield with N-
isopropylaniline as the substrate. The structure of 3e
was further confirmed by single-crystal X-ray
analysis (for details, see the Supporting
Information).[16] Notably, only para-substituted
products were observed, which indicated that the
reaction proceeded in a highly regiospecific manner.
Ortho-substituted N-alkyl anilines were also
investigated. Only moderate yields were obtained
with N-methyl aniline derivatives (3f–3i), whereas N-
ethyl-2-methylaniline gave the corresponding product
in good yield (3i). Interestingly, when the para-
position on the benzene ring of the aniline was
2.5
2.5
2.5
74
71
66
NaHCO3 2.5
NaOAc
--
Na2CO3 2.5
Na2CO3 2.5
Na2CO3 3.5
24
2.5
2.5
56
28
Trace
87
56
23g)
Na2CO3 3.5
Na2CO3 3.5
95
78
24h)
a)
Reaction conditions: 1d (0.2 mmol), HFIP (2, 2 mL),
base (0.3 equiv), and O2 (1 atm) in a Schlenk tube at 50 °C
occupied,
no
reaction
occurred
(3j–3l).
b)
c)
for 3 h. Isolated yields. Under irradiation by white or
Tetrahydroquinoline derivatives were also examined
in the oxidative coupling reaction, and the 4-
substituted products were isolated in 63%–76% yield
as the only isomer (3m–3o).
d)
blue light. The reaction was carried out in air. e) In 2.5
f)
g)
mL of HFIP. 5 mol% bpy was added as a ligand.
5
h)
mol% of Cu(OTf)2, 2.5 mol% bpy.
phenanthroline. N.D.: No product was detected.
2.5 mol% 1,10-
Moreover, the reaction also proceeded in moderate
yields with N-allyl, N-benzyl aniline and its
heteroaromatic analogues (3p–3s). With various
diarylamine substrates, 3t–3w were obtained
regiospecifically in moderate to good yields.
Furthermore, even with a hydroxyl group-containing
aniline substrate, a 71% yield was achieved (3x).
Next, various tertiary arylamine substrates were
investigated under the optimised reaction conditions
(Table 3). Tertiary anilines, such as N,N-
To our delight, the reaction proceeded in the
presence of most of the copper salts (copper(I) or
copper(II)) to give yields of ~20%–70%. Among the
investigated salts, Cu(OTf)2 gave the best result (entry
7). A nanometric semiconductor material, Cu/C3N4,
was also applied as a catalyst under blue or white
light irradiation. However, only a trace amount of
product was formed (entry 11).
diethylaniline,
1-phenylpiperidine,
1-
With Cu(OTf)2 as the catalyst, the reaction time
was shortened, and a yield of 79% was achieved after
2.5 h (entries 12 and 13). Subsequently, various bases,
phenylmorpholine, and N-phenylpyrrolidine, gave the
corresponding products in good yields (5a–5d). With
2
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10.1002/adsc.202001048
Advanced Synthesis & Catalysis
N-methyltetrahydroquinoline as a substrate, desired
product 5e was generated in 72% yield.
Furthermore, to illustrate the practicality of this
approach, a gram-scale reaction was performed with 5
mmol (0.675 g) of N-isopropylaniline (Scheme 3).
Under the standard conditions, product 3d was
isolated in 87% yield (1.31 g).
Table 2. Screening of secondary aromatic amines.a)
Table 3. Screening of tertiary aromatic amines.a)
a)
Reaction conditions: 4 (0.2 mmol), HFIP (2, 2.5 mL),
Cu(OTf)2 (5 mol%), bpy (2.5 mol%), and Na2CO3 (0.3
equiv) under O2 at 50 °C for 3.5 h. Isolated yield. b) 30 min.
Scheme 2. Coupling reactions with a) aniline and b) N-
phenylpyrrole as substrates.
Scheme 3. Gram-scale preparation of 3d
.
a)
Reaction conditions:
1 (0.2 mmol), HFIP (2, 2.5
mL), Cu(OTf)2 (5 mol%), bpy (2.5 mol%), and
Na2CO3 (0.3 equiv) under O2 at 50 °C for 3.5 h.
Isolated yield. b) 30 min.
In addition to the substituted anilines above, aniline
(6) and N-phenylpyrrole (8) were also tested as
substrates for the coupling reaction. Although aniline
was inert to the reaction (Scheme 2a), to our surprise,
N-phenylpyrrole gave 9, which was fluorinated at the
para-position of the benzene ring, as the only product
in 72% yield (Scheme 2b).
Scheme 4. Reaction of 1d in hexafluoroacetone and HFIP
under a N2 atmosphere.
3
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10.1002/adsc.202001048
Advanced Synthesis & Catalysis
To explore the mechanism of the oxidative
coupling reaction, various control experiments were
designed. For the reaction of 1d, when a mixture of
HFIP and hexafluoroacetone (1:1, v/v) was utilised as
the solvent under a N2 atmosphere, the yield of 3d
was only 14% (Scheme 4a). Under the same
conditions, pure HFIP gave 3d in 15% yield (Scheme
4b).
We also tracked the standard reaction between 1d
and HFIP using 19F NMR spectroscopy. After
reaction for 1, 2, and 3.5 h, all the observed signals
corresponded to 3d and HFIP, and no other species
were observed (see S1.4 in the Supporting
Information). Thus, based on the results of both these
experiments, hexafluoroacetone might be irrelevant in
the current reaction.
Furthermore, a radical trap experiment was carried
out. When TEMPO (2 equiv) was added as a radical
scavenger under the standard conditions, the reaction
of 1d and HFIP was completely suppressed and the
formation of target product 3d was not observed (for
details, see S1.5 in the Supporting Information). This
result, which differed from that observed for the
copper-catalysed coupling reaction of HFIP and
indole derivatives,[14] suggested that the reaction
might involve a radical process.
To further explore the mechanism of the current
reaction, the reaction of 1a and HFIP was investigated
in detail. As shown in Table 2, an interesting anomaly
in the yield is observed when N-methylaniline (1a) as
the substrate is contrasted with other N-alkylanilines,
as 3a was only isolated in 62% yield (3a vs. 3b–3e).
The reaction mixture also contained ~20% of by-
product 10 (Scheme 5), which is believed to form via
an SEO process. In this process, an N-methylaniline
cation radical (intermediate A, Scheme 6) is generated,
which then undergoes a multistep conversion process
to generate a diphenylmethane derivative (10) as the
final product (Path A, Scheme 6).[17]
Scheme 6. Proposed reaction mechanism.
Simultaneously, O2 is reduced by the Cu(I) species
to generate a superoxide radical anion. Subsequently,
following the transfer of a single electron from HFIP
(2) to the superoxide radical anion, radical D and
-
HO2 are formed.[18] Finally, desired product 3a is
formed via radical–radical coupling between C (or C′)
and D.
Moreover, it is also possible for radical D and
aniline to form sigma-complex F, which could
undergo an SEO process followed by deprotonation to
give final product 3a (Path C, Scheme 6).[13]
In conclusion, we have developed
a
new
methodology for constructing fluorinated compounds
via the copper-catalysed selective coupling of
arylamines and hexafluoroisopropanol under mild
conditions in an oxygen atmosphere. This aerobic
oxidative coupling reaction provided the desired
products in good to excellent yields and exhibited
good substrate tolerance, excellent functional group
compatibility, and high regioselectivity. Further
studies to elucidate additional mechanistic details and
to apply this strategy to other fluorination reactions
are ongoing in our laboratory.
Scheme 5. Products isolated from the reaction of 1a and
HFIP
Experimental Section
Thus, based on the above experimental results and
previous reports,[13,17,18] we proposed a plausible
pathway for the oxidative coupling reaction, which is
also initialised by an N-methylaniline cation radical
(Path B, Scheme 6).
First, with a Cu(II) species as the oxidant, N-
methylaniline 1a is oxidised to give radical cationic
species A and a Cu(I) species via an SEO process.[13,15]
Then, through electron transfer and the release of a
proton, which is promoted by the base additive,
radical intermediate C, which might tautomerize to C′,
is formed.
All chemicals and solvents were purchased from
commercial sources and used without any purification.
General procedure for copper(II)-catalysed synthesis of
hydroxyhexafluoroisopropyl arylamines
N-isopropylaniline (1d, 27 mg, 0.2 mmol), HFIP (2, 2.5
mL), Na2CO3 (6.36 mg, 0.3 equiv), Cu(OTf)2 (3.61 mg, 5
mol%), and bpy (0.78 mg, 2.5 mol%) were added into a 25
mL Schlenk tube and stirred at 50 °C for 3.5 h under an O2
atmosphere. The reaction mixture was cooled to room
temperature and excess HFIP was removed by rotary
4
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10.1002/adsc.202001048
Advanced Synthesis & Catalysis
evaporation. The residue was then purified by flash column
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chromatography
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silica
gel
(petroleum
ether/dichloromethane = 1:2, v/v) to give the desired
product (3d) in 95% yield (57.2 mg).
The detailed characterisation data for compounds 3, 5, 9,
and 10 are provided in the Supporting Information.
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Acknowledgements
We are grateful for financial support from the National Natural
Science Foundation of China (21772091 to XY). This is a project
funded by the Priority Academic Program Development of
Jiangsu Higher Education Institutions.
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6
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Advanced Synthesis & Catalysis
UPDATE
Copper(II)-Catalysed Aerobic Oxidative
Coupling of Arylamines with
Hexafluoroisopropanol: An Alternative
Methodology for Constructing Fluorinated
Compounds
Adv. Synth. Catal. Year, Volume, Page – Page
Liangying Wu, Yang Song, Zhanchong Li, Jiabao
Guo, Xiaoquan Yao*
7
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