Metal-free C-H amination of arene with: N -fluorobenzenesulfonimide catalysed by nitroxyl radicals at room temperature

Article abstract of DOI:10.1039/c9cc02739d

A TEMPO-catalysed direct amination of arene through C-H bond cleavage employing N-fluorobenzenesulfonimide (NFSI) as the amination reagent in good to excellent yields with broad arene scope in the absence of any metal, ligand or additive is reported. Unli

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Metal-free C-H Amination of Arene with N-
Fluorobenzenesulfonimide Catalysed by Nitroxyl Radical at Room
Temperature
Received 00th January 20xx,
Accepted 00th January 20xx
Qi Miao,a Zhong Shao,a Cuiying Shi,a Lifang Ma,a Fang Wang,a Ruoqi Fu,a Haochen Gaoa and Ziyuan
Li*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
A TEMPO-catalysed direct amination of arene through C-H bond
cleavage employing N-fluorobenzenesulfonimide (NFSI) as the
amination reagent in good to excellent yields with broad arene
scope in absence of any metal, ligand or additive is reported. Unlike
previous transition metal-catalysed aminations in which high
reaction temperatures were usually necessary, this novel reaction
at room temperature is the first example of C-H amination with
NFSI that is realised through organocatalysis. Probable mechanism
of this concise amination is also proposed.
(a) Transition metal-catalysed
SO2Ph
C-H amination with NFSI
SO2Ph
SO2Ph
TM
70~100 o
Ar
N
Ar
H
F
N
+
C
SO2Ph
TM
= [Pd]
[Cu]
Zhang Ritter
,
Itami Pan, Lu, Zhang Song
, by
, by
,
,
[Au], by Itami
[Fe] our group
, by
(b) Transition metal-free
C-H amination with NFSI
metal-free
SO2Ph
SO2Ph
SO2Ph
Ar
N
Ar
H
F
N
+
SO2Ph 60~110 o
C
With K2CO3 (cat.)
Oxidant (stoic.)
Yang
Zhang, Hajra
by
by
(c) This work: Nitroxyl radical-catalysed
C-H amination with NFSI
Aminoarenes are among the most privileged scaffolds not only
due to their existence in miscellaneous bioactive molecules1
and functional material,2 but also owing to their broad
application in organic synthesis such as ligands in
organometallic chemistry.3 The introduction of amino groups
on arenes is therefore a very significant transformation in
organic chemistry. Traditionally, aryl C-N bond formation can be
achieved through carbon-halogen bond cleavage in aryl halides,
such as copper-mediated Ullman-type amination or amidation,4
and palladium-catalysed Buchward-Hartwig reaction.5
However, preactivated arene substrates were required in these
reactions. As a concise and atom-economic alternative to such
aminations via carbon-halogen bond cleavage, tremendous
progress in transition metal-catalysed direct amination of
arenes with amines and stoichiometric oxidants through C-H/N-
H cleavages has been witnessed during the past few decades.6
Yet prerequisite directing groups, large excess of arenes, and/or
stoichiometric amount of oxidants limited the wide applications
of these efficient C-H aminations.
SO2Ph
SO2Ph
TEMPO (15 mol%)
25 o
SO2Ph
SO2Ph
Ar
N
Ar
H
F
N
+
C
2
1
SO2Ph
SO2Ph
room temperature
SO2Ph
SO2Ph
F
N
N
A
(
)
F
2
H
1
N
N
O
O
TEMPO
TEMPO+
B
)
(
)
(
,
H
N
H
SO2Ph
SO2Ph
SO2Ph
SO2Ph
N
D
C
( )
(
)
Organocatalytic under mild conditions (at room temperature)
Totally metal-free and additive-free
Broad substrate scope
Scheme 1 C-H aminations of arenes with NFSI
reactions including C-H amination of arenes7-18 and aminative
bisfunctionalization of alkenes19 or alkynes20, since it could
easily generate an electrophilic amino radical through oxidative
addition to transition metals. In 2011, a pioneering work on Pd-
catalysed C-H amination of anilides with NFSI was disclosed by
Zhang group,7 followed by another report by Ritter group8 on
Pd- and Ag-cocatalysed C-N coupling with broader arene scope
including simple benzenes and some heteroarenes at room
temperature. Itami group9 reported a couple of significant
works on copper-catalysed C-H amination of both simple
benzene derivatives and miscellaneous heteroarenes with NFSI.
Such Cu-catalysed C-N couplings with NFSI have also been
reported by Pan,10 Lu,11 Zhang,12 and Song.13 In addition, the
first Au-catalysed and the first Fe-catalysed C-N coupling of
Recently, N-fluorobenzenesulfonimide (NFSI), which was
usually employed as an electrophilic fluorination reagent, has
been broadly used in a variety of aminative functionalization
a. Department of Pharmaceutical and Biological Engineering, School of Chemical
Engineering, Sichuan University, Chengdu 610065, China.
Email: liziyuan@scu.edu.cn; mlfang11@scu.edu.cn
Electronic Supplementary Information (ESI) available: Detailed experimental
procedures, 1H and 13C NMR data and spectra. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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arenes with NFSI have been achieved by Itami14 and our group15, maintained when decreasing the loading of TEMPO to 15 mol%
View Article Online
DOI: 10.1039/C9CC02739D
respectively, along with a Ni-promoted amidation reported by (entry 9), yet it would decline if further decreasing the loading
Wu16. Beside the above examples realised via transition metal of TEMPO to 10 mol% (entry 10) or decreasing the loading of
catalysis (Scheme 1a), transition metal-free aminations with NFSI to 3 eq (entry 12). No aminated product was generated in
NFSI have been achieved in the presence of catalytic amount of the absence of TEMPO, supporting our proposal that this
inorganic base17 or stoichiometric amount of oxidant18 (Scheme amination is enabled by the SET redox cycle of TEMPO (entry
1b). Except for Ritter’s study on the Pd/Ag-cocatalysed 11). Therefore, reactions conditions in entry 9 were selected as
amination,8 all these aminations with NFSI share a common the optimized conditions for this C-H amination.
drawback: high reaction temperatures were necessary,
Table 1 The TEMPO-catalysed C-H animation of azoles with NFSIa
probably due to the good stability of NFSI itself, which required
SO2Ph
H
X
N
SO2Ph
elevated temperatures to cleave its N-F bond to generate the
active amino radical. Therefore, developing more efficient and
environment-benign catalytic approaches to fulfil this C-H
amination with broad arene scope under mild conditions is
challenging but quite valuable.
N
TEMPO (15 mol%)
R1
X
N
SO2Ph
F
N
+
EtOAc (2 mL), 25 o
Ar (1 atm), 24 h
C
R1
COYR2
1a-n
(0.3 mmol)
SO2Ph
COYR2
2a-n
NFSI
SO2Ph
SO2Ph
N
SO2Ph
N
N
O
N
2a
(90%)
O
O
SO2Ph
SO2Ph
SO2Ph
F3C
MeO
N
2c
(51%)
N
2b
(95%)
Nitroxyl radicals, such as 2,2,6,6-tetramethyl-piperidine-1-
oxyl (TEMPO) or its sodium salt (TEMPONa), are environment-
benign and highly stable free radicals,21 which have been widely
used as efficient reagents catalysing or mediating miscellaneous
oxidative organic reactions via single electron transfer (SET)
redox process between TEMPONa and TEMPO, or between
TEMPO and its oxoammonium counterpart (TEMPO+). Notably,
many of these reactions could be realised at low temperatures.
Enlightened by these TEMPO-catalysed or mediated reactions,
we proposed that (Scheme 1c), unlike previous transition metal-
catalysed amination in which an oxidative addition of NFSI to
transition metals at high temperatures provided an imidyl
radical (A, Scheme 1a),9b this radical could alternatively be
generated upon oxidation of TEMPO by NFSI at room
temperature, along with TEMPO+ (B, Scheme 1c),22 followed by
an electrophilic attack of radical A to arene substrate 1, giving
an aryl radical C.9b Subsequently, this aryl radical could be
oxidized by B due to the high reductive tendency of B,23 which
gives an aryl cation D9b and TEMPO,22-23 closing the SET redox
cycle. The aminated product 2 would eventually be obtained
after deprotonation and aromatization.9b
COOMe
COOMe
COOMe
SO2Ph
SO2Ph
N
SO2Ph
N
Cl
N
O
SO2Ph
COOMe
O
O
SO2Ph
SO2Ph
F
Cl
N
N
2e
N
COOMe
COOMe
2d
2f
(79%)
(63%)
(67%)
SO2Ph
SO2Ph
SO2Ph
N
N
N
O
N
O
N
2i
(81%)
SO2Ph
COOMe
O
N
2h
(77%)
SO2Ph
SO2Ph
CONHnBu
CONHEt
2g
(66%)
SO2Ph
SO2Ph
N
SO2Ph
N
OMe
N
S
N
2l
(91%)
S
SO2Ph
S
N
SO2Ph
SO2Ph
Me
N
2k
(81%)
COOMe
COOMe
COOMe
2j
(65%)
SO2Ph
SO2Ph
N
N
S
SO2Ph
COOMe
S
N
SO2Ph
F
N
2m
(62%)
CONHEt
2n
(61%)
a The reaction of azole 1 (0.3 mmol) was performed with NFSI (1.2 mmol)
and TEMPO (0.045 mmol) in EtOAc (2 mL) under argon (1 atm) at 25 oC for
24 h. Isolated yields of 2 after column chromatography on silica gel.
Herein, as an advancement of our previous works on
19i-j
aminative functionalization with NFSI,15,
as well as our
With the optimized conditions acquired, miscellaneous
substituted oxazoles were first explored for this nitroxyl radical-
catalysed C-H amination as shown in Table 1. For 2-
phenyloxazole-4-carboxylate substrates (1a-f), electron-rich
methoxyl-substituted oxazoles provided correspond C5-
aminated products 2a-b in considerably higher yields than
elctron-deficient ones did (2c-f), suggesting that this amination
is probably an electrophilic substitution. However, steric
hindrance showed little impact on this reaction, since the otho-
substituted oxazole 1f provided its aminated product (2f) in an
approximate yield comparing to the para-substituted oxazole
1e did. Beside 2-phenyloxazole-4-carboxylates, this efficient
amination at room temperature could react smoothly on 2-
alkyloxazole and oxazole-4-formamide, giving corresponding
products 2g-i in moderate to good yields. Moreover, thiazole
substrates underwent this facile reaction effectively, providing
C5-aminated thiazoles 2j-n in moderate to excellent yields, and
similar patterns on the influence of electron density and steric
hindrance were also observed.
continuous efforts on transition metal-catalysed C-H
functionalizations,15, 24 we would like to report our recent study
on the metal-free TEMPO-catalysed25 C-H amination of arene
with NFSI as the amino precursor at room temperature (Scheme
1c). To our knowledge, C-H amination of arene with NFSI was
rarely achieved at room temperature, and it has not yet been
realized through organocatalysis.
Our study commenced with the optimization of reaction
conditions for this novel nitroxyl radical-catalysed C-H
amination, using methyl 2-phenyloxazole-4-carboxylate (1a) as
the model substrate15, 24a-g as summarized in Table S1.26 Initially,
the C5-aminated product 3a was obtained in 84% yield when 1a
was treated with 4 eq of NFSI and 40 mol% of TEMPO in 2mL of
o
TCE at 25 C under argon for 12 hours (entry 1), but the yield
declined when the loading of TEMPO was decreased (entry 2).
Then the screening of solvents (entries 3-8) revealed that, when
the reaction time was prolonged to 24 hours, the yield of 3a was
elevated to 88% with 20 mol% of TEMPO in an environment-
benign solvent EtOAc (entry 8). This excellent yield could be
2 | J. Name., 2012, 00, 1-3
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and 1d, or thiophene 3f and 3h (0.25 mmol each) was subjected
to insufficient loadings of NFSI (0.4 mmol), the electron-rich
View Article Online
DOI: 10.1039/C9CC02739D
Table 2 The TEMPO-catalysed C-H animation on miscellaneous arenesa
SO2Ph
SO2Ph
TEMPO (15 mol%)
Ar
H
product 2b and 4f was isolated predominantly, indicating that
this novel nitroxyl radical-catalysed amination with NFSI is an
electrophilic substitution. Meanwhile, when the amination was
conducted with D2O for insufficient reaction time, no deuterium
incorporation was observed either on the recovered substrate
or the amination product (Scheme S2),26 suggesting that the
cleavage of C-H bond in this amination is irreversible.
Interestingly, the value of intermolecular kinetic isotope effect
(KIE) was calculated to be 1.92 (Scheme 2a),26 indicating that
the final deprotonation process might be involved in the rate-
limiting step in this nitroxyl radical-catalysed amination, which
is different from Ritter’s Pd/Ag-cocatalysed amination wherein
the oxidative addition of NFSI to the palladium catalyst is the
rate-limiting step,8 or from Itami’s Cu-catalysed amination
wherein the addition of the imidyl radical to the arene is the
rate-determining step.9 It is rather uncommon that the re-
aromatisation step from D (Scheme 1) should be rate-
determining, and the precise mechanism of this amination
requires further studies. In addition, the sulfonyl groups could
be effectively deprotected with TfOH in DCE while the
vulnerable methyl ester group remained intact (Scheme 2b),26
demonstrating the promising potentials in the application of
this TEMPO-catalysed amination.
F
N
Ar
+
N
EtOAc (2 mL), 25 o
Ar (1 atm), 24 h
C
SO2Ph
SO2Ph
3a-s
(0.3 mmol)
NFSI
4a-s
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
N
SO2Ph
N
N
N
O
SO2Ph
O
S
O
MeO2C
Me3Si
4a
O
4b
(90%c,e
4d
(62%)
4c
(91%b)
(76%c)
)
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
N
N
N
S
N
S
S
S
SO2Ph
Me
Ph
4f
O
4h
(57%e)
4e
4g
(87%d)
(72%d,e
)
(82%)
PhO2S
R
N
CO2
Me
N
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
N
N
R
CO2
N
SO2Ph
N
SO2Ph
EtO2C
R
O2C
N
N
Ac
Ac
Ac
Ac
4k
(90%)
4i R = Me (78%)
4j R = Et (82%)
4l R = Me (87%)
4m R = Et (95%)
4n R = Me (71%e)
4o R = Et (83%e)
PhO2S
PhO2S
SO2Ph
N
O
O
N
SO2Ph
CO2Et
N
SO2Ph
SO2Ph
N
Me
R
SO2Ph
CO2Et
SO2Ph
N
N
Cl
Me
Me
Ac
Ac
4r
4p R = F (62%)
4q R = Cl (63%)
4s
(58%b)
4t
(41%)
(76%e)
a The reaction of arene 3 (0.3 mmol) was performed with NFSI (0.6 mmol)
and TEMPO (0.045 mmol) in EtOAc (2 mL) under argon (1 atm) at 25 oC for
24 h. Isolated yields of 4 after column chromatography on silica gel. b The
reactions were conducted in DCE (2 mL). c The reactions were conducted in
MeCN (2 mL). d The reactions were conducted in 1,4-dioxane (2 mL). e With
1.2 mmol of NFSI.
(a) Independent kinetic isotope effect (KIE) experiments
Subsequently, a variety of different categories of arenes
were explored for this nitroxyl radical-catalysed C-H amination
with NFSI as shown in Table 2. Generally, this TEMPO-catalysed
C-H amination was conducted efficiently on furan (including
benzofuran), thiophene (including thianaphthene), pyrrole,
indole and flavone. To our delight, most furans and thiophenes
could be aminated effectively with 2 eq of NFSI, while electron-
withdrawing acetyl substituted arenes 3b and 3h required 4 eq
of NFSI to guarantee the good yields. Although the conversions
of furans were poor in ethyl acetate, these substrates
underwent this C-H amination smoothly in 1,2-dichloroethane
or in acetonitrile, affording corresponding C2-aminated furans
(4a-c) in excellent yields. Likewise, some thiophenes also
converted poorly in ethyl acetate, but their C2-aminated
thiophenes 4d and 4g were obtained in good yields using 1,4-
dioxane as the solvent instead. When pyrroles and indoles were
employed as the substrates, the C2-aminated products 4i-m
were acquired in good to excellent yields with 2 eq of NFSI. On
the other hand, C3-aminated indoles 4n-r were generated in
slightly lower yields when the C2-position was substituted, and
increasing the loading of NFSI could elevate their yields (4n-o,
4r). Beside these five-membered heterocyclic arenes, a six-
membered heterocyclic arene, flavone, and an electron rich
benzene derivative, mesitylene, could also underwent this
amination, affording 4s and 4t in moderate yields.
3a
H
TEMPO (15 mol%)
DCE (2 mL)
Ar (1 atm), 25 o
(0.3 mmol)
SO2Ph
SO2Ph
O
SO2Ph
SO2Ph
N
or
F
N
+
C
O
3a-d
(0.3 mmol)
4a
D
Intermolecular KIE: kH / kD = 1.92
O
(b) Deprotection of sulfonyl groups
SO2Ph
N
TfOH (15 eq)
DCE (2 mL)
90 oC, 8 h
NH2
O
SO2Ph
COOMe
O
78% yield
N
N
COOMe
2a
5a
Scheme 2 KIE and deprotection experiments
In conclusion, a novel nitroxyl radical-catalysed C-H
amination with NFSI at room temperature has been described,
providing a concise and efficient C-N coupling methodology
under mild conditions in absence of any metal, ligand or
additive, which is the first example of organocatalysed C-H
amination with NFSI. Further studies to fully uncover the precise
mechanism of this amination, as well as to expand the arene
scope from heteroarenes to simple benzenes, are undergoing.
This work is financially supported by the National Natural
Science Foundation of China (No. 21801177). We thank Tao Lu
and Dong Yang in this group for reproducing the results of 2b,
2d, 2k, 4c and 4m.
To gain more evidence supporting the reaction mechanism
proposed in Scheme 1c, several control experiments were
conducted. A competition experiment was performed to
further elucidate the electronic preference of this amination
(Scheme S1).26 When an equimolecular mixture of oxazoles 1b
Notes and references
1
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Ricci, Ed., Amino Group Chemistry: From Synthesis to the Life
Sciences, Wiley-VCH, Weinheim, 2007.
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4 | J. Name., 2012, 00, 1-3
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SO2Ph
SO2Ph
TEMPO (15 mol%)
25 oC
DOI: 10.1039/C9CC02739D
SO2Ph
SO2Ph
Ar
N
Ar
H
F
N
+
The first C-H amination with NFSI via organocatalysis
Totally metal-free, ligand-free and additive-free
At room temperature
Broad substrate scope
The first C-H amination of arene with NFSI through organocatalysis is disclosed, which can be
achieved at room temperature with broad substrate scope.