Synthesis of α-CF3 and α-CF2H amines: Via the aminofluorination of fluorinated alkenes

Article abstract of DOI:10.1039/c8cc03364a

A novel synthesis of α-CF₃ and α-CF₂H amines via the aminofluorination of gem-difluoroalkenes and mono-fluoroalkenes, respectively, is reported. The method employs Selectfluor as an electrophilic fluorine source and acetonitrile as a nitrogen source. Mechanistic studies revealed a single-electron oxidation/fluorine-abstraction/Ritter-type amination pathway. The protocol allowed the synthesis of a broad range of fluorinated amines including those bearing quaternary carbon centers with good efficiency and functional group tolerance.

Full text of DOI:10.1039/c8cc03364a

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
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Synthesis of α-CF3 and α-CF2H Amines via Aminofluorination of
Fluorinated Alkenes
Ling Yang,‡ Wen-Xin Fan,‡ E Lin, Dong-Hang Tan, Qingjiang Li and Honggen Wang*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
previous work:
dimerization
A
novel synthesis of α-CF3 and α-CF2H amines via the
F
Ag
(a)
F
F
F
R
R1
aminofluorination
of
gem-difluoroalkenes
and
mono-
CF3 R1
R2
fluoroalkenes, respectively, is reported. The method employs
Selectfluor as an electrophilic fluorine source and acetonitrile as
R2
carbon radical
R
R3
CF3 R3
OBoc
the nitrogen source. Mechanistic studies revealed
a single-
R4
R4
cat. Pd
R
electron oxidation/fluorine-abstraction/Ritter-type amination
pathway. The protocol allowed the synthesis of a broad range of
fluorinated amines including those bearing quaternary carbon
centers with good efficiency and functional group tolerance.
F
F
CF3
F
F
Ar X
R
R
F
F
R
Ar
(b)
cat. Pd
CF3
carbon anion
H
R
H
The fluorine-containing compounds have found widespread
applications in pharmaceuticals, agrochemicals as well as
materials.1 The trifluoromethyl (CF3) and difluoromethyl (CF2H)
structural motifs have gained particular attention in drug
discovery2 and therefore attracted significant synthetic efforts
(Fig. 1).3 Recently, the gem-difluoroalkenes have proved to be
useful synthon in organofluorine synthesis4 via mono-
defluorinative5 or fluorine-retentive6 functionalization
reactions. Interestingly, with the judicious employment of
additional fluorine source, the fluorine-addition reaction of
gem-difluoroalkenes also allowed the efficient synthesis of
CF3-containing molecules, which is complementary to the
F
CF3
O
F
F
CH3CN, H2
O
R
F
(c)
R
N
this work
H
carbon cation
Scheme 1. Toward the synthesis of trifluoromethylated molecules starting from gem-
difluoroalkenes
typical trifluoromethylation reaction wherein a CF3-containing
source was used.7 In 2014, Hu discovered that the reaction of
gem-difluoroalkene with AgF deliverd a ɑ-trifluoromethylated
carbon-centered radical, which could then undergo
dimerization reaction8a or radical addition reaction to alkenes
(Scheme 1a).8b The use of a F- source was found to be able to
CF3
O
O
CF3
F3C
N
H
N
OH
NH
O
H
N
Ph
participate the nucleophilic addition reaction to generate a β-
N
HN
O
Insecticide
Antitumor agent
trifluorocarbanion (Scheme 1b). By quenching with a Brønsted
acid, the corresponding trifluoroethyl group was formed.9 Loh
and Feng elegantly incorporated this process into the
palladium-catalyzed allylation10 and arylation11 reaction. In
continuation with our interest in the functionalization
reactions of gem-difluoroalkenes,5a,5b,5c,12 herein, we reported
an unprecedented trifluoromethylation reaction toward the
synthesis ɑ-CF3 amines via the aminofluorination of gem-
F
F
NH2
N
N
N
O
N
O
HO
F
N
N
O
N
N
O
N
F
F
OH
F
OH
Gemcitabine
FT671
Fig. 1 Representative bioactive ɑ-CF3 and ɑ-CF2H amines.
difluoroalkene with
a A β-
F+ source (Scheme 1c).
trifluorocarbocation, which was trapped by CH3CN, was
believed to be involved in the mechanism. The protocol was
also applicable to the aminofluorination of mono-
fluoroalkenes, leading to the synthesis of ɑ-CF2H amines in
good efficiency.
This journal is © The Royal Society of Chemistry 20xx
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Our reaction design was guided by the fact that Selectfluor is a 11
Tf2NH (2 equiv)
Selectfluor
0.05 58 /trace/42
0.03 75/trace/17
0.03 27/trace/54
0.03 38/trace/41
strong oxidant capable of accepting one electron from olefins
12
Tf2NH (2 equiv)
Selectfluor
to generate the corresponding radical cations, which could
13
Tf2NH (0.2 equiv) Selectfluor
Tf2NH (1 equiv) Selectfluor
a1a (0.2 mmol, 1.0 equiv), Selectfluor (0.4 mmol, 2.0 equiv), MeCN, 60 oC, under air,
further undergo fluorine abstraction to form α-fluorinated
carbocations.13 The reaction of gem-difluoroalkenes with
14
Selectfluor would, in principle, provide the carbocation
isolated yields. ND: Not detected.
intermediates bearing
a
α-CF3 substituent. However,
challenges may exist due to the electron-deficient nature of
gem-difluoroalkenes, which may lead to the single-electron
transfer difficult. To test the feasibility of the envisioned
process, gem-difluoroalkene 1a was treated with Selectfluor in
acetonitrile (Table 1). As expected, the electrophilic
fluorination/Ritter-type amidation product α-CF3 amine 2a was
found, although in low yield (entry 1). Two side products (3a
and 4a) were identified to be derived from the competitive
nucleophilic attack from H2O and the reduced amino motif of
Selectfluor. We speculated the addition of Brønsted acid might
help circumvent these side reactions: first, the Brønsted acid
would ionize the alcohol 3a to regenerate the benzylic cation,
offering a second chance for Ritter amination; second, the
protonation of the reduced amino motif would eliminate its
F
Cl
Cl
O
O
N
N
N
N
N
S
S
N
N
O O
2BF4
N
F
2BF4
2PF6
F
F
F
BF4
Selectfluor
NFSI
F-I
F-II
F-III
With the optimized reaction conditions in hand (entry 12,
Table 1), the generality of the reaction was then explored.
gem-Difluorostyrenes 1b bearing electron-donating isopropyl
substituent also gave the corresponding product in good yield.
Substrates with an additional methyl group also delivered the
desired products (2c-2e), but accompanied by the formation of
minor trifluomethylated alkene byproducts. These byproducts
were assumed to be derived from the competitive
deprotonation reaction of the benzylic cation intermediate
(see Scheme 3). As expected, the diaryl gem-difluoroalkenes
were excellent substrates for the reaction. In these cases, a
variety of functional groups such as trifluoromethyl (2k),
nucleophilicity, thereby minimizing the formation of 4a
.
Indeed, we found that the employment of 2 equivalents of
acid gave a better yield of the desired product 2a, with Tf2NH
being the optimal (entries 2-5). Other F+ sources were also
screened. While NSFI and F-I showed no reactivity (entries 6
and 7), F-II and F-III gave a similar result as Selectfluor (entries
8 and 9). A good yield of 75% was obtained by diluting the
reaction mixture to 0.03 M (entries 10-12). Attempts to lower
the acid loading resulted in the formation of more 4a, again,
confirming the important role of acid for the reaction (entries
13 and 14).
methoxy (2l), methyl (2g-2i), bromo (2j and 2p), fluoro (2m
-
2o), nitro (2q) could be well tolerated. Unfortunately, no
reaction was found with aliphatic gem-difluoroalkenes (1r and
1s) under the standard reaction conditions.
Table 2. Substrate scope for the synthesis of α-CF3 amines
Table 1. Optimization of the reaction conditionsa
Entry
Additive
F+ resource
Conc.
Yield (%)
2a/3a/4a
1
2
3
4
5
6
7
8
9
10
None
Selectfluor
Selectfluor
Selectfluor
Selectfluor
Selectfluor
NFSI
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
33/6/54
TFA (2 equiv)
38/5/31
51/trace/40
42/7/50
45/trace/33
0
H2SO4 (2 equiv)
TfOH (2 equiv)
Tf2NH (2 equiv)
Tf2NH (2 equiv)
Tf2NH (2 equiv)
Tf2NH (2 equiv)
Tf2NH (2 equiv)
Tf2NH (2 equiv)
F-I
0
With the aminofluorination of gem-difluoroalkenes
established, we then questioned the feasibility of similar
reaction by using monofluoroalkenes as substrate.
Monofluoroalkenes are more electron-rich than gem-
difluoroalkenes and therefore are expected to be more
reactive toward aminofluorination. If successful, the reaction
F-II
47/trace/ND
45/trace/49
31/trace/60
F-III
Selectfluor
2 | J. Name., 2012, 00, 1-3
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Scheme 2. Derivatization of products and mechanistic studies
should provide a ɑ-CF2H amine product, which is also
interesting structural motif in medicinal chemistry.2c,2d,2f
Based on the above experimental results and literature
precedents,13 the following mechanism was proposed. The
aminofluorination reactions of gem-difluoroalkenes and
Indeed, the reaction of (
provided the desired product 6a in 48% isolated yield (Table
3). The type substrate gave a comparable yield. Thus, the
mixtures of and isomers of monofluoroalkenes were used
Z)-5a in the above standard reaction
E
monofluoroalkene were believed to share
a
similar
E
Z
mechanism. Initially, the strong oxidizing property of
to investigate the scope. Again, in addition to the aryl
Selectfluor leads to a single electron oxidation of gem-
monofluoroalkenes (6a and 6b), substrates with additional
difluoroalkene to form an alkene radical cation I. This species
methyl (6c) and aryl group (6d-6n) were also applicable for
would then undergo an in-cage regioselective fluorine atom
abstraction from the reduced Selectfluor, providing a benzylic
aminofluorination, delivering the desired product in moderate
to excellent yields.
cation II and the corresponding tertiary amine III
nucleophilic attack of the III forms the sideproduct
Alternatively, Ritter-type amination gives desired
aminofluorination product . The presence of water in the
reaction mixture also leads to the generation of alcohol
With a methyl group substituted, a deprotonation reaction can
occur to furnish trifluoromethylated alkene. The acid
employed might protonate amine III, thereby minimizing the
formation of
. The
Table 3. Substrate scope for the synthesis of ɑ-CF2H amines
4.
a
2
3.
a
4
.
The acetyl group in 2a and 6a could be removed under acidic
conditions to give the free ɑ-CF3 amine
7 and ɑ-CF2H amine 8
in good yields (Scheme 2a and 2b), which offered good
opportunities for further elaboration on the nitrogen atom. To
verify our mechanistic hypothesis, experimental studies were
conducted. Both of the aminofluorination reactions were
inhibited by radical scavenger BHT (Scheme 2c and 2d). In
addition, the ring opening product 10 was observed when
Scheme 3. Mechanistic proposals
In conclusion, a facile synthesis of ɑ-CF3 and ɑ-CF2H amine was
developed via the aminofluorination of gem-difluoroalkenes
and monofluoroalkenes, respectively. The protocol employs
Selectfluor as the fluorine source and acetonitrile as the
nitrogen source. Mechanistic studies pointed out that a single-
electron-transfer is involved in the mechanism. Broad
substrate scope and generally good yield were observed. Given
the importance of nitrogen groups in bioactive compounds,
this novel synthesis of fluoroamines is expected to find
application in medicinal chemistry.
cyclopropyl-substituted substrate
9
was employed. These
radical in the
results suggested the involvement of
mechanism.
a
Acknowledgement
Financial support from the National Natural Science
Foundation of China (21472250), the Key Project of Chinese
National Programs for Fundamental Research and
Development (2016YFA0602900), the National Science and
Technology Major Project of the Ministry of Science and
Technology of China (2018ZX09735010), and the "1000-Youth
Talents Plan" are gratefully acknowledged.
Conflicts of interest
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DOI: 10.1039/C8CC03364A
A novel synthesis of ɑ-CF3 and α-CF2H amines via the aminofluorination of gem-difluoroalkenes
and monofluoroalkenes, respectively, is reported.