Perfluoroalkylation of Unactivated Alkenes with Acid Anhydrides as the Perfluoroalkyl Source

Article abstract of DOI:10.1002/anie.201604127

An efficient perfluoroalkylation of unactivated alkenes with perfluoro acid anhydrides was developed. Copper salts play a crucial role as a catalyst to achieve allylic perfluoroalkylation with the in situ generated bis(perfluoroacyl) peroxides. Furthermore, carboperfluoroalkylation of alkene bearing an aromatic ring at an appropriate position on the carbon side chain was found to proceed under metal-free conditions to afford carbocycles or heterocycles bearing a perfluoroalkyl group. This method, which makes use of readily available perfluoroalkyl sources, offers a convenient and powerful tool for introducing a perfluoroalkyl group onto an sp³carbon to construct synthetically useful skeletons.

Full text of DOI:10.1002/anie.201604127

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Communications
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International Edition: DOI: 10.1002/anie.201604127
German Edition: DOI: 10.1002/ange.201604127
Fluorine
Perfluoroalkylation of Unactivated Alkenes with Acid Anhydrides as
the Perfluoroalkyl Source
Shintaro Kawamura and Mikiko Sodeoka*
Abstract: An efficient perfluoroalkylation of unactivated
alkenes with perfluoro acid anhydrides was developed.
Copper salts play a crucial role as a catalyst to achieve allylic
perfluoroalkylation with the in situ generated bis(perfluoro-
acyl) peroxides. Furthermore, carboperfluoroalkylation of
alkene bearing an aromatic ring at an appropriate position
on the carbon side chain was found to proceed under metal-
free conditions to afford carbocycles or heterocycles bearing
a perfluoroalkyl group. This method, which makes use of
readily available perfluoroalkyl sources, offers a convenient
and powerful tool for introducing a perfluoroalkyl group onto
an sp3 carbon to construct synthetically useful skeletons.
unactivated, with TFAA as a trifluoromethyl source remains
an important challenge. Indeed, our preliminary examination
of the reaction of an unactivated alkene 1a with BTFAP
[10,15]
generated in situ from TFAA and urea·H2O2
was unsuc-
cessful, and a large amount of starting material was recovered
along with a complex mixture of trifluoromethylated products
(Scheme 1a).[16]
P
erfluoroalkyl compounds, in particular trifluoromethyl
compounds, are of considerable interest as drugs, agrochem-
icals, and functional materials because of the unique proper-
ties of the fluorine atom.[1,2] Therefore, there is great demand
for convenient and practical synthetic methods.
Recently, alkene trifluoromethylation has been realized
through the development of excellent electrophilic trifluoro-
methylating reagents such as the Togni reagent and the
Umemoto reagent, which enable the direct construction of
synthetically important organic frameworks bearing a trifluor-
omethyl group on an sp3 carbon.[3–7] We have developed
various difunctionalization-type trifluoromethylation reac-
tions using the Togni reagent,[4e,5a,6a,7] and a diverse array of
trifluoromethylated compounds can now be accessed. The
high cost and multistep preparation of these sophisticated
reagents, however, might hinder industrial application. There-
fore, a convenient and practical alternative trifluoromethyl
source is still needed.
Trifluoroacetic anhydride (TFAA) is inexpensively pro-
duced on a large scale and is commonly used as a reagent in
organic syntheses; it could thus be a suitable alternative
trifluoromethyl source.[8] Indeed, oxidized TFAAs such as
bis(trifluoroacetyl) peroxide (BTFAP)[9–11] and a pyridine N-
oxide/TFAA adduct[12] have been used as trifluoromethyl
radical sources for the trifluoromethylation of aromatic
compounds and limited types of alkenes.[11–14] However,
trifluoromethylation of alkenes, in particular those that are
Scheme 1. a) Preliminary result of trifluoromethylation of unactivated
alkene 1a with TFAA/urea·H2O2. b) Reactivity control of the alkyl
radical.
The reaction at higher temperature accelerated the
consumption of 1a, but many products were formed
(Table S1 and Figure S1 in the Supporting Information).
The observed low product selectivity suggests that an accel-
eration of CF3 radical generation as attempted in the aromatic
trifluoromethylations[9–14] is not sufficient to achieve trifluoro-
methylation of unactivated alkenes.[9b] Instead, selective
transformation of a highly reactive alkyl radical, resulting
from the reaction of an alkene with a CF3 radical, into the
product would be the key to success for efficient trifluoro-
methylation of alkenes. We found two principles for control-
ling the reactivity of the radical intermediate: rapid oxidation
to the cation and intramolecular trapping (Scheme 1b).
Herein, we disclose a high-yielding copper-catalyzed allylic
trifluoromethylation of alkenes with TFAA as the trifluoro-
methyl source, and its extension to allylic perfluoroalkylation.
In addition, we report carboperfluoroalkylation of alkenes
under metal-free conditions, which is useful for the construc-
tion of various carbocycles.
[*] Dr. S. Kawamura, Prof. Dr. M. Sodeoka
Synthetic Organic Chemistry Laboratory, RIKEN
2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)
and
We speculated that a transition-metal catalyst could act as
an electron acceptor and oxidize the alkyl radical to the cation
through single electron transfer (SET). We thus examined the
effects of transition-metal salts (Table 1 and Table S1).[17]
First, Cu(O2CCF3)2 was selected as the catalyst for this
purpose. Fortunately, we found that it selectively gave allylic
RIKEN Center for Sustainable Resource Science
2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)
E-mail: sodeoka@riken.jp
Supporting information for this article can be found under:
http://dx.doi.org/10.1002/anie.201604127.
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Table 1: Allylic trifluoromethylation of 1a with TFAA.
Table 2: Substrate scope for the Cu-catalyzed perfluoroalkylation with
perfluoro acid anhydride.
Entry Catalyst
Yield of 2a [%] (E/Z)[a] Recov. of 1a [%][a]
1
2
none
Cu(O2CCF3)2
not detected
64 (76:24)
72
32
5
3
[Cu(CH3CN)4]PF6 92 (78:22)
4[b]
[Cu(CH3CN)4]PF6 95 (78:22)[c]
4
[a] Yields and E/Z ratios were determined by 1H and 19F NMR analysis.
[b] The reaction was conducted in 0.4m CH2Cl2. [c] Yield of isolated
product.
trifluoromethylation product 2a,[4] which was not detected in
the reaction without the catalyst (entry 1), as the major
product in 64% yield (entry 2). After further screening of
catalysts and optimization of the reaction conditions,[17]
[Cu(CH3CN)4]PF6 was found to give the best result (entries 3
and 4), affording 2a in 95% yield when using 0.4m CH2Cl2
(entry 4). CuI species probably accelerate the initial CF3
radical generation through SET with BTFAP,[18] and the
resulting CuII species would then play a role in controlling the
product selectivity. It is noteworthy that this reaction could be
conducted on a gram scale without problems.[17]
We next examined the substrate scope of the reaction
under the optimal conditions (Table 2). When 1-decene 1b,
which is without any influential functional groups, was
subjected to the reaction, the desired trifluoromethyl product
2b was obtained in 82% yield (entry 1). The reaction of an
alkene bearing aromatic rings proceeded selectively at the
double bond, affording the desired products in 71–77% yield
(entries 2–4). Cu(O2CCF3)2 gave better results (73% yield)
than [Cu(CH3CN)4]PF6 (36% yield) in the reaction of the
anisyl substrate 1e (entry 4). Ketone (1 f and 1g) and bromo
(1h) substituents were tolerated under these conditions
(entries 5–7, 83%, 49%, and 92% yield, respectively). An
alkene bearing a free hydroxy group (1i) afforded 2i in 80%
yield after hydrolysis of the trifluoroacetylated hydroxyl
group with Et3N-pretreated silica gel[19] (entry 8). The phtha-
limide substrate 1j gave the product 2j in excellent yield
(entry 9, 93%). Allylic trifluoromethylation of 1k also
proceeded efficiently, and removal of the Boc group, probably
by TFA generated during the reaction, and subsequent
trifluoroacetylation afforded 2k’ in excellent yield (entry 7,
91%). Acyclic (1l) and cyclic (1m) internal alkenes were also
amenable to the reaction (entries 11 and 12, 75% and 48%
yield, respectively). Notably, tetradecene 1l gave the product
2l with a higher E/Z ratio than terminal alkenes (E/Z =
96:4).[20] In addition, this method was applicable to perfluoro-
alkylation with perfluoro acid anhydrides possessing a longer
perfluoroalkyl group, as well as trifluoromethylation
[a] E/Z ratios were determined by 19F NMR analysis. [b] The reaction was
conducted in 0.2m CH2Cl2 at 08C. [c] 20 mol% of the catalyst was used.
[d] Cu(O2CCF3)2 was used instead of [Cu(CH3CN)4]PF6. [e] The crude
product was hydrolyzed with Et3N/SiO2.
yield). After examination of the reaction conditions, the
reaction of 1c with TFAA/urea·H2O2 was found to proceed
selectively under metal-free conditions, affording the carbo-
cyclic product 3c in 91% yield (Scheme 2b). The current
(entries 13–15).
The
desired
pentafluoroethyl
and
heptafluoropropyl compounds were obtained from Ts-pro-
tected alkenyl amine 1n in 80% and 72% yield, respectively.
Based on our original work (Scheme 2a),[5a,6a] we next
considered carbotrifluoromethylation using TFAA. In the
reaction of 1c shown in Table 2 (entry 2), the carbotrifluoro-
methylation product 3c was formed as a byproduct (21%
Scheme 2. Carbotrifluoromethylation throughintramolecular carbocycle
formation.
2
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method gave the product in higher yield and under milder
conditions than our previous reaction using the Togni reagent,
and catalyst-controlled switching of the allylic and
carbotrifluoromethylation reaction was achieved.
We then examined the scope of the reaction (Table 3). We
found that 4-fluorophenylpentene 1d furnished the desired
product 3d in excellent yield (96%). A substrate with an
electron-rich methoxyphenyl group also gave the desired
Table 3: Substrate scope for the carboperfluoroalkylation.
[a] The reaction was conducted in 0.4m CH2Cl2. [b] The reaction was
conducted in 0.02m CH2Cl2. [c] 1,2-Dichloroethane was used instead of
CH2Cl2.
Scheme 3. a) Proposed mechanism of the present reactions. b) Com-
parison of the activation energies of SET and intramolecular carbocyc-
lization.
product 3e in 64% yield under dilute conditions. A phenol
substituent was tolerated in the reaction (3o; 95%), and the
gem-disubstituted alkene 1p afforded the desired product 3p
in 99% yield. Allylated biphenyl 1q provided the desired
carbocyclic product 3q in 92% yield without formation of the
allylic trifluoromethylation product. A five-membered ring
was also successfully constructed in 1,2-dichloroethane at
608C (3r; 89% yield). In addition, this method was applicable
to reaction with perfluoro acid anhydrides possessing longer
perfluoroalkyl groups, affording the desired products 3c’ and
3c’’ in 77% and 72% yield, respectively. Furthermore,
trifluoromethyloxindoles were synthesized from acrylamides
under the current reaction conditions.[6] When N-methyl-N-
phenylmethacrylamide 1s was employed in the reaction,
oxindole 3s was obtained in 90% yield. Bromo and ethyl ester
substituents on the phenyl group were well tolerated and
oxindoles 3t and 3u were obtained in 95% and 99% yields,
respectively.
through a radical chain reaction (path 2). Initial formation of
the perfluoroalkyl radical should occur through thermal
decomposition of the peroxide and/or SET between the
substrate and the peroxide.[9b] The perfluoroalkyl radical
reacts with the double bond and the resulting alkyl radical
undergoes intramolecular reaction with the aromatic ring.
Then an aromatization through SET to the diacyl peroxide
and subsequent deprotonation affords the desired product
and regenerates the perfluoroalkyl radical. In addition, DFT
studies suggested that SET from the alkyl radical to the CuII
catalyst should be faster than cyclization in the reaction of 1c,
which is in agreement with the experimental result regarding
catalyst-controlled switching of the product generated (Sche-
me 3b).[17,22]
Although details of the reaction mechanism are still
unclear, a possible mechanism is shown in Scheme 3a. First,
the diacyl peroxide is generated from the acid anhydride and
urea·H2O2. In the case of allylic perfluoroalkylation (path 1),
SET between the diacyl peroxide and the CuI catalyst triggers
the generation of a perfluoroalkyl radical through decarbox-
ylation.[18] The perfluoroalkyl radical reacts with the alkene,
affording an alkyl radical intermediate.[21] At the final step of
the catalytic cycle, the product is formed through oxidation of
the radical by the CuII species, followed by deprotonation. In
the absence of a copper catalyst, the reaction would proceed
In conclusion, we have developed a highly practical and
efficient method for allylic and carboperfluoroalkylation of
unactivated alkenes, with perfluoro acid anhydrides as an
expedient perfluoroalkyl source. We believe that this con-
venient and straightforward method will facilitate the discov-
ery of new drugs, agrochemicals, and functional materials
bearing perfluoroalkyl groups, which are often incorporated
into candidate molecules to improve characteristics such as
lipophilicity, metabolic stability, and pharmacokinetics. Fur-
ther investigation of the substrate scope and mechanistic
studies are ongoing.
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Acknowledgements
This work was supported by JSPS KAKENHI (No.
15K17860) and Project Funding from RIKEN. The computa-
tional study was conducted on the HOKUSAI-GW
(RIKEN).
Keywords: alkenes · copper · homogeneous catalysis ·
perfluoroalkylation · peroxide
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Received: April 28, 2016
Published online: && &&, &&&&
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Communications
Fluorine
S. Kawamura,
M. Sodeoka*
&&&& — &&&&
Perfluoroalkylation of Unactivated
Alkenes with Acid Anhydrides as the
Perfluoroalkyl Source
F for effective: Perfluoroalkylation of
unactivated alkenes with perfluoro acid
anhydrides as the perfluoroalkyl source
was achieved. A copper catalyst enabled
efficient allylic perfluoroalkylation with
in situ generated diacyl peroxide. In
addition, alkenes bearing an aromatic
ring at an appropriate position on the
carbon side chain afforded carboper-
fluoroalkylation products under metal-
free conditions.
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