Direct oxidative isoperfluoropropylation of terminal alkenes: Via hexafluoropropylene (HFP) and silver fluoride

Article abstract of DOI:10.1039/c7cc07614b

A copper-mediated oxidative isoperfluoropropylation of unactivated terminal alkenes with commercially available hexafluoropropylene (HFP) has been developed. With operational simplicity of the procedure and broad substrate applicability, this strategy pro

Full text of DOI:10.1039/c7cc07614b

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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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DOI: 10.1039/C7CC07614B
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COMMUNICATION
Direct oxidative isoperfluoropropylation of terminal alkenes via
hexafluoropropylene (HFP) and silver fluoride †
Xiaojun Wang and Yongming Wu*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
copper-mediated oxidative isoperfluoropropylation of trifluoromethylation and trfluoromethylthiolation, a general
unactivated terminal alkenes with commercially available pathway of introducing an i-C3F7 group into organic compounds
hexafluoropropylene (HFP) has been developed. With operational is rarely reported. Conventional approaches of installing an i-
simplicity of the procedure and broad substrate applicability, this C3F7 group into aliphatic compounds rely on i-C3F7 moiety
strategy provides a general and straightforward way for the nucleophilic addition to carbonyl compounds or nucleophilic
construction of C(sp3)-C3F7-i bond.
A
variety of allylic isoperfluoropropylation of ally halides (Scheme 1, a, b).2a,7
isoperfluoropropylated compounds have been efficiently However, these methods required pre-functionalized
synthesized using this strategy.
precursors hence narrowed applications. Therefore, it is highly
desirable to develop more efficient synthetic approaches to
make a breakthrough.
It is worth noting that hexafluoropropylene (HFP) is the
starting material for the synthesis of i-C3F7X and MC3F7-i
reagents.8,6c-6e In fact, HFP is the most economical and
convenient precursor for i-C3F7 source. There is no doubt that
the process of introducing i-C3F7 group into molecules is
Compounds with a fluoroalkyl group at their allylic positions are
versatile precursors for the synthesis of varieties of fluoroalkyl-
containing molecules with a wide-range of biological activities.1
Therefore,great efforts have been made toward the installation
of the fluoroalkyl group into the allylic positions of organic
molecules through nucleophilic substitution or cross-coupling
reactions.2 Moreover, the formation of an allylic-fluoroalkyl
group bond from unactivated alkenes has been recently
established.3 These methods generally include copper-
mediated allylic trifluoromethylation of terminal alkenes using
Togni’s and Umemoto’s reagents, as well as oxidative allylic
trifluoromethylation and trifluoromethylthiolation of terminal
alkenes using nucleophilic fluoroalkylation reagents.4
An analogue of trifluoromethyl group, namely
isoperfluoropropyl group (i-C3F7), featuring stronger electron-
withdrawing effect and more steric hindrance compared to
trifluoromethyl group, plays an unique role in pesticides,
organocatalysts, and functional materials.5 Nevertheless, unlike
incorporating trifluoromethyl groups into organic molecules,
which has diversified over the years, primary means of
greatly simplified
by
directly
using
HFP
as
isoperfluoropropylation reagent. In 1968, Burnard has found
HFP reacts with silver fluoride to form isoperfluoropropyl
carbanion.9 Chambers’s and Makosza’s groups have reported
incorporating i-C3F7 group into pyridine and azines by using HFP
directly.10
Most
recently,
our
group
arylboronic
has
accomplished
acids and
isoperfluoropropylation
of
arenediazoniumsalts.11 As our continuing efforts to develop
efficient methods of introducing i-C3F7 group into aliphatic
compounds and also inspired by trifluoromethylation and
trifluoromethylthiolation of alkenes through allylic C-H
activation, we sought to develop
a direct oxidative
isoperfluoropropylation of unactivated olefins by using HFP. We
assumed that an oxidative isoperfluoropropylation might be
feasibly similar to oxidative trifluoromethylation. Herein we
reported an efficient copper-mediated direct oxidative
isoperfluoropropylation of unactivated terminal alkenes. In
comparison with previous methods, our new reaction does not
need pre-functionalized substrates and proceeds smoothly at
room temperature (Scheme 1, c).
introducing i-C3F7 have been limited to
a
few
isoperfluoropropylation reagents, such as isoperfluoropropyl
halides (i-C3F7X) and isoperfluoropropyl metals (MC3F7-i)
reagents.6 Although various methods are available for the allylic
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032,
China. E-mail: ymwu@sioc.ac.cn
Inspired by our previous study, perfluoropropyl carbanion
derived from HFP and silver fluoride in acetonitrile was chosen.
†Electronic
Supplementary
Information
(ESI)
available.
See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 2017
Chem. Commun., 2017, 00, 1-4 | 1
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Page 2 of 4
COMMUNICATION
ChemComm
-
a
b
e
i C3F7Ag M CN
Table
1
Optimization
of
conditions
for
dirVeicetw ArtoicxleidOantliivnee
a
or
-
DOI: 10.1039/C7CC07614B
rev ous wor
i k
isoperfluoropropylation of unactivated terminal alkenes.
P
-
,
,
n
c
)
2
i C3F7I Z Pd OA
(
C3F7
i
r
B
R
+
-
HFP AgF
R
-
Ph
C3F7 i
+
Ph
C3F7 i
HFP AgF
,
CN 2h
e
M
+
s wor
Thi
k
-
a
3
a
2
AgC F
i
]
[
-
3
7
c
-
7 i
AgC F
i
]
[
3
7
-
R
R
C3
F
Ph
,
o
e
r
u sa ox an
th C3F7 i
l
t
di
t
C
-
con a n n
,
u
ox an
id
t
]
+
a
1
t
i i
g
Ph
i
C3F7
C
[
+
Scheme 1 Methods for the preparation of allylic isoperfluoropropylated
com oun
p
d
a
4
a
5
compounds.
Entry
Cu source
Oxidant
K2S2O8
Cu(OAc)2
BQ
TBHP
MeCO3H
(30%)
NHPI
BPO
Yield of 2a (%) b
1
2
3
4
5
Cu(OAc)2
CuI
CuI
CuI
CuI
none
none
none
none
6c
We began the study with testing the reaction of allylbenzene
(
1a) and isoperfluoropropylation reagent (Table 1). Several
research groups reported that K2S2O8 was an efficient oxidant
for oxidative trifluoromethylation and oxidative
trifluoromethylthiolation through free radical mechanism.4e, 12
Unfortunately, it did not work in this reaction (Table 1, entry 1).
Cu(OAc)2 and benzoquinone (BQ) also showed no desired
product 2a being generated (Table 1, entry 2-3). As a precursor
of the radical, a radical initiator was often used for initiating free
radical reactions.13 Therefore, an array of radical initiators had
been screened to decide if they could be used to initiate this
reaction. In Qing’s work, tert-butyl hydroperoxide (TBHP) was
an efficient oxidant for CuBr-catalyzed oxidative
difluoromethylation.13a Howerer, no product was observed in
this oxidative isoperfluoropropylation (Table 1, entry 4). To our
delight, subsequent study showed that when peroxyacetic acid
was added, trace amount of desired product 2a was observed
based on 19F NMR spectroscopy, implying that radical initiator
is a feasible oxidant to this reaction potentially (Table 1, entry
5). Further study showed that the product yield could be
improved to 36% by using N-hydroxyphthalimide (NHPI) as the
oxidant (Table 1, entry 6). When benzoyl peroxide (BPO) was
used as the oxidant the yield was further increased to 75%
(Table 1, entry 7). Control experiments showed that both
copper source and oxidant were essential and they have to
work in tandem. The absence of either of them made desired
product impossible (Table 1, entry 8-9).
6
7
CuI
CuI
36
75
8
9
-
BPO
-
BPO
BPO
BPO
BPO
BPO
none
none
31
11
21
29
53
43
24
32
55
83
69
CuI
Cu
CuBr2
Cu(OAc)2
CuCl
CuBr
10
11
12
13
14
15
16
17
18
19
20
21
CuOTf•2MeCN BPO
CuOAc
CuId
CuIe
CuI
CuIg
CuIh
BPO
BPO
BPO
BPOf
BPO
BPO
74
a Reaction conditions: 1a (0.2 mmol), Cu source (0.32 mmol), AgF (0.4 mmol),
HFP (adequate), oxidant (0.2 mmol), MeCN (2 mL), rt, 24 h, under N2
atmosphere. b Yield of isolated product given. c Yield determined by 19F NMR
d
e
analysis versus PhCF3 as an internal standard. CuI (0.1mmol). CuI (0.20
f
g
mmol). BPO (0.3 mmol); 2a
:
3a
:
4a
:
5a>50:2:1:2. CuI(0.10 mmol) and DBU
3a 4a 5a>17:1:3:1.
(0.2 mmol). h CuI (0.04 mmol) and DBU (0.26 mmol); 2a
:
:
:
Various copper sources were investigated, copper powder
and cupric compounds also can achieve the desired product
with descent yield (Table 1, entry 10-12). Several other copper
species were also screened, such as CuCl, CuBr, CuOAc, CuOTf
•2MeCN, but none of them showed better results than CuI
(Table 1, entry 13-16). It was found that the reaction needed
equivalents of CuI, and the yield of 2a decreased rapidly with
the decreased equivalent of CuI (Table 1, entry 17-18). A further
study indicated that when 1.5 equivalents of BPO were added,
the yield was increased to 83% (Table 1, entry 19). Similar to the
Liu’s work,4b several kinds of isoperfluoropropyl-Containing
byproducts were found in this case, and they can hardly be
isolated by column chromatography. On the basis of literature
data and NMR analysis as well as mass spectrum, the ratio of 2a
yield of oxidative isoperfluoropropylation product 2a was
obtained in the presence of 1,5-diazabicyclo[5.4.0]-5-undecene
(DBU) and catalytic amount of CuI, the selectivity of the reaction
became relatively worse (Table 1, entry 20-21).
Upon optimization of the reaction conditions (Table 1, entry
19), the scope of this oxidative isoperfluoropropylation reaction
was explored (Scheme 2). Most of the terminal alkenes
be transformed to the ensuing allylic isoperfluoropropylated
compounds in moderate to good yields. In most cases,
predominant products are the E-configuration, but 2g derived
from allylic ether is Z-configuration. In all cases, the ratio of
product and side products ( ) was moderate. Allyl arenes
1 could
2
2
2
3,4,5
bearing both electron-rich and electron-withdrawing groups
reacted smoothly to give the corresponding products in
and unidentified byproducts is 2a:3a:4a:5a>50:2:1:2. As an
effort to improve the reaction efficiency and the selectivity
further, some attempts had been made by cutting down the
amount of CuI and adding base as additive.4e However, no
better results were found. Though good
moderate to good yields (2a
proceeded in high efficiently
-
2f). Linear aliphatic olefins
2h). In addition, allylic
(
isoperfluoropropylated compounds featuring aromatic acid
2 | Chem. Commun., 2017, 00, 1-4
This journal is © The Royal Society of Chemistry 2017
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Page 3 of 4
ChemComm
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COMMUNICATION
-
+
-
+
HFP AgF
-
,
HFP AgF
R
C3F7 i
R
C3F7
i
ex rac on concen ra on
R
C3F7
i
1
t
ti
t ti
)
,
,
+
-
e
e
View Article Online
M
CN 2h
M
CN 2h
-
,
, ,
r
t
3
e
M
24D48OhI: 10.1039/C7CC07614B
2
Pd/C
OH
3
2
)
-
i
7
-
AgC F
AgC3F7
i
]
[
]
,
3
[
-
7 i
R
R
o
er
th C3
i i
F
,
, ,
r
t
24h
u
C
,
,
r
BP
O
t
I
BPO
con a n n
+
u
I
R
C3F7
i
+
t
g
1
24h
1
C
,
O
com oun
p
-
d
ex rac on concen ra on
1
-
t
ti
t
ti
)
R
C3F7 i
4
5
℃
-
,
r
t
48h
,
,
m
u
er
2
)
CPBA DCM/ b ff
0
10
-
C3
F7 i
-
C3F7
i
-
C3
F
7 i
C3
F
7 i
______________________________________________________________
e
M
R
CO2
O
CO2Et
,
,
,
,
,
,
=
=
=
a
a: a: a: a>
: : :
R
R
R
H
2
2
83%
,
3
4
5
5 2 1 2
O
0
,
e
5
9%
,
2
2
2d 74
%
,
2f 45
-
C3F7 i
:
,
:
>
:
:
:
%
-
F
e
:
H
OM 2b 67% 2b 3b 4b 5b 100 1 1 0
Ph
e: e: e: e>
: : :
1 12 5 2
00 8
:
:
:
>
1
:
:
:
3
4
5
C3
7 i
2d 3d 4d 5d
1 4
00 0
:
:
:
>
:
:
:
0
,
,
=
2f 3f 4f 5f 25 1 1
c
c: c: c: c>
: : :
2
R
Ph 58%
2
3
4 5
100 0 3 0
H
H
-
,
-
C8H17
a
i
-
C3
F7
O
3
,
43
60%
e
C3
F
7 i
M
O
O
C3
F
7 i
10
%
-
O
O
-
X
=
C3F7
i
C3
F
7 i
,
x
3
5
8%
O
O
,
2h
:
,
,
:
,
,
,
,
,
:
:
:
4
:
:
5
>
:
:
:
2g
4
86%
2i
7
:
X
X
O
S
2
j
63
2
j
3
100 0 9 5
9
%
9%
%
%
Scheme
4 Further conversion of the allylic isoperfluoropropylated
j
j
j
>
,
=
=
:
:
>
:
5
0
:
:
:
:
:
:
:
:
:
>
1
:
:
:
:
: : :
2h 3h 4h 5h
2 1 4
2g 3g 4g 5g
1
00 0 0 0
2i 3i 4i 5i
1
2k 80 2k 3k 4k 5k 100 2 6 7
00 0 9
compounds
2
.
-
C3
F7 i
-
F7 i
-
C3
O
O
S
-
O
u
t B
C3
F
7 i
-
C3F7
N
O
i
O
-
u
O
t B
R
=
O
R
,
,
,
,
,
,
,
,
,
,
,
=
:
:
>
:
:
:
n
o
2p
o
:
o:
:
:
o
:
:
:
o>
: : :
:
2
2
71
2
7
52%
2
3
4
5
,
2t
5
3%
2t 3t 4t 5t
R
H
2l 67% 2l 3l 4l 5l 100 1 3 8
%
4
R
R
R
R
R
NO2
6
%
100 0 1 8
,
,
,
=
=
=
=
,
=
Further conversion of the allylic isoperfluoropropylated
compounds were investigated. As shown in Scheme 4,
reduction or epoxidation of the allylic isoperfluoropropylated
compounds proceeded conveniently and efficiently, affording
isoperfluoropropylated alkanes 3 or isoperfluoropropylated epoxide
10 in moderate total yield.
According to previous reports,4a-4c it is reasonable to propose
a mechanism involving radical species for this reaction. To gain
insights into the reaction mechanism, we had tested whether
this transformation proceeds via radical intermediate (Scheme
5). When 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), a well-
known radical scavenger, was added in the standard reaction
conditions, the desired transformation was completely
inhibited (Scheme 5, a). This result showed that this reaction
most likely involves a free radical pathway. However, neither an
n:
3
n
:
n: n>
:
:
:
>
>
m
m: m: m: m>
3
:
:
:
:
: : :
: : :
e
M
R
2
68%
4
5
100 1 5 8
2
5
1
00
1 7 11
CHO
2p 3p 4p 5p
100 1 6
7
:
:
:
>
: : :
00 8
1 1
1
,
:
CF3 2q 64% 2q 3q 4q 5q 50 0 2 1
,
,
,
r: r: r: r>
2
100 0 5 7
90%
r
: : :
I
2
2
3
4 5
2
,
,
,
s
s: s: s: s>
2
:
:
:
O
3
4
5
100 1 5 8
CO2Et
68%
-
O
C3
F
7 i
-
H
C3
F
7 i
O
N
HO
-
i
C3F7
H
H
:
2
-
i C3F7
O
,
,
,
x
2
,
w
u
2
2
2
2
2
%
4
v
6
8
1
%
4
59%
x: x: x: x>
2
2
57
%
w: w: w: w>
3
:
:
:
u: u: u: u>
:
00
:
:
:
:
5
1
2
3
7
v: v: v: v>
:
:
:
00 0
2
3
5
1
1 1 7
3
4 5
100 1 1 9
3
4
5
5
0 3 0 0
Scheme 2 Scope of the reaction. Reaction conditions:
mmol), AgF (0.4 mmol), HFP (adequate), BPO (0.3 mmol), MeCN (2 mL), rt,
24 h, under N2 atmosphere. Isolated yields are reported. The ratios
were determined by 19F NMR analysis and are shown below the yield
1 (0.2 mmol), CuI (0.32
2:3:4:5
.
esters (2i
aryl ethers (2o
useful functional groups, such as ester (2d
ketone (2x), hydroxyl (2w), and even formyl (2p) were all well
tolerated. It is noteworthy that substrate bearing iodo (2r
-
2k), arylsulphonates (2l
2v) were obtained in good yield. Synthetically
2e 2s), nitro (2o),
-2m), phthalimide (2n), and
-
,
,
)
ally-TEMPO nor
a TEMPO-C3F7-i adduct was detected,
proceeded efficiently giving the desired product in good yield,
which is potentially useful for subsequent modification at the
halogenated position. Finally, we found out that internal
alkenes cannot be converted by this method.
Under the same reactions conditions, 1,1-disubstituted
alkenes and terminal alkynes could also be transformed to the
isoperfluoropropylated products by relatively low effciency
(Scheme 3). Isoprene (6a) reacted with isoperfluoropropylation
precluding the involvement of the allylic radical or
isoperfluoropropyl radical in this process.4d Thus, BQ was added
to the reaction mixture when using 1i as substrate. As a result,
normal oxidative isoperfluoropropylation product 2i was
isolated in 12% yield and the difunctionalized product 11 was
isolated in 55% yield (Scheme 5, b). These results suggested that
a radical intermediate
isoperfluoropropylation.5e,14 Moreover, in the absence of CuI,
addition of 4-
A was formed in this oxidative
reagent giving the solely difunctionalized product 7a
Arylacetylenes (8a 8b) were isoperfluoropropylated to give
.
,
(ethoxycarbonyl)benzenediazoniumtetrafluoroborate to the
reaction mixture led to the formation of difunctionalized
product 12 in 67% yield (Scheme 5, c). It seems that the
formation of radical intermediate A does not need the help of
the copper species, which plays a role in the process of radical
both alkynes and difunctionalized products, while the linear
alkyne 8c generated difunctionalized product 9c with
high selectivity.
+
HFP AgF
,
intermediate
products.
A transforming into allylic isoperfluoropropylated
e
M
CN 2h
i
]
R
R
-
6
8
AgC F
3
[
7
ro uc
t
p
d
,
,
,
u
r
t
24h
C
I
BPO
A
plausible mechanism for this direct oxidative
ro uc
su s ra e
t
p
d
b
t t
isoperfluoropropylation reaction of terminal alkenes is
-
C3F7
i
PhCO2
Ph
.
e
u v
3 q
i
( )
,
,
,
u
-
C
I
BPO TEMPO
a
a
7
57
6
%
C3F7
i
a
)
-
,
i
,
24 h
r
t
]
AgC F7
[
-
3
-
-
Ph
+
Ph
C3F7
i
+
+
Ph
C3F7
i
i
a
2
C3F7
a
,
CN 2 h
1
e
M
+
-
no
o serve
b d
t
C3F7
i
,
7
%
HFP AgF
,
,
c
a
7b
7b
7bb
Ph
38%
31%
6b
PhCOO
,
.
e
u v
q
i
)
,
,
2i 12
%
u
I
-
C
BPO
B
2
,
O
Q
-
(
C3
F7
i
Ph
b
)
C3F7
%
i
PhCOO
Ph
Ph
+
-
,
r
AgC3F7
i
t
24 h
I
[
]
,
,
a
b
a
8
aa
9
9
14
%
1
O
3
1i
,
CN 2 h
-
e
M
+
C3F7
i
PhCOO
Ph
-
HFP AgF
+
i
,
C3
F7
Ph
11 55
%
-
-
i
R
C3F7
C3F7
i
,
a
9b 44
A
8b
%
I
N2BF4
CO2Et
,
9bb
2
3%
BPO
C10H21
C10H21
I
-
-
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Scheme 3 Reactions of 1,1-disubstituted alkenes and terminal alkynes.
12
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Scheme 5 Mechanistic experiments.
This journal is © The Royal Society of Chemistry 2017
Chem. Commun., 2017, 00, 1-4 | 3
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ChemComm
Page 4 of 4
COMMUNICATION
ChemComm
+
HFP AgF
Furukawa, T. Nishimine, E. Tokunaga, K. Hasegawa, M. Shiro
,
e
M
CN 2h
View Article Online
-
-
-
and N. Shibata, Org. Lett., 2011,13, 3972-3975; (k) Y. Li, F.
AgC F
3
i
]
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7
DOI: 10.1039/C7CC07614B
+
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R
,
,
,
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t
24h
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I
B
BPO
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1
2
4
-
H
SET
BPO
-
-
i
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i
AgC F
i
]
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ET
R
C3F7
R
R
C3F7
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3
7
II
A
a
hyd
u
C
[
B
]
C
s rac
ro en
g
b
t
t
BPO
or
PhCOO
-
R
i
C3F7
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[
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3
Scheme 6 Proposed mechanism.
therefore proposed (Scheme 6). Initially, in presence of benzoyl
peroxide, the olefins might be oxidized to a radical cation via
single electron transfer (SET),4d and subsequently react with
isoperfluoropropyl silver forming the radical intermediate
Then the radical intermediate could be further oxidized to
form the cation intermediate via SET in presence of copper
3
4
B
A
.
A
C
species and oxidant.4e Finally, the cation intermediate
underwent deprotonation to give the desired products.
C
In summary, an efficient copper-mediated oxidative
isoperfluoropropylation of inactivated terminal olefins involving
allylic C-H bond activation has been developed. In this protocol,
hexafluoropropylene has been used as start material directly,
which simplifies the process of introducing i-C3F7 group into
allylic compounds. Under mild conditions, this transformation
renders a range of allylic isoperfluoropropylated compounds
and shows good functional group tolerance. The olefin moiety
in the products ensures subsequent modification. Further
investigations will focus on clarification the reaction mechanism
and expanding the scope of this transformation.
5
6
This work was supported by the National Basic Research
Program of China (2012CB821600) .
7
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Soc., 1962, 1993-1999; (b) N. J. O’Reilly, M. Maruta and N.
Ishiiawa, Chem. Lett., 1984, 517-520; (c) G. Dubot, D. Mansuy,
Conflicts of interest
There are no conflicts to declare.
S. Lecolier and J. F. Normant, J. Organomet. Chem., 1972, 42
C105-C106.
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4 | Chem. Commun., 2017, 00, 1-4
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