Selective nickel-catalyzed fluoroalkylations of olefins

Article abstract of DOI:10.1039/d0cc06652d

Mild and selective nickel-catalyzed trifluoromethylation and perfluoroalkylation reactions of alkenes were developed to provide fluorinated olefins, including natural products, pharmaceuticals, and variety of synthetic building blocks in good to excellent

Full text of DOI:10.1039/d0cc06652d

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DOI: 10.1039/D0CC06652D
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Selective Nickel-catalyzed Fluoroalkylations of Olefins
Shaoke Zhang,†a Florian Weniger,†a Fei Ye,a Jabor Rabeah,a Stefan Ellinger,b Florencio Zaragoza,b
Christoph Taeschler,b Helfried Neumann,a Angelika Brückner,a and Matthias Beller*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Mild and selective nickel-catalyzed trifluoromethylation and olefins from ketones,7 and the first selective carbonylations of
perfluoroalkylation reactions of alkenes were developed to provide gem-difluoroalkenes leading to difluoromethylated esters.8
fluorinated olefins, including natural products, pharmaceuticals, Inspired by these works and the known versatility of
and variety of synthetic building blocks in good to excellent yields (per)fluoroalkyl-substituted olefins, we became interested in
(38 examples). Control experiments, kinetic measurements and in their preparations (Scheme 1).9 An obvious approach to access
situ EPR studies reveal the importance of radical species and the this kind of molecules makes use of metal-mediated cross
formation of 1,2-adducts as intermediates.
coupling reactions between vinyl halides and the (in situ)
formed fluoroalkyl metal species.10 However, the need of
stoichiometric amounts of transition metals and the availability
of the substrates limits such procedures. Following the same
strategy, (per)fluoroalkyl-substituted olefins have been
synthesized by reaction of perfluoroalkyl reagents with vinyl
boronic acids,11 vinyl zirconium complexes,12 or alkynes.13 In all
these cases only very few examples could be realized, and the
reaction conditions are sensitive. Alternatively, the direct
functionalization of alkenes with (per)fluoroalkyl halides RFX (X
= I, Br) represents an advantageous and straightforward
methodology. Notably, both kinds of substrates (alkenes and
RFX) are commercially available at reasonable prices. Hence, it
is surprising that this transformation was scarcely investigated.
In fact, only photochemical14 and noble metal catalyzed15
protocols are known. Complementary to these examples,
herein we report a general nickel-catalyzed protocol for the
perfluoroalkylation of alkenes to offer selectively fluorinated
olefins.
For our initial studies, the perfluorodecylation of 3,3-
dimethylbutene was selected as a model system to avoid
unwanted side reactions (e.g. olefin isomerization). As
alternative catalysts we envisioned nickel complexes, which can
be often used as a substitute for palladium in cross coupling
reactions.16 More specifically, the commercially available air-
and moisture-stable dppfNi(o-tol)Cl complex was applied as
pre-catalyst,17 because of its activity in the perfluoroalkylation
of (hetero)arenes.18 To trap the potentially formed acid (HX),
most test reactions were performed in the presence of base (2
equiv). Indeed, without base no conversion occurred at 50-80°C
even after 16 h. Similar results were obtained in the presence
of alkali carbonates and acetates (Na2CO3, Cs2CO3, and NaOAc)
Organofluorine compounds have significantly different
chemical and physical properties compared to their parent
hydrocarbons because of the high electronegativity (3.98,
Pauling scale) and at the same time very small size of fluorine
atoms (50 pm).1 Hence, their synthesis and applications
continue to attract the attention of many researchers in
industry and academia.2 Apart from the fundamental scientific
interest in fluorinated chemicals, they are also used in diverse
applications ranging from material (e.g. refrigerants, oil and
water repellents) to life sciences (pharmaceuticals,
agrochemicals, etc.).3 Especially, in this latter area several
methodologies enabling the synthesis of new bioactive
compounds were disclosed in recent years.4
Nevertheless, the preparation of advanced fluorinated building
blocks generally requires special techniques associated with the
handling of sensitive and expensive reagents.5 To overcome
these limitations, we started a program investigating catalytic
coupling processes of commercially available perfluoroalkyl
halides including trifluoromethyl bromide and iodide with
(hetero)arenes.6 Most recently, we also reported a facile and
practical method for the stereoselective synthesis of fluorinated
a. Dr. S. Zhang, F. Weniger, Dr. F. Ye, Dr. J. Rabeah, Dr. H. Neumann, Prof. Dr. A.
Brückner and Prof. Dr. M. Beller*
Leibniz-Institut für Katalyse e.V.
Albert-Einstein-Straße 29a, 18059 Rostock (Germany)
E-mail: matthias.beller@catalysis.de
b. Dr. S. Ellinger, Dr. F. Zaragoza, Dr. C. Taeschler
Lonza Ltd
Rottenstrasse 6, 3930 Visp (Switzerland)
† These authors contributed equally to this work.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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(Table 1, entries 1-3). Likewise, using a weak organic base products in good to excellent yields. Interestingly,
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DOI: 10.1039/D0CC06652D
(TMEDA) showed no desired product formation (Table 1, entry perfluorodecyl iodide is selectively activated in the presence of
4). However, applying stronger bases t-BuONa and t-BuOK a an alkenyl bromide (2n). Furthermore, amino groups (2o) are
Heck-type vinylation occurred and E-1-perfluorodecyl-3,3- well tolerated in this procedure, too. Using substrate 1p,
dimethyl-but-1-ene 2a is obtained in 86-87% yield (Table 1, containing internal and terminal double bonds, only the latter
entries 5-6). It is noteworthy that the test reaction also took reacted affording 2p in 68% yield. Nevertheless, without
place at room temperature giving 48% of the desired product, terminal double bond present also cyclohexene can be
while reactions at higher temperature did not improve the perfluoroalkylated, albeit in lower yield. From a synthetic point
product yield further on (Table 1, entries 7-8). Blank of view, the reactions of quinidine to give 2r in 90% and
experiments without nickel catalyst gave only negligible naturally occurring nerol to provide 2s are notable.
conversion.
dppfNi(o-tol)Cl (5 mol%)
t-BuONa (2 equiv)
Table 1. Ni-catalyzed perfluorodecylation of 3,3-dimethylbutene.
C10F21
dppfNi(o-tol)Cl (5 mol%)
C
+
10F
21I
R
R
perfluorobenzene (0.5 mL)
50 oC, 16 h
base (2 equiv)
C10F21
Me
Me
Me
Me
0.2 mmol
+
C10
F
21I
1
, 2 equiv
C10F21
2
solvent (0.5 mL)
50 ºC, 16 h
Me
Me
1a
0.2 mmol
C10F21
Me
R
C10F21
Et
Et
2a
Si
R
Si
Me
Entry
1
Base
Solvent
T / °C
50
Yield / %
2b
, R = n-C4H9-
87%, E/Z = 84:16
2c
Et
2f,
2e
2g
, R = Me-, 78%
, R = Ph-, 67%
Na2CO3
Cs2CO3
NaOAc
--
-
72%
, R = n-C6H13
81%, E/Z = 87:13
2d
-
E/Z = 84:16
2
--
50
-
3
--
50
-
C10F21
EtO
C10F21
O
, R = n-C10H21
-
4
TMEDA
t-BuONa
t-BuOK
--
50
-
88%, E/Z = 88:12
OEt
2i
O
5
--
50
87
86
48
85
19
17
75
15
21
, 76%
E/Z = 87:13
C10F21
2h
, 71%
6
--
50
C10F21
O
7
t-BuONa
t-BuONa
t-BuONa
t-BuONa
t-BuONa
t-BuONa
t-BuONa
--
--
25
C10F21
Me
3
8
120
50
HO
Me
9
benzene
DMF
2j
, 89%
E/Z = 82:18
2k
, 87%
10
11
12
13
50
2l
, 88%
C10F21
perfluorobenzene
CH3CN
THF
50
Me
C10F21
Br
50
C10F21
N
3
Me
2
50
2m
2n
, 90%
E/Z = 83:17
, 50%
2o
, 73%
E/Z = 59:41
Reaction conditions: 1a (2 equiv in case of using additional solvent, 0.5 mL for all other
entries), Ar, yields were determined by 19F NMR.
E/Z = 78:22
C10F21
C10F21
In all previously described experiments, 3,3-dimethylbutene
was used both as substrate and solvent. Although it is beneficial
for inexpensive olefins to run this transformation in neat media,
for structurally more advanced olefins the use of an external
solvent will be obviously preferred. Thus, experiments in the
presence of different solvents were investigated. As shown in
Table 1 (entries 9-13), this transformation is quite sensitive
towards solvents. While standard aromatic (benzene) and
dipolar aprotic (DMF) solvents showed low product yields (17-
19%), in the presence of perfluorobenzene a comparable yield
of 2a (75%) with the neat condition could be obtained. Using
THF and CH3CN as solvent, as the major reaction pathway
reductive dehalogenation occurred and a significant amount of
C10F21H is detected by 19F NMR (33% and 76%, respectively).
With suitable reaction conditions in hand, the
perfluoroalkylation of various alkenes was tested. Apart from
3,3-dimethylbutene, linear aliphatic alkenes with different
chain length are converted to the corresponding products 2b –
2d in high yields (>81%). Here, no olefin isomerization is
occurring and the E-products prevail. Fluoroalkylated
vinylsilanes 2e – 2g are obtained (67–78% yields) by smooth
transformation of vinylsilanes, which can be easily transformed
into other useful products.19 Next, various alkenes with 1,3-
dioxa-2-cyclopentyl (2h), ethoxy (2i), benzyloxy (2j), hydroxy
(2k), cyclohexyl (2l), and phenyl (2m) groups were all
successfully perfluoroalkylated to give the corresponding
2p
, 68%
2q
, 13%
E/Z = 89:11
C10F21
HO
N
H
O
O
2r [a]
,
90%
C10F21
E/Z = 81:19
2s
, 49%
E/Z = 83:17
N
Scheme 1. Nickel-catalyzed perfluorodecylation of alkenes. Yields were determined by
19F NMR. [a] 4 equiv t-BuONa.
To demonstrate the generality of our protocol and this specific
catalyst system, other perfluoroalkyl reagents including
trifluoromethyl bromide and iodide were explored. As shown in
Scheme 2, perfluoroalkyl iodides containing three to eight
carbons all let to excellent yields of the desired products 4a –
4d. Using commercially available perfluoroisopropyl iodide, the
perfluoroisopropylated 4-phenylbutene 4e was obtained in
quantitative yield selectively as E-isomer. Notably,
perfluoroalkyl bromides underwent similar perfluoroalkylations
in the presence of this Ni catalyst. For example, 4-bromo-
perfluorobutyl bromide was successfully used to functionalize
3,3-dimethylbutene in good yield to give 4f.
Among the possible fluoroalkylation reactions, trifluoro-
methylations are synthetically amongst the most interesting
ones. Hence, we studied such reactions using either CF3Br or
CF3I. In general, both reagents can be used, but CF3I is more
active than CF3Br in the presence of the Ni catalyst.
2 | J. Name., 2012, 00, 1-3
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Trifluoromethylations of structurally diverse alkenes including (Scheme 4): Initially, the air- and water-stable NViiepwreAr-tcicaletOanlylinset
DOI: 10.1039/D0CC06652D
the anti-arrhythmia drug quinidine and isosorbide gave the forms an active Ni(I) species A, which is detected by in situ EPR
corresponding products 4g–4p in up to 97% yield.
spectroscopy (see SI Figure S2). A control experiment (50 mg
catalyst with 0.4 mmol t-BuONa in 0.5 mL perfluorobenzene)
revealed at the same time the formation of 2,2’-
dimethylbiphenyl (GCMS). Then, the Ni(I) species A reacts with
RFX to give the more stable complex B and a perfluoroalkyl
radical, which is again supported by in situ EPR studies (see SI,
Figure S3). After addition of this radical to the alkene substrate,
a new radical species C is formed, this is supposed to have a very
short living time.20 As a major pathway C leads to the respective
1,2-addition product, which eliminates HX via an E2 process.
However, based on the minor formation of 2t, we cannot
exclude a direct perfluoroalkylation pathway, in which C directly
forms the desired product. Finally, the resulting NiIII complex
(dppf)Ni(o-tol)Cl (5 mol%)
t-BuONa (2 equiv)
RF
+
R
FX
R
R
perfluorobenzene (1 mL)
50 ºC, 16 h
3
, 0.5 mmol
1
, 2 equiv
4
RF
Me
Me
CF3
Me
R
Si
RF
Me
C F
Me
4a [a]
R
2
,
FX =
17I, 89%
13I, 95%
8
4c R
C F
9I
4
,
FX =
99% (E/Z = 81:19)
4d R C F
R
CF
FX =
3I
4b [a]
R
C F
,
FX =
6
4h
, R = Me-
88% (E/Z = 84:16)
4i
4f [a]
R
BrC F
,
FX =
8Br, 69%
4
,
FX =
98% (E/Z = 80:20)
4e R CF(CF )
3 2I
7I
3
4g [b]
R
FX =
CF
3Br, 23%
,
, R = Ph-
88% (E/Z = 84:16)
4g R
FX =
CF
3I
,
,
FX =
99% (pure E)
92% (E/Z = 84:16)
CF3
R
regenerates the active nickel(I) complex A.21
CF3
EtO
R
4j
CF
FX =
3I
, R = n-C10H21
70% (E/Z = 87:13)
a) Conversion of 1,2-adduct to the Heck-type product with t-BuONa
OEt
4m R
-
CF
I
,
FX =
3I
CF3
t-BuONa (1 equiv)
CF3
3,3-dimethylbutene (0.5 mL) Me
C10F21
61% (E/Z = 76:24)
C10F21
Me
Me
4k
, R = Cy-, 97%
Me
4l
, R = PhCH2CH2-
50 ºC, 16 h
Me
2a
Me
63% (E/Z = 84:16)
8a
0.2 mmol
, 91%
CF3
O
H
O
HO
H
H
b) Perfluoroalkylation of cyclopentene
dppfNi(o-tol)Cl (5 mol%)
O
N
O
H
C10F21
O
C10F21
O
t-BuONa (2 equiv)
O
+
H
+
C10F
21I
O
HO
solvent (0.5 mL)
50 ºC, 16 h
N
I
8b
, 77%
4p [d]
R
CF
3I
4o [d]
R
CF
3I
4n [c]
R
CF
FX =
,
FX =
,
FX =
2t
, 8%
,
3I
25% (E/Z = 86:14)
76% (E/Z = 90:10)
41%
c) Conversion of 1,2-adduct to the Heck-type product
Scheme 2. Nickel-catalyzed fluoroalkylation of alkenes with different perfluoro-alkyl
reagents. Yields were determined by 19F NMR. [a] 1 mL 3,3-dimethylbutene, no
perfluorobenzene. [b] 0.5 mmol 3,3-dimethylbutene, 5 bar CF3Br, 40 bar N2. [c] 0.5 mmol
alkene, 2 equiv CF3I. [d] DCE as the solvent.
dppfNi(o-tol)Cl (5 mol%)
t-BuONa (2 equiv)
C10F21
C10F21
solvent (0.5 mL)
50 ºC, 16 h
I
8b
2t
not observed
To understand this novel methodology and get mechanistic
insights, a kinetic profile of the perfluorodecylation of 3,3-
dimethylbutene was performed under standard reaction
conditions (5 mol% dppfNi(o-tol)Cl, 2 equiv t-BuONa, 50 °C; see
SI, Figure S1). Notably, the activation of C10F21I is very fast and
full conversion is observed within 10 min. The initially formed
product was identified as the corresponding 1,2-adduct 8a,
which slowly underwent base induced elimination of HI to give
the final product 2a.
d) Radical trap experiment with TEMPO
dppfNi(o-tol)Cl (5 mol%)
t-BuONa (2 equiv)
C10F21
Me
Me
Me
Me
TEMPO (10 mol%)
+
C10
F
21I
perfluorobenzene (1 mL)
50 ºC, 16 h
Me
Me
1a
2 equiv
0.2 mmol
2a
not observed
Scheme 3. Mechanistic control experiments
[dppfNi(o-tol)Cl]
Control experiments revealed that this E2-elimination process
is solely mediated by the strong base and does not need the
presence of the nickel catalyst (Scheme 3a). To understand the
low product yields in case of cyclic olefins, the
perfluorodecylation of cyclopentene was re-investigated in
more detail. In fact, fast conversion of the perfluoroalkylation
reagent occurred, too. However, only small amounts of the
desired olefin 2t (8%) were obtained. Instead, the
corresponding 1,2-adduct 8b could be isolated as the major
product (77%). Notably, 8b failed to undergo further
transformation under standard reaction conditions, which is
explained by the lower acidity of the secondary alklyl carbon
substituted with the perfluoroalkyl group (Schemes 3b and 3c).
Next, the benchmark reaction was completed in the presence
of 10 mol% TEMPO to study the importance of radical
intermediates in this process. As shown in Scheme 3d neither
the desired product nor the 1,2-adduct 8a are observed after
adding TEMPO. Thus, the following catalytic cycle is proposed
Indirect addition-
elimination mechanism
Direct perfluoroalkylation
detected by GC-MS
[NiI]X
baseHX
A
base
RF
R
•RF
III X
X
D
baseH
H[Ni ]
2
R
RFX
base
RF
•
RF
R
R
X
C
RF
R
•
RF
[NiII]X2
B
R
X = Cl, Br, I
C
Scheme 4. Proposed catalytic mechanism
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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6
(a) R. J. Lundgren, M. Stradiotto, Angew. Chem. Int. Ed. 2010, 49,
In conclusion, we have developed a mild and versatile protocol
for the fluoroalkylation of alkenes including synthetically
interesting trifluoromethylations. Using terminal olefins
including a variety of functionalized ones, the corresponding
fluoroalkylated alkenes are obtained in good yields and E/Z-
selectivity. Advantageously, the presented nickel catalyst is
comparatively inexpensive as well as air- and moisture-stable.
Mechanistic investigations reveal that this transformation
mainly proceeds via fast formation of the 1,2-adduct, which
subsequently undergoes slow base-catalyzed elimination. EPR
measurements also provide evidence for the importance of
radical intermediates.
View Article Online
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8
9
We are grateful for the financial support from the State
Mecklenburg-Western Pomerania, the federal German Ministry
BMBF and LONZA.
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Conflicts of interest
There are no conflicts to declare.
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DOI: 10.1039/D0CC06652D
CF3
RF
or
dppfNi(o-tol)Cl
(5 mol%)
R
R
R
Ph
CF
3X
NaOtBu (2 - 4 equiv)
or
P
or
+
or
Cl
50 ºC, 16 h
RF
R
FX
Ph
NiII
Ph
Fe
P
38 examples,
C F
Yield up to 99%
E selectivity up to 100%
Ph
R
C F
8
C F
6
C F
8Br,
FX =
21I,
17I,
13I,
9I,
10
4
C3F CF(CF ) BrC F
7I, 3 2I,
dppfNi(o-tol)Cl
4
CF
CF CF
3I, 3Br
3X =
Fluoroalkylated olefins made easy: A mild and selective nickel-catalyzed fluoroalkylation
including trifluoromethylation of alkenes was developed. Various fluorinated olefins, including
natural products, pharmaceuticals, and variety of synthetic building blocks were provided in good
to excellent yields.