Hydrodefluorination of Fluoroarenes Using Hydrogen Transfer Catalysts with a Bifunctional Iridium/NH Moiety

Article abstract of DOI:10.1021/acscatal.6b01590

The hydrodefluorination of fluoroarenes with transfer hydrogenation catalysts using 2-propanol or potassium formate is described. With the aid of metal/NH cooperation, the C-N chelating Ir complexes derived from benzylic amines can efficiently promote the reduction involving the C-F bond cleavage under ambient conditions even in the absence of hydrosilanes or H₂ gas, leading to the partially fluorinated products in good yields and with high selectivity.

Full text of DOI:10.1021/acscatal.6b01590

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Letter
Hydrodefluorination of Fluoroarenes Using Hydrogen
Transfer Catalysts with a Bifunctional Iridium/NH Moiety
Asuka Matsunami, Shigeki Kuwata, and Yoshihito Kayaki
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.6b01590 • Publication Date (Web): 30 Jun 2016
Downloaded from http://pubs.acs.org on July 2, 2016
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ACS Catalysis
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Hydrodefluorination of Fluoroarenes Using Hydrogen Transfer Cata-
lysts with a Bifunctional Iridium/NH Moiety
Asuka Matsunami†, Shigeki Kuwata†‡, and Yoshihito Kayaki*†
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† Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of
Technology, 2-12-1-E4-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan
‡ PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
from the primary and secondary alcohols to the carbonyl com-
ABSTRACT: The hydrodefluorination of fluoroarenes
pounds (Scheme 1).10 Significant progress in the applications
with transfer hydrogenation catalysts using 2-propanol
of this bifunctional catalysis has been made by structural mod-
ification of the prototype N-sulfonylated diamine complexes.
For example, we have found that a family of half-sandwich Ru,
or potassium formate is described. With the aid of met-
al/NH cooperation, the C–N chelating Ir complexes de-
rived from benzylic amines can efficiently promote the
reduction involving the C–F bond cleavage under ambi-
ent conditions even in the absence of hydrosilanes or H2
gas, leading to the partially fluorinated products in good
yields and with high selectivity.
Rh, and Ir complexes with a C–N chelating benzylic amine
moiety behave as highly efficient hydrogen transfer promot-
ers.11,12 The enhancement of hydrogen delivery is possibly
induced by the nucleophilicity of the hydrido ligand, originat-
ing from the pronounced -donor nature of the chelating car-
bon atom. As a part of our ongoing efforts to extend the utility
of the privileged hydrogen transfer catalyst, we disclose here
the selective hydrodefluorination of perfluoroarenes under
transfer hydrogenation conditions using 2-propanol or formate
salts.
KEYWORDS: Iridium catalysis, transfer hydrogenation,
hydrodefluorination, fluoroarenes, formate salts
Due to the growing demands for organofluorine molecules
possessing unique and value-added properties, transformation
of perfluorinated compounds has been extensively studied as a
promising synthetic approach for obtaining partially fluorinat-
ed skeletons that allows fine tuning of the functional features
as well as further derivatization.1 In particular, much attention
has been directed to the catalytic conversion of a carbon–
fluorine bond into a carbon–hydrogen bond, referred to as
hydrodefluorination.2 Since the seminal report of Milstein on a
homogeneous catalysis of hydrodefluorination based on the
carbon-fluorine bond cleavage of hexafluorobenzene by a
silylrhodium(I) complex in 1994,3 various transition metal
complexes have emerged as potential catalysts. Most of these
systems employed fluorophilic reducing agents including hy-
drosilanes4 and aluminum hydrides5 to facilitate the hydride
substitution, but were inevitably accompanied by formation of
undesirable reaction side products. Other catalysts applied for
the H2-hydrogenation of fluoroarenes required pressurized
hydrogen or resulted in modest activity under mild condi-
tions.6 Transfer hydrogenation using H2 equivalents such as
alcohols and formic acid has been recognized as a beneficial
alternative process7 that overcomes these shortcomings. Re-
cently, transfer hydrogenation of perfluoroarenes was execut-
ed in CH3CN at 80 °C by using sodium formate in the pres-
ence of [Co(PMe3)4] albeit with a limited turnover number up
to 8.57.8 Weaver et al. reported a photocatalytic approach to
the hydrodefluorination with 2-phenylpyridine-Ir complex in
the presence of amines as sacrificial reagents.9
Scheme 1. Hydrogen Transfer to Ketones Based on the
Amine/Amido Interconversion
We initially investigated the reaction of pentafluoropyridine
(1a) as a benchmark substrate in the presence of a bifunctional
C–N chelating amido complex (3) derived from cumylamine
with a substrate/catalyst ratio of 100 in 2-propanol at 30 C.
As summarized in Table 1, a smooth hydrodefluorination pro-
ceeded to afford 2,3,5,6-tetrafluoropyridine (2a) in 30% yield
after 5 h (entry 1). Addition of a base to abstract the releasing
hydrogen fluoride proved to be effective for accelerating the
reaction. Among the tested carbonate salts (entries 2-5),
K2CO3 significantly improved the product yield to 87% with a
perfect selectivity (entry 4). A favorable result with CaO ra-
ther than with CaCO3 (entries 5 and 6) also indicated that a
higher catalytic activity is presumably obtained with increas-
ing the basicity of the additive; however, the addition of KOH
gave rise to competitive formation of 4-hydroxy-2,3,5,6-
tetrafluoropyridine in 62% yield via nucleophilic substitution
with OH– (entry 7). Triethylamine also contributed to promot-
ing the reaction in 90% yield within 1 h (entry 8). It is note-
Metal-ligand cooperation in protic amine complexes has
been exploited for the redox catalysis in which interconversion
between NH(amido) and NH2(amine) ligands on the metal
center proceeds concurrently with a smooth hydrogen transfer
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worthy that further improvement was achieved with HCOOK stracts HF to drive the catalytic cycle with forming the catalyt-
1
to furnish 2a in 94% yield (entry 9).
ically active amidoiridium intermediate.
2
3
4
5
Table 1. Catalytic Hydrodefluorination of 1a in 2-Propanol
Using Ir Catalystsa
Table 2. Catalytic Hydrodefluorination of 1a with Formate
Salts a
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7
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9
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entry
base
—
time, h % yieldb
1
2
3
4
5
6
7
8
9
5
1
1
1
1
1
1
1
1
30
56
84
87
43
c
Li2CO3 c
Na2CO3
c
K2CO3c
CaCO3
CaOc
66
KOHd
38 (62e)
90
d
NEt3
HCOOKd
94
entry catalyst time, h
% yieldb
aReaction conditions: The reaction was carried out with 1a (0.5 mmol) and
b
1
2
3
4
5
6
7
8
1
1
5
5
5
5
5
5
100
97
0
4
5
6
7
8
9
10
11
catalyst 3 (0.005 mmol) in 2-propanol (5.0 mL) at 30 °C. Determined by
19F NMR using trifluoromethylbenzene as an internal standard. cA half
d
molar amount (0.25 mmol) of base was used. An equimolar amount (0.5
mmol) of base was used. The yield of a side product (4-hydroxy-2,3,5,6-
tetrafluoropyridine).
e
1
10
10
4
The fascinating outcome for the reaction with the formate
salt prompted us to explore the hydrogen transfer without 2-
propanol. When we submitted 1a to the transfer hydrogenation
using HCOOK, an optimum result was obtained in a 1:1
mixed solvent of DME and water (see Supporting Information,
Table S1). The precursory C–N chelating chloroiridium com-
plexes, [Cp*Ir(Cl){2(N,C)-NH2CR2-2-C6H4}] (R = CH3, 4; R
= C6H5, 5), could promote the hydrodefluorination as well13, as
shown in entries 1 and 2 of Table 2. The reaction was com-
pleted with 1 mol% of 4 in the presence of 2 equiv of HCOOK
at 30 °C within 1 h. The positive effect of the C–N chelating
skeleton was confirmed by the fact that [IrCl(-Cl)Cp*]2 (6,
entry 3) and a N–N chelating iridium complex (7, entry 4) did
not catalyze the hydrodefluorination. The C–N chelating com-
plexes derived from N,N-dimethylbenzylamine and 2-
phenylpyridine (8 and 9) contributed little to the catalysis,
supporting the important role of the metal/NH moiety in the
acceleration of the hydrogen transfer (entries 5, 6). The Ru and
Rh analogues (10 and 11) exhibited poor catalytic activity
(entries 7 and 8). Notably, the turnover number (TON) for the
hydrodefluorination of 1a exceeded 250 at the catalyst load-
ings of 0.2 mol% after 1 h.
6
aReaction conditions: 1a (0.5 mmol), catalyst (0.005 mmol per metal), and
sodium formate (1.0 mmol) in DME (2.5 mL) and water (2.5 mL) at 30 °C.
bDetermined by 19F NMR using trifluoromethylbenzene as an internal
standard.
Scheme 2. Stoichiometric Reaction of Hydrido Complex 12
and Pentafluoropyridine 1a
Having obtained the optimal catalyst, we explored the sub-
strate scope of this hydrodefluorination with a variety of high-
ly electron-deficient perfluoroarenes as shown in Table 3.
Similar to 1a listed in entry 1 of Table 2, pentafluorobenzo-
nitrile
(1b)
was
transformed
into
2,3,5,6-
tetrafluorobenzonitrile (2b) within 1 h as a sole product (entry
1). The reduction of N,N-dimethyl pentafluorobenzenesulfon-
In a separate NMR experiment, treatment of a catalytic in-
termediate model, [Cp*Ir(H){2(N,C)-NH2C(CH3)2-2-C6H4}]
(12), with a slight excess amount of 1a in the absence of base
in THF-d8 at room temperature resulted in prompt formation
of 2a, which was characterized by 1H and 19F NMR spectra. In
conjunction with disappearance of the hydride species, the 19F
NMR spectrum displayed a new singlet peak at –100.6 ppm
that is presumably ascribed to the fluoride anion released from
1a, implying the simultaneous formation of a cationic species
13 or a neutral fluoride complex (Scheme 2 and Figure S1).
Under the catalytic conditions, the added base smoothly ab-
amide
(1c)
afforded
the
corresponding
2,3,5,6-
tetrafluorobenzenesulfonamide (2c) in 92% yield (entry 2). In
contrast, pentafluoronitrobenzene (1d) reacted at the 4- and 2-
positions to give a mixture of monohydrodefluorinated prod-
ucts (p- and o-2d) in 61% and 20% respectively, along with a
slight amount of dihydrodefluorinated products of 2,3,5-
trifluoronitrobenzene and 3,4,5-trifluoronitrobenzene (entry 3).
Although the reaction of octafluorotoluene (1e) and methyl
pentafluorobenzoate (1f) required a higher catalyst loading to
2 mol% and a prolonged reaction time to 2 h, the hydrodefluo-
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ACS Catalysis
Table 3. Catalytic Hydrodefluorination of Perfluoroarenes Using Potassium Formate
1
2
3
4
5
6
7
8
9
entry
1
substrate
catalyst, mol%
1
time, h
1
products, % yieldb,c
10
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12
13
14
15
16
17
18
19
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2b, 100
1b
2
3
4
5
1
1
2
2
1
1
2
2
2c, 92
p-2d, 61
2e, 97
1c
1d
1e
o-2d, 20
p-2f, 88
o-2d, 2
1f
6
7
1
1
100
1g
1h
1
12
12
0
8
9
10
2i, 64
2i’, 21
1i
10
1
12
1
2j, 66
2j’, 24
2k’, 2
1j
10d
11e
2k, 91(88)
1k
1
1
2k’, 100(86)
1k
aReaction conditions: 1 (0.5 mmol), catalyst (0.005 mmol), and sodium formate (1.0 mmol) in DME (2.5 mL) and water (2.5 mL) at 30 °C. bDetermined by
19F NMR using trifluoromethylbenzene as an internal standard. cIsolated yield in parenthesis. dHCOOK (0.5 mmol). eHCOOK (1.5 mmol).
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rination at the 4-position proceeded with a considerably high aspects of this catalysis, expanding the substrate scope, and
1
2
3
4
5
6
7
8
selectivity (entries 4 and 5). The cyano, nitro and ester groups
were tolerated under these hydrogen transfer conditions,
whereas the ketonic carbonyl group in 2,3,4,5,6-
pentafluoroacetophenone (1g) was reduced in preference to
the hydrodefluorination to form the corresponding alcoholic
product (entry 6). A substrate (1h) containing electron-
donating OCH3 group remained intact after the reaction under
the identical conditions (entry 7). Based on these results, it is
clear that the attachment of electron deficient substituents is
effective for facilitating the nucleophilic attack of the iridium
hydride. Decafluorobiphenyl (1i) was also reducible at a rela-
tively high catalyst concentration (10 mol%) to give 4-
hydrononafluorobiphenyl (2i, 64% yield) accompanied with
4,4’-dihydrooctafluorobiphenyl (2i’, 21% yield) as a doubly-
hydrodefluorinated product (entry 8). Notably, in the reaction
of octafluoronaphthalene (1j), the C–F bond cleavage took
place selectively at the -position, yielding 2-
applications to other challenging substrates are ongoing.
AUTHOR INFORMATION
Corresponding Author
*E-mail for Y. K.: ykayaki@o.cc.titech.ac.jp.
Notes
9
The authors declare no competing financial interest.
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ASSOCIATED CONTENT
Supporting Information.
Experimental details and characterization data, and NMR
spectra of the products.Supporting Information is available
free of charge on the ACS Publications website at
http://pubs.acs.org.
hydroheptafluoronaphthalene
(2j)
and
2,6-
dihydrohexafluoronaphthalene (2j’) in 66% and 24% (entry 9).
Such a consecutive hydride substitution could be controlled in
the reaction of tetrafluorophthalonitrile (1k). The mono
defluorinated product (2k) was obtained in 91% yield by using
an equimolar amount (0.5 mmol) of potassium formate (entry
10). Addition of three molar amounts of the formate salt led to
ACKNOWLEDGMENT
This study was financially supported by JSPS KAKENHI
Grant Number 24350079 and 26621043 and in part by
Grant for Basic Science Research Projects from The Sumi-
tomo Foundation and by Grant for Engineering Research
from Mizuho Foundation for the Promotion of Sciences.
further
hydrodefluorination
to
provide
3,6-
difluorophthalonitrile (2k’) with perfect selectivity (entry 11).
These products (2k and 2k’) could be isolated in 88% and
86% respectively after purification by silica gel column chro-
matography.
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In conclusion, we achieved the efficient hydrodefluorination
of perfluoroarenes by transfer hydrogenation catalysts pos-
sessing metal/NH cooperating functions. These findings have
significant implications for the design of practical hydro-
defluorination catalysts without using hydrosilanes or hydro-
gen gas. The transfer hydrogenation system is characterized by
excellent catalytic performance even at the ambient tempera-
ture and offers advantages in terms of operational simplicity
using mild reducing agents. The strong -donating nature of
the C–N chelating ligands should play a pivotal part in the
catalysis, giving rise to the smooth hydride transfer from the
nucleophilic hydrido complexes to the fluoroarene substrate.
Further studies directed towards elucidating the mechanistic
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(13) The activity of 4 was comparable to that of 3 in the hydro-
defluorination using potassium formate.
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