Site-Selective C(sp3)–H Functionalization of Fluorinated Alkanes Driven by Polar Effects Using a Tungstate Photocatalyst

Article abstract of DOI:10.1002/ejoc.201901135

The TBADT-catalyzed C(sp³)–H functionalization of perfluorophenyl- and perfluoroalkyl-substituted alkanes was studied to determine how the fluorous substituents affect site-selectivity. Alkylation of alkyl-substituted perfluorobenzene avoids α-C–H bonds, unlike their alkylbenzene counterparts, allowing site-selective functionalization of C–H bonds remote to the aromatic ring. Alkylation of alkanes having a perfluoroalkyl group also avoided α-C–H bonds. Radical polar effects in the S_H2 transition states could explain this avoidance of α-C–H functionalization.

Full text of DOI:10.1002/ejoc.201901135

A Journal of
Accepted Article
Title: Polar Effects Driven Site-Selective C(sp3)-H Functionalization of
Fluorinated Alkanes by TBADT Photo Catalyst
Authors: Takahide Fukuyama, Tomohiro Nishikawa, and Ilhyong Ryu
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201901135
Link to VoR: http://dx.doi.org/10.1002/ejoc.201901135
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10.1002/ejoc.201901135
European Journal of Organic Chemistry
COMMUNICATION
Polar Effects Driven Site-Selective C(sp3)-H Functionalization of
Fluorinated Alkanes by TBADT Photo Catalyst
Takahide Fukuyama,[a] Tomohiro Nishikawa,[a] and Ilhyong Ryu*[a,b]
Abstract: The TBADT-catalyzed C(sp3)-H functionalization of
perfluorophenyl- and perfluoroalkyl-substituted alkanes was studied
to determine how the fluorous substituents affect site-selectivity.
Alkylation of alkyl-substituted perfluorobenzene avoids -C-H bonds,
unlike their alkylbenzene counterparts, allowing site-selective
functionalization of C-H bonds remote to the aromatic ring.
Alkylation of alkanes having a perfluoroalkyl group also avoided -C-
H bonds. Radical polar effects in the SH2 transition states could
explain this avoidance of -C-H functionalization.
development of methods to introduce fluorine or fluorine-
containing units to organic molecules is important,12 so, too, is
developing a method for the direct C-H functionalization of
readily available organofluorine compounds. Subsequently, we
became convinced that the lack of -C-H functionalization in
pyridyl alkanes might also occur in alkylbenzenes with fluorine or
fluorine-containing groups in the aromatic ring, and the synthesis
of a new class of organofluorine-containing compounds could be
possible via site-selective C-H functionalization (Scheme 1).
Herein, we report the results of a systematic study using
structurally varied perfluoroalkyl or perfluoroaryl-substituted
alkanes.
Introduction
Site-selective catalytic functionalization of C(sp3)-H bonds is one
of the most important challenges in organic chemistry.1,2 Under
photo-irradiation
conditions,
tetrakis(tetrabutylammonium)
decatungstate (TBADT: (Bu4N)4W10O32) abstracts hydrogen
from C(sp3)-H bonds to generate alkyl radicals, which can be
applied to a variety of C-H functionalization reactions including
cascade radical reactions.3,4 We have been curious about the
effect imparted by a given functionality on an alkane scaffold in
terms of site-selectivity in the C-H cleavage reaction promoted
by TBADT and consequently, we were able to find noteworthy
examples of site-selectivity for alcohols, ketones, esters, and
nitriles, in which the SH2 (bimolecular homolytic substitution)
transition states between a C-H bond and a decatungstate anion
are highly affected by radical polar and steric effects, which
render the functionalization of C(sp3)-H bonds site-selective.5,6 In
a pursuit of examples including hetero-aromatic rings, we
recently
studied
the
TBADT-photocatalyzed
C(sp3)-H
functionalization of alkylpyridines.7 Unlike their alkylbenzene
counterparts, we were able to demonstrate an avoidance of the
-C-H functionalization of alkylpyridines (Scheme 1).
Although organofluorine compounds are rare in nature,
they have come to play increasingly significant roles in material
science,8
pesticides,9
fluoro-liquid
crystals,10
and
pharmaceuticals.11 The existence of one or more fluorine atoms
in a drug molecule could have a decisive effect in changing its
biological and chemical properties. Therefore, while the
Scheme 1. Concept of this work: Polar-effects driven C-H functionalization of
organofluorine compounds.
[a]
Prof. T. Fukuyama, T. Nishikawa, Prof. I. Ryu
Department of Chemistry, Graduate School of Science
Osaka Prefecture University
Sakai, Osaka 599-8531 (Japan)
E-mail: ryu@c.s.osakafu-u.ac.jp
http://www.c.s.osakafu-u.ac.jp/~ryu/?lang=en
Prof. I. Ryu
Academic titles, Initial(s), Surname(s) of Author(s)
Department of Applied Chemistry
National Chiao Tung University
Results and Discussion
[b]
At the outset we examined site-selectivity in the C-H
functionalization of perfluorohexyl alkanes by TBADT
photocatalysis. Due to the low solubility of perfluoroalkanes to
acetonitrile, we used a 1:1 mixed solvent of acetonitrile and
Hsinchu 30010, Taiwan
perfluorohexane for this study. When
acetonitrile and perfluorobenzene,
a
1:1 solution of
containing
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejoc.201901135
European Journal of Organic Chemistry
COMMUNICATION
-
cat
d
perfluorohexylbutane (1a) (10 equiv), dimethyl maleate (2a), and
R1
R1
R1
H
4
mol% of TBADT was irradiated by black light (peak
d+
d+
d+
Rf
Rf
H
wavelength: 352 nm) for 48 h, C-H functionalization proceeded
at the -, -, and -positions to give a mixture of 3a-, 3a- and
3a- in a ratio of 4/86/10 (Table 1, entry 1). The reaction of 5
equivalents of 1a with 2a gave lower yield of the products with
similar selectivity. The reaction of 4-perfluorohexyl-substituted
isopentane 1b with 2a proceeded with complete site-selectivity
at the methine C-H bond to give 3b- as the sole product (entry
Rf
H
cat
d-
cat
d-
TS-A
unfavorable TS
TS-B
less favorabole TS
TS-C
favorabole TS
Figure 1. Possible TSs and polar effects.
2).
In the case of the corresponding alkanes with a
perfluorooctyl group, a similar level of site-selectivity was
observed (entries 3 and 4). In all cases, -functionalized
products were not formed, which suggested that polar effects
work to destabilize the SH2 transition states.
Figure 1 illustrates the possible SH2 transition states in the
reaction of perfluoroalkyl alkanes with the decatungstate anion,
which is regarded as akin to huge oxygen-centered radicals that
It was apparent that a perfluoroalkyl group avoided -C-H
functionalization in perfluoroalkyl-substituted alkanes, and,
therefore, we decided to study the C-H functionalization of
fluorinated aromatic-substituted alkanes. The results are
summarized in Table 2. The TBADT-catalyzed photo reaction of
1,3-difluoro-5-propylbenzene (1e) with fumaronitrile (2b) in
acetonitrile gave a mixture of an -alkylated product (3e- , a
are thought to be nucleophilic.
TS-A would be highly
destabilized by an adjacent electron-withdrawing perfluoroalkyl
group. TS-B, available for -functionalization, would be slightly
destabilized by the induction of a perfluoroalkyl group via an -
-functionalization
-alkylated product (3e-
and a -alkylated product (3e- in
a 50% total yield with an // ratio of 60/32/8 (Table 2, entry 1).
In a similar manner, ortho-fluoro-propylbenzene (1f) gave a
similar set of three products in a 30% total yield with a ratio of
55/38/7 (Table 2, entry 2). We then examined p-trifluoromethyl-
substituted propylbenzene (1g), which gave a 53% yield of
//productsin a 53/40/7 ratio (Table 2, entry 3). By contrast,
however, 2,3,4,5,6-pentafluoropropylbenzene (1h) gave no -C-
H alkylated product, but instead gave mainly a -alkylated
product, /
preferentially proceeded via a favorable TS-C.
Table 1. TBADT-photocatalyzed C-H functionalization of perfluoroalkyl
alkanes[a]
TBADT (4 mol%)
Black light (15 W x 2, Pyrex)
R1
R1
CO2Me
CO2Me
+
Rf
CO2Me
CO2Me
Rf
CH3CN (1 mL), C6F6 (1 mL)
48 h
manner,
the
reaction
of
2,3,5,6-tetrafluoro-4-
R' = H, CH3
(trifluoromethyl)benzene (1i) avoided -C-H functionalization to
give an 86/14 mixture of β- and -alkylated products (Table 2,
entry 5). The use of 2,3,5,6-tetrafluoro-4-(trifluoromethyl)-iso-
butylbenzene (1j) (Table 2, entry 6) produced a high level of
methine C-H selective functionalization (90/10). The reaction of
1,2,4,5-tetrafluoro-3-isopentyl-6-(trifluoromethyl)benzene with 1k,
which has a methine C-H at the -position, gave -alkylated
product 3k- selectively (Table 2, entry 7). The difference in
reactivity between the two methine-containing substrates 1j and
1k is ascribed to a partial destabilization caused by inductive
polar effects, which would be more effective with a closer -
position.
1a-d
2a
3a-3d
10 equiv
0.25 mmol
Entry
1
Fluorinated alkanes 1
Product
Yield[b]
39%
86
C6F13
CO2Me
CO2Me
C6F13
3a-g
10
4
1a
2
3
34%
23%
We also examined fluorinated alkylpyridines 1k, 1l, 1m,
C6F13
CO2Me
CO2Me
3b-g
C6F13
and
1n
(entry
8-11).
The
(1l)
reaction
and
of
2,3,5,6-
2,3,5,6-
tetrafluoropropylpyridine
100
1b
tetrafluoroisobutylpyridine (1m) avoided -C-H functionalization
to give a mixture of - and -alkylated products with ratios of
83/17 and 92/8, respectively (Table 2, entries 8 and 9), with
results akin to those of non-fluorinated alkylpyridines.10 In the
case of 2,3,5,6-tetrafluorobutylpyridine (1n), alkylation took
place preferentially at the -position (Table 2, entry 10). When
2,3,5,6-tetrafluoroisopentylpyridine (1o) was used, alkylation
took place selectively at the -methine C-H bond to give 3o- as
the sole product (Table 2, entry 11).
88
C8F17
CO2Me
CO2Me
3c-g
C8F17
6
6
1c
4
58%
C8F17
CO2Me
CO2Me
3d-g
C8F17
1d
100
[a] Reaction Conditions: 1 (2.5 mmol), 2a (0.25 mmol), TBADT (4 mol %),
MeCN (1 mL), C6F6 (1 mL). Irradiation was performed using Black Lights (15
W x 2, Pyrex) for 48 h. [b] Yield after flash chromatography on SiO2.
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10.1002/ejoc.201901135
European Journal of Organic Chemistry
COMMUNICATION
10
11
F
2a
2a
63%[f]
23
F
5
F
F
N
CO2Me
N
CO2Me
Table 2. TBADT-photocatalyzed C-H/C-C conversion of fluorinated
alkylarenes with electron-deficient alkenes[a]
F
F
F
F
F
3n-g
1n
R1
TBADT (4 mol%)
Black light (15 W x 2, Pyrex)
72
R2
E
R1
R2
H
E
Ar
+
E
Ar
m
F
40%
100
m
E
CH3CN (1 mL), 48 h
F
F
1
N
CO2Me
2
E = CO2Me, CN
N
3
10 equiv
CO2Me
0.5 mmol
F
F
F
F
1o
3o-g
En
try
Arylalkane 1
Alkene 2
Major product 3
Total
yield[b]
[a] Reaction conditions: 1 (5.0 mmol), 2 (0.5 mmol), TBADT (4 mol%), MeCN
(1 mL). Irradiation carried out using a Black light (15 W x 2, Pyrex) for 48 h. [b]
Isolated yield after flash chromatography on SiO2. [c] 5 equivalents of 1 were
used. [d] Xe lamp (300 W, Pyrex) was used as a light source. [e] MeCN (3
mL) was used. [f] 52 h.
50%[c]
NC
F
F
1
CN
32
2b
F
F
CN
1e
NC
3e-a
8
60
38
F
F
2
3
2b
2b
30%[c]
CN
NC
3f-a
1f
7
55
53%[c]
40
CF3
CF3
CN
NC
3g-a
1g
7
53
84
F
F
F
4
34%
CO2Me
F
F
F
F
F
CO2Me
2a
F
CO2Me
CO2Me
3h-b
F
Scheme 2. Possible Catalytic Mechanism.
1h
16
86
A possible catalytic reaction mechanism is depicted in Scheme 2.
Photo-excited decatungstate anion (W10O324-*) has an
electronegative oxygen character, but would not abstract-
hydrogen leading to radical A and only reluctantly abstracts -
hydrogen due to a high level of inductive effects of the
perfluorohexyl group. As a result, abstraction of -hydrogen
F
F
5
6
2a
2a
34%
CF3
F
F
CF3
F
F
CO2Me
CO2Me
F
1i
F
F
3i-b
14
54%[d]
F
should preferentially give radical B. The radical
B then
CF3
F
F
CF3
F
F
10
undergoes addition to electron-deficient alkene 2a to form an
adduct radical. Back-hydrogen atom transfer from the reduced
form of the tungstate anion to the radical gives the desired
product 3a, thus restoring the starting TBADT catalyst.
CO2Me
CO2Me
3j-b
F
F
F
1j
90
We believe that the different site-selectivity for
propylarenes, 1e, 1f, 1g, 1h, 1i, and 1l, could be ascribed to
polar effects in the SH2 transition states, and this led us to
consider comparing the 1H-NMR chemical shifts of benzylic
protons (-protons) with the 13C-NMR chemical shifts of -
7
8
9
2a
2a
2a
44%[d]
F
100
CF3
F
F
CF3
F
F
CO2Me
CO2Me
F
1k
F
3k-g
1
carbons. Typically, the H-NMR signals of benzylic methylene
F
F
protons with electron-withdrawing arenes are observed in lower-
field chemical shifts. For example, whereas the benzylic proton
of propylbenzene is observed at 2.58 ppm, the benzylic proton
of p-nitropropylbenzene in CDCl3 is observed at 2.70 ppm. On
43%
83
F
F
N
F
N
F
CO2Me
CO2Me
F
F
F
the other hand,
a
13C-NMR signal of the -carbon of
1l
3l-b
17
propylarenes with electron-withdrawing arenes has been
43%[e]
F
1
reported at higher-field chemical shifts.13 Figure 2 shows the H
F
F
8
N
F
N
F
and 13C NMR chemical shifts of propylarenes and the possible
1
CO2Me
CO2Me
3m-b
SH2 transition states of H-abstraction at the -position. The H-
F
1m
F
NMR signals of benzylic protons for 1h, 1i, and 1l, which
avoided -C-H functionalization, were observed at higher
chemical shifts (2.67-2.81 ppm) compared with those of 1e, 1f,
92
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10.1002/ejoc.201901135
European Journal of Organic Chemistry
COMMUNICATION
and 1g (2.57-2.64 ppm). In a similar manner, the 13C-NMR
signals of -carbons for 1h, 1i, and 1l, were also observed at
higher chemical shifts (21.9-22.6 ppm) compared with those of
1e, 1f, and 1g (23.3-24.3 ppm). These observations agree with a
This work was supported by a Grant-in-Aid (B) (19H02722) from
the JSPS and Scientific Research on Innovative Areas 2707
Middle molecular strategy (JP15H05850) from the MEXT.
scenario
whereby
pentafluorophenyl,
p-
Keywords: Photocatalyst • C-H functionalization•Site-selective •
Radical polar effect • fluorine-containing compounds
trifluoromethyl(tetrafluorophenyl), and 4-tetrafluoropyridyl groups
are sufficiently electron withdrawing to exert radical polar effects
that allow them to avoid  C-H functionalization.
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In summary, we have demonstrated that TBADT-photocatalyzed
C-H functionalization of perfuloroalkyl- and perfluoroarene-
substituted alkanes exhibits site-selectivity that results in an
avoidance of -C-H functionalization, unlike the corresponding
alkylbenzenes. On the other hand, the degree of site-selectivity
in aromatic alkanes is dependent on the number of fluorine
substituents on the ring, and neither mono- and difluorinated
benzene rings nor trifluoromethyl-substututed benzene rings
showed -CH avoidance. Radical polar effects in the SH2
transition states can explain the unfavorable -C-H
functionalization and we believe that polar-effects-driven design
for site-selective C(sp3)-H functionalization could be extended to
other substrates, and research along this line is ongoing in our
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Acknowledgments
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COMMUNICATION
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
(Bu4N)4W10O32
86%
Black light
The TBADT-catalyzed C(sp3)-H
C-H Functionalization
E
functionalization of perfluorophenyl-
E
C6F13
E
C6F13
Takahide Fukuyama
Tomohiro Nishikawa
Ilhyong Ryu*
CH3CN
and perfluoroalkyl-substituted
alkanes was investigated. Alkylation
of alkanes having a perfluoroalkyl
group and alkyl-substituted
perfluorobenzenes avoided -C-H
bonds. Radical polar effects in the
SH2 transition states could explain
this avoidance of -C-H
E
E = CO2Me, CN
F
F
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E
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Polar Effects Driven Site-Selective
C(sp3)-H Functionalization of
Fluorinated Alkanes by TBADT
Photo Catalyst
functionalization.
*one or two words that highlight the emphasis of the paper or the field of the study
Layout 2:
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