Trifluoroethoxy-Coated Subphthalocyanine affects Trifluoromethylation of Alkenes and Alkynes even under Low-Energy Red-Light Irradiation

Article abstract of DOI:10.1002/open.201600172

Photoredox chemical reactions induced by visible light have undergone a renaissance in recent years. Polypyridyl dyes such as Ir(ppy)₃ and Ru(bpy)₃ are key catalysts in this event, and blue- or white-light irradiation is required for the chemical transformations. However, it remains a challenge to achieve reactions under the lower energy of red light. We disclose, herein, that trifluoroethoxy-coated subphthalocyanine realizes the red-light-driven trifluoromethylation of alkenes and alkynes with trifluoromethyl iodide in good-to-high yields. Perfluoroalkylations were also achieved under red light. The reaction mechanism is discussed with the support of UV/Vis spectroscopy and cyclic voltammetry of trifluoroethoxy-coated subphthalocyanine. Light irradiation/dark study also supports the proposed mechanism.

Full text of DOI:10.1002/open.201600172

DOI: 10.1002/open.201600172
Trifluoroethoxy-Coated Subphthalocyanine affects
Trifluoromethylation of Alkenes and Alkynes even under
Low-Energy Red-Light Irradiation
Kohei Matsuzaki, Tomoya Hiromura, Etsuko Tokunaga, and Norio Shibata*[a]
Photoredox chemical reactions induced by visible light have
undergone a renaissance in recent years. Polypyridyl dyes such
as Ir(ppy)3 and Ru(bpy)3 are key catalysts in this event, and
blue- or white-light irradiation is required for the chemical
transformations. However, it remains a challenge to achieve re-
actions under the lower energy of red light. We disclose,
herein, that trifluoroethoxy-coated subphthalocyanine realizes
the red-light-driven trifluoromethylation of alkenes and alkynes
with trifluoromethyl iodide in good-to-high yields. Perfluoroal-
kylations were also achieved under red light. The reaction
mechanism is discussed with the support of UV/Vis spectrosco-
py and cyclic voltammetry of trifluoroethoxy-coated subphtha-
locyanine. Light irradiation/dark study also supports the pro-
posed mechanism.
damage to eyes (retina) by the blue light.[3] Green light
(500 nm), however, is one-tenth as hazardous to the retina as
blue light.[4]
The move towards an “all-green” process by using lower
power light for chemical reactions remains a challenge to ach-
ieve non-toxic, eco-friendly, mild, and selective transformations.
In this context, red light has gained attention for its application
in “greener” visible-light photoredox reactions.[5] Red light has
the benefits of low power (600–700 nm), no risk of light
hazard, and cheap lamps. More interestingly, it penetrates
even bulk turbid media. Although versatile photocatalytic sys-
tems have been well researched to date, there are very few ex-
amples of the application of red light for organic synthesis,
owing to a poor range of absorption windows for general pho-
[5]
tocatalysts
(e.g. maximum excitation wavelengths of lem =
452 nm for Ru(bpy)3,[6] 375 nm for fac-Ir(ppy)3,[7] and 539 nm
for eosin Y).[8] To expand the utilizable wavelength range of
visible light for photochemical reactions, an OsII/ReI supra-
molecular complexed photosensitizer was designed for red-
light-driven photocatalytic reactions.[9] This system is limited to
the reduction of CO2 and the catalyst requires a multi-step
synthesis.
Visible-light-mediated chemical transformations of organic
molecules under photoredox catalysis has dramatically
changed the realm of photochemical reactions in organic syn-
thesis. Classical photochemical reactions under ultraviolet (UV)-
light irradiation often damage substrates/products, resulting in
undesired complex mixtures.[1] Owing to the high energy of UV
irradiation (290–366 nm), control of the reaction is problematic,
and thus careful and strict design of substrates/reactions is re-
quired.[1] More importantly, UV light is toxic. On the other
hand, visible light is a longer wavelength light with lower
energy (380–780 nm), and chemical transformations proceed
efficiently under mild conditions in the presence of photore-
dox catalysts.[2] Polypyridyl dyes complexed with transition
metals, such as Ir(ppy)3 and Ru(bpy)3, are the most powerful
catalysts when irradiated by visible light. Although these pho-
toredox systems are mild, high-energy photon sources such as
blue light (400–500 nm) are still necessary for the chemical
transformations.[2] In addition, there is a risk of photo-oxidative
Phthalocyanines 1 are dyes with the most potential to be
red-light-driven photocatalysts, owing to their absorption
bands at around 600–700 nm,[10] followed closely by subphtha-
locyanines 2 at 500–600 nm.[11] However, the poor solubility of
1 and the instability of 2 strictly limit their utility in organic re-
actions.[12] Our group has researched a series of trifluoroe-
thoxy-coated phthalocyanines and subphthalocyanines for the
photodynamic therapy of cancer and electronic materials (Fig-
ure 1a).[13] Drawing motivation form this background, we de-
cided to develop a new utility of 1 and 2 for the photoredox
catalytic system, especially under the low energy of red light.
Trifluoromethylation is an attractive target reaction under
a photoredox system.[14] Indeed, trifluoromethylation reactions
induced by visible light constitute a recent breakthrough in or-
ganic chemistry.[15] However, all of the reported methods for
trifluoromethylation reactions strictly require high-energy
photon sources such as blue light-emitting diode (LED) photo-
irradiation (Figure 1b). Before the completion of our research,
You and co-workers reported the first attempt at the photore-
dox catalytic generation of trifluoromethyl radicals under low-
energy photoirradiation.[16] Metal–porphyrins were selected for
the trifluoromethylation of alkenes with trifluoromethyl iodide
(CF3I) by using LEDs. In the presence of oxalate, Pt–porphyrin
was best for this transformation under green LEDs, but the
substrate scope was narrow and limited, yields were low to
[a] K. Matsuzaki, T. Hiromura, E. Tokunaga, Prof. Dr. N. Shibata
Department of Nanopharmaceutical Sciences &
Department of Life and Applied Chemistry
Nagoya Institute of Technology
Gokiso, Showa-ku, Nagoya, 466–8555 (Japan)
E-mail: nozshiba@nitech.ac.jp
Supporting Information and the ORCID identification number(s) for the
author(s) of this article can be found under http://dx.doi.org/10.1002/
open.201600172.
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Table 1. Optimization of trifluoromethylation of alkene 3a with CF3I
under visible-light irradiation mediated by photoredox catalysts.[a]
Run
Catalyst
LED
Additive
Time [h]
Yield [%][b]
1
2
3
4
5
6
7[c]
8[c]
9
10[c]
11[c]
12[c]
13[c]
14[c]
15[c]
16[e]
17[c]
18
[Ru(bpy)3](PF6)2
Eosin Y
Methylene blue
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
–
–
–
–
–
–
–
–
6
6
6
6
6
6
3
1
6
1
1
1
1
1
3
3
3
0.5
<5
<5
<5
12
<5
92
62
35
<5
65
99
99
99
96
<5
<5
<5
90
1a
1b
2a
2a
2a
2b
2a
2a
2a
2a
2a
–
–
LiBr
Figure 1. a) Structures of phthalocyanines 1 and subphthalocyanines 2.
b) Photoredox trifluoromethylation under visible light (previous reports).
c) This work of photoredox trifluoromethylation under red light.
NaOAc
LiOAc
CsOAc
NaOAc[d]
NaOAc
NaOAc
NaOAc
–
moderate, and products were mixtures of trifluoromethyl al-
kenes and trifluoromethylethyl iodides. Moreover, red LEDs
were not as efficient as green LEDs when using metal–porphyr-
ins.[16] We, herein, disclose that trifluoroethoxy-coated sub-
phthalocyanine 2a dramatically catalyzes the trifluoromethyla-
tion of alkenes 3, including alkynes with CF3I, under red-light-
driven photoredox conditions to provide the corresponding tri-
fluoromethylethyl iodides 4 in a short space of time and with
very high yields (Figure 1c). The reaction mechanism is dis-
cussed based on cyclic voltammetry and the absorption spec-
tra of 2a.
2a
2a
2a
[f]
–
white
[a] The reaction of alkene 3a (0.25 mmol) with CF3I (excess) was carried
out in the presence of 1 or 2 (0.0025 mmol) and sodium l-ascorbate
(0.0875 mmol) in MeCN (1.0 mL) and MeOH (0.75 mL) at room tempera-
ture. [b] Yields were determined by using 19F NMR spectra of the crude
product with PhCF3 as an internal standard. [c] 5 mol% of Na ascorbate
was used. [d] 20 mol% of NaOAc was used. [e] In the absence of Na as-
corbate. [f] The reaction was carried out in the dark.
We first investigated the trifluoromethylation of hex-5-en-1-
ol (3a) with CF3I by using various photocatalysts under red-
light irradiation (Table 1). Following an earlier report by Ste-
phenson and co-workers, a catalytic amount of sodium l-ascor-
bate (35 mol%) was used as the initial reductant in a MeCN/
MeOH system.[15b,17] Apparently, in the red-light-driven system,
powerful photocatalysts such as [Ru(bpy)3](PF6)2, eosin Y, and
methylene blue were completely useless (runs 1–3). We next
examined the reaction using trifluoroethoxy-coated phthalo-
cyanine 1a. To our disappointment, the desired 6-trifluoro-
methyl-5-iodohexan-1-ol (4a) was obtained only in 12% yield
(run 4). The performance of non-substituted phthalocyanine
1b was even worse (run 5). We, thus, reverted to our second
choice of catalyst, subphthalocyanines 2. We were excited to
observe that trifluoroethoxy-coated subphthalocyanine 2a was
very effective for the transformation of 3a with CF3I under red
LED irradiation for 6 h, furnishing 4a in a high yield of 92%
(run 6). The yields decreased to 35% with 5 mol% of sodium l-
ascorbate in a shorter reaction time (runs 7 and 8). The reac-
tion was not catalyzed by non-substituted subphthalocyanine
2b (run 9); thus, the effect of the trifluoroethoxy coating on 2
is obvious. The trifluoroethoxy effect should increase the solu-
bility and stability of subphthalocyanine.[13b] We next examined
the effect of additives on the reaction. Stephenson and co-
workers reported that LiBr affects the atom-transfer radical ad-
dition (ATRA) of CF3I to alkenes as Lewis acid.[15b,f] Indeed, an
improvement was observed to 65% within 1 h (run 10). It
should be noted that the yield and reaction time improved fur-
ther in the presence of sodium acetate, even within 1 h
(run 11, 99%). This phenomenon is in good agreement with
the report by Sajiki and co-workers that sodium acetate is an
efficient auxiliary agent for the radical pathway of ATRA of flu-
oroalkyl iodine to olefins in thermal conditions.[18] The same
effect was observed by using lithium acetate and cesium ace-
tate (runs 12 and 13). The amount of sodium acetate could
also be reduced (run 14, 96%). In the control experiment, the
reaction did not take place without 2a, sodium ascorbate or
red light (runs 15–17). Additional optimization of reaction con-
ditions, including screening of additives and solvents, are
shown in Table S1. We also attempted the transformation of
3a under the stronger energy light of white LED irradiation in
the presence of 2a. The reaction proceeded very smoothly to
provide 4a in 90% yield (run 18). These results indicate that
trifluoroethoxy 2a catalyzes the photoredox reaction under
the low energy of red LED, whereas non-fluorinated 2b, phtha-
locyanines 1a, and 1b are entirely useless.
Although the effect of light was clear (Table 1, run 17), a fur-
ther investigation was attempted to confirm the necessity of
light to maintain the transformation or whether it was only re-
quired to initiate a reaction, according to a light irradiation/
dark study (Scheme S1). These results clearly indicate that the
light must be maintained during the transformation as well.
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The effectiveness of 2a rather than 1a, 1b, or 2b, can be
explained by the UV/Vis spectra of catalysts and LED lights.
The UV/Vis spectra of 1 and 2 were recorded in MeCN/MeOH
and/or 1,4-dioxane at a concentration of 1ꢁ10À5 m, depending
on the solubility (Figure 2, also see Figure S1). Their Q bands
Table 2. Substrate scope of trifluoromethylation of alkenes 3 with 2a cat-
alysis under red-light irradiation.[a]
Figure 2. UV/Vis spectra of phthalocyanines 1 and subphthalocyanines 2 at
1ꢁ10À5 m and absorption of blue, white, and red LEDs.
were slightly blue shifted in MeCN/MeOH compared to 1,4-di-
oxane, but the differences were small. These spectra indicate
that all phthalocyanines 1 and subphthalocyanines 2 were
present solely as monomers and were characterized by sharp
absorption bands in the Q-band region. Strong absorption
peaks were observed at 710 or 703 nm for 1a, 666 nm for 1b,
603 and 598 nm for 2a, and 563 nm for 2b. On the other
hand, white LEDs showed broad spectrum of 430–700 nm with
two peaks, and red LEDs displayed a sharp absorption at 600–
650 nm. These results suggest that the absorption of 2a shows
a suitable overlap with red LEDs, resulting in a 99% yield of
4a, whereas catalysts 1b and 2b were useless, owing to the
lack of overlapping spectra. The 12% formation of 4a from 1a
is reasonable, as 1a has an overlapping shoulder peak at 638
or 632 nm. White LEDs are effective enough for the activation
of 2a with a wide range of overlapping spectra.
With the optimized conditions under red light in hand, the
substrate scope of 3 was investigated (Table 2). Terminal olefin-
like 3a–j finely reacted with CF3I to afford the desired adducts
4a–j under the red-light-induced photocatalytic system by
using 2a. Common functional groups such as tosyl 3d, ester
3e, alkyl- and aryl-halide 3 f, h, i, carbamate 3m, and electron-
rich aromatic groups 3g were tolerated under these condi-
tions. Internal olefin 3k and exo-olefin 3l also gave good
yields. The alkene 3n, appending a b-keto ester functionality,
reacted selectively with CF3I at the olefinic moiety to provide
4n (66% 19F NMR yield and 59% isolated yield), whereas the
active methylene of 3n was touched with only 2% 19F NMR
yield. The result is worth noting, because the b-keto esters re-
acted with CF3I under white LEDs or radical conditions.[19] Not
only alkenes 3, but also alkynes 3o and 3p, were converted
into the corresponding adducts 4o and 4p in 70 and 44%
yield, respectively. In all cases, the regioselectivity was almost
[a] The reaction of alkenes 3 (0.25 mmol) with CF3I (26–29 equiv) was car-
ried out in the presence of 2a (0.0025 mmol), sodium l-ascorbate
(0.0125 mmol), and sodium acetate (0.25 mmol) in MeCN (1.0 mL) and
MeOH (0.75 mL) at room temperature. [b] RFI (1.5 equiv) was employed.
[c] 4d/4d’= >25:1. [d] The minor isomer 4b’ was characterized through
the total synthesis of 4b’ by using a different method (see the Support-
ing Information). [e] 35 mol% of sodium l-ascorbate was used without
the addition of sodium acetate. [f] 19F NMR yield of 4n is 66%. [g] 2% of
a-trifluoromethylated b-keto ester was observed in the crude 19F NMR.
perfect and only a trace amount of regioisomers, such as 4b’,
were observed in the 19F NMR (<4% as a doublet at around d-
70 ppm in the 19F NMR analysis). The red-light methodology
was extended to the perfluoroalkylation of 2a using nC4F9-I
and nC8F17-I to give perfluoroalkylation adducts 5a and 6a in
92 and 85%, respectively. Although the reaction has a wide
scope, electron-deficient alkenes and styrene were not
accepted.
A plausible reaction mechanism involving both a closed cat-
alytic cycle A and chain propagation cycle B was proposed
(Scheme 1) with the support of cyclic voltammetry of 2a (Fig-
ure S2). Earlier reports of CF3-I ATRA reactions have shown that
the reaction is based on an effective radical chain reaction that
can be initiated through visible-light irradiation even without
photocatalysts;[20] however, our system requires both photoca-
talyst 2a (run 15, Table 1) and light (run 17, Table 1). Thus, in
the initial step, photo-excited trifluoroethoxy subphthalocya-
nine 2a receives one electron from sodium ascorbate to form
an anion radical of 2a.[15b,17] The anion radical [Eo’(2a/2a·À)=
À0.69 V vs. SCE] should reduce CF3I (Eo’=À1.22 V vs. SCE)[21] to
generate the CF3 radical (·CF3) (Scheme S3). Although this re-
duction process is a thermodynamically unfavorable electron
transfer[22] from the reduced photocatalyst to CF3I (about
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Conflict of Interest
The authors declare no conflict of interest.
Keywords: photoredox catalysis · phthalocyanine · red light ·
subphthalocyanine · trifluoromethylation
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In conclusion, we have disclosed that trifluoroethoxy-coated
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Acknowledgements
This research is partially supported by the Daiko Foundation,
ACT-C from the JST, JSPS KAKENHI (JP16H01017 in Precisely De-
signed Catalysts with Customized Scaffolding, 15J06852 for KM),
and the Asahi Glass Foundation.
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Received: December 25, 2016
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Published online on && &&, 2017
ChemistryOpen 2017, 00, 0 – 0
www.chemistryopen.org
5
ꢀ 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

COMMUNICATIONS
K. Matsuzaki, T. Hiromura, E. Tokunaga,
N. Shibata*
&& – &&
Trifluoroethoxy-Coated
Subphthalocyanine affects
Trifluoromethylation of Alkenes and
Alkynes even under Low-Energy Red-
Light Irradiation
Red is the new “green”! Trifluoro-
ethoxy-coated subphthalocyanine
(TFEO-SubPc) realizes red-light-driven
trifluoromethylation of alkenes and al-
kynes with trifluoromethyl iodide in
good-to-high yields. The reaction mech-
anism is discussed with the support of
UV/Vis spectra and cyclic voltammetry
of TFEO-SubPc.
&
ChemistryOpen 2017, 00, 0 – 0
www.chemistryopen.org
6
ꢀ 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!