Visible Light-Mediated Trifluoromethylation of Fluorinated Alkenes via C?F Bond Cleavage

Article abstract of DOI:10.1002/adsc.201800740

A convenient photoredox-catalyzed defluorinative trifluoromethylation of α-trifluoromethyl alkenes and gem-difluoroalkenes is developed. The reactions proceeded efficiently via trifluoromethyl radical addition followed by β-fluorine elimination process, providing a new entry to multifluorinated alkenes in moderate to good yields with excellent stereoselectivity. (Figure presented.).

Full text of DOI:10.1002/adsc.201800740

Title: Visible Light-Mediated Trifluoromethylation of Fluorinated
Alkenes via C–F Bond Cleavage
Authors: Liu-Hai Wu, Jun-Kee Cheng, Liang Shen, Zhi-Liang Shen,
and Teck-Peng Loh
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800740
Link to VoR: http://dx.doi.org/10.1002/adsc.201800740

10.1002/adsc.201800740
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Visible Light-Mediated Trifluoromethylation of Fluorinated
Alkenes via C–F Bond Cleavage
Liu-Hai Wu,b Jun-Kee Cheng,b Liang Shen,b Zhi-Liang Shen,a,* and Teck-Peng Loha,b,*
a
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic
Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 210009, China.
E-mail: ias_zlshen@njtech.edu.cn
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang
b
Technological University, Singapore 637371, Singapore.
E-mail: teckpeng@ntu.edu.sg
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
transition metal has also been explored.[6] Particularly,
Abstract:
A
convenient
photoredox-catalyzed
defluorinative trifluoromethylation of α-trifluoromethyl
alkenes and gem-difluoroalkenes is developed. The reactions
proceeded efficiently via trifluoromethyl radical addition
followed by β-fluorine elimination process, providing a new
entry to multifluorinated alkenes in moderate to good yields
with excellent stereoselectivity.
an efficient visible light photoredox-catalyzed
monofluoroalkenylation of gem-difluoroalkenes has
been reported by the Hashmi and Fu groups (Scheme
1b).[7]
In
the
last
few
years,
photocatalytic
trifluoromethylation has received considerable attention
from synthetic chemists and has been widely
investigated.[8] Meanwhile, our group has reported a
series of work on trifluoromethylation of alkenes and
C–F bond functionalization.[9] However, we realized
that the synthesis of multifluorinated molecules by
means of trifluoromethylation via β-fluorine
elimination is still underdeveloped. Moreover, due to
the involvement of radical process in photocatalysis, the
Keywords: Photocatalysis; C-F bond cleavage;
Trifluoromethylation; Iridium; Sodium triflinate
Organofluorine compounds play a very important role
in pharmaceutical chemistry and agriculture chemistry,
mainly owing to their unique chemical and biological
properties.[1] Therefore, the construction of fluorinated
compounds has gained considerable momentum in
recent years. Transformation of multifluorinated
compounds via C–F bond functionalization provides a
novel approach for the preparation of functional and
bioactive fluorine-containing molecules. Despite the C–
F bond’s high dissociation energy, numerous strategies
have been developed to achieve the cleavage of C–F
bonds.[2] Compared to traditional methods, which
normally need harsh reaction conditions or
stoichiometric organometallic reagents, visible light-
mediated C–F bond cleavage by using photoredox
catalysis has emerged as a promising option for the
functionalization of multifluorinated compounds under
mild reaction condition.[3]
stereoselectivity
is
poorly
controlled
when
unsymmetrical gem-difluoroalkenes are employed as
substrates. Herein, we reported an efficient and practical
photoredox-catalyzed
trifluoromethylation
of
fluorinated alkenes through C–F bond cleavage by
using CF3SO2Na as trifluoromethyl source,[10]
providing CF3-containing multifluorinated molecules
with excellent stereoselectivity (Scheme 1c).
Among the various multifluorinated compounds, α-
trifluoromethyl alkenes are considered to be versatile
building blocks which generally undergo SN2’-type
reactions with nucleophiles to achieve C–F bond
cleavage of the CF3 group (Scheme 1a).[4] Recently,
radical processes to access gem-difluoroalkenes from α-
trifluoromethyl alkenes by employing photoredox
catalysis have been achieved.[5] Meanwhile, the
functionalization of gem-difluoroalkenes by using
nucleophiles via C–F bond cleavage in the presence of
Scheme 1. Strategies to functionalize multifluorinated
compounds via C–F bond cleavage.
1
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10.1002/adsc.201800740
Advanced Synthesis & Catalysis
Initially, 4-(3,3,3-trifluoroprop-1-en-2-yl)biphenyl modification. Moreover, the reaction was compatible to
(1a) and CF3SO2Na (2) were chosen as the model both naphthalene-substituted and heteroaryl-substituted
substrates to explore the optimum reaction conditions substrates, giving rise to 3n and 3o in moderate to good
under the irradiation of blue LEDs (Table 1). Among yields. Especially noteworthy is that protected aldehyde
different solvents screened in the presence of and ketone (3p and 3q) also proved to be suitable
[Ir(ppy)2dtbpy]PF6 (PC1), the use of CH3CN, DMSO, candidates for this organic transformation. Furthermore,
or acetone led to poor product yields (entries 1-3), while enynyl substrate, 2-trifluoromethyl-1,3-enyne, was also
the use of DMF provided a moderate product yield capable of undergoing the present trifluoromethylation
(entry 4). Subsequent optimization showed that smoothly to produce the corresponding 1,1-difluoro-
[Ir(dF(CF3)ppy)2(dtbpy)]PF6 (PC2) was more efficient, 1,3-enyne 3r in 53% yield.
improving the yield of 3a to 71% (entry 5), which might
be rationalized by PC2’s higher oxidizing excited state Table 2. Defluorinative trifluoromethylation of α-
III*/II
(E1/2
= +1.21 V vs SCE), as compared with PC1 trifluoromethyl alkenes.[a]
(E1/2III*/II = +0.66 V vs SCE).[11] Based on the results, it
seemed that polar solvents were preferred in this
transformation. A further survey of other polar solvents
showed that DMA was the solvent of choice, producing
3a in 90% yield (entry 6).[12] Notably, halving the
catalyst would reduce the product yield (entry 7), and
control experiments demonstrated that both light and
photocatalyst are essential in this reaction (entries 8 and
9).
Table 1. Optimization of visible light-mediated
defluorinative trifluoromethylation of 1a.[a]
Entry
Catalyst
PC1
PC1
PC1
PC1
PC2
PC2
PC2
PC2
--
Solvent
CH3CN
DMSO
acetone
DMF
Yield [%][b]
1
2
3
4
5
6
7
8
9
21
22
15
48
71
90
83[c]
0[d]
0
DMF
DMA
DMA
DMA
DMA
[a]
Reaction conditions: 1a (0.2 mmol), 2 (0.3 mmol),
photocatalyst (0.004 mmol), blue LEDs, solvent (1 mL), rt,
12 h.
[b] Isolated yield.
[c] Photocatalyst (0.002 mmol).
[d] Without light.
[a] Reaction conditions: 1 (0.2 mmol), 2 (0.3 mmol), PC2
(0.004 mmol), blue LEDs, DMA (1 mL), rt, 12 h. Yields
of isolated products are given.
With the optimized reaction conditions in hand
(Table 1, entry 6), we then investigated the substrate
scope of the present transformation (Table 2).
Substrates containing electron-donating, electron-
withdrawing, or halide substituents in ortho, meta or
para position were amenable to the reaction conditions
to give products 3b-l in 62-89% yields. It was
noteworthy that a substrate bearing a silyl group
underwent the reaction smoothly, even in the presence
of F-, leading to the product 3m in an excellent yield,
which is a versatile building block suitable for further
Encouraged by the results of trifluoromethylation via
C–F bond cleavage of α-trifluoromethyl alkenes, we
further explored the defluorinative trifluoromethylation
of gem-difluoroalkenes in this transformation (Table 3).
Unfortunately, under the afore-mentioned reaction
conditions, the reaction involving gem-difluorostyrene
4a only provided the desired product 5a in a low yield
with extremely poor stereoselectivity (entries 1-3).
Compared to PC2, the use of [Ir(dF(CF3)ppy)2(5,5’-
2
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10.1002/adsc.201800740
Advanced Synthesis & Catalysis
d(CF3)bpy)]PF6 (PC3), whose reduced IrII state has mL), rt, 36 h. Yields of isolated products are given. Z/E ratio
higher reduction potential (E1/2III/II = -1.07 V vs Fc+/Fc), was determined by crude 19F NMR.
as compared to the reduced state of PC1 and PC2,[13]
led to good stereoselectivity (Z/E = 94:6) with slightly
Next, the substrate scope and limitations with gem-
higher yield (entry 4). Among the various solvents and difluoroalkene derivatives were investigated (Table 4).
additives surveyed in this reaction (entries 5-9), PC3 in In this transformation, substrates bearing electron-
combination with LiClO4[14] as additive in acetone was withdrawing groups reacted smoothly to deliver the
identified as the best choice to afford the product 5a in corresponding products 5a-f in moderate yields.
52% yield with excellent stereoselectivity (Z/E = 99:1, However, substrates containing electron-donating
entry 9), indicating that less polar solvent is more groups were not suitable in this reaction, which was
appropriate for this transformation.[15]
possibly ascribed to its low reactivity or the instability
of the formed α-trifluoromethylcarbanion intermediate
Table 3. Optimization of the visible light-mediated during the course of the transformation. Notably, gem-
defluorinative trifluoromethylation of 4a.[a]
difluoroalkenes bearing important functional groups
such as ester, cyanide, organophosphate, and amide
were amenable to this reaction. The transformation
proceeded with excellent stereoselectivity (up to 99:1
Z/E). This result is in agreement with the reported result
based on calculation,[16a] where the Z isomer displays
thermodynamically higher stability and kinetically
lower energy barrier in the transition state. Also,
compared to fluoride, the trifluoromethyl group is
bulkier and thus it prefers to attack the C-C triple bond
via an orientation trans to the sterically hindered aryl
group, thereby giving a less hindered Z isomer.[16] In
addition, it should be mentioned that when the
optimized reaction conditions were applied to the
trifluoromethylation of compound 3a which also
contains a gem-difluoroalkene moiety, only traces of the
defluorinative product was obtained.
To gain mechanistic insight into this defluorinative
trifluoromethylation, radical trapping experiments were
performed. When the reaction mixture of 1a/4a and 2
were treated with 2,2,6,6-tetramethyl-1-piperidinyloxy
(TEMPO) under the standard reaction conditions, the
defluorinative trifluoromethylation was completely
inhibited (Scheme 2a and 2b). The results implied that
a radical process is likely involved in this reaction. In
order to further explore possible isomerization
mechanism of 5, E/Z-5a was introduced into the
reaction system under standard reaction conditions
(Table 3, entry 9). However, the E/Z ratio remained the
same after reaction, suggesting that isomerization was
not likely induced through energy transfer process.[3d,17]
Entry Catalyst Additive Solvent Yield
[%][b]
Z/E[c]
1
2
3
PC2
PC2
PC1
--
--
--
DMA
DMSO
DMSO
15
22
15
50:50
50:50
55:45
4
5
6
7
8
9
PC3
PC3
PC3
PC3
PC3
PC3
--
--
--
--
DMSO
CH3CN
acetone
acetone
28
94:6
99:1
99:1
99:1
99:1
99:1
33
37
43[d]
45[d]
52[e]
Li2CO3 acetone
LiClO4 acetone
LiClO
[a]
Reaction conditions: 4a (0.2 mmol), 2 (0.4 mmol),
photocatalyst (0.004 mmol), additive (0.3 mmol), blue
LEDs, solvent (1 mL), rt, 12 h.
[b] Isolated yield.
[c] The Z/E ratio was determined by crude 19F NMR.
[d] Photocatalyst (0.006 mmol).
[e] Photocatalyst (0.006 mmol), 36 h.
Table 4. Defluorinative trifluoromethylation of gem-
difluoroalkenes.[a]
Scheme 2. Control experiments.
On the basis of above experimental results, a
plausible reaction mechanism was proposed (Scheme 3).
Initially, NaSO2CF3 is oxidized by visible light-excited
*IrIII via a single electron transfer (SET) process to
[a] Reaction conditions: 4 (0.2 mmol), 2 (0.4 mmol), PC3
(0.006 mmol), LiClO4 (0.3 mmol), blue LEDs, acetone (1
3
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10.1002/adsc.201800740
Advanced Synthesis & Catalysis
•
vacuum. Purification by silica gel column chromatograph
using CH2Cl2 and hexane as eluent afforded the target product.
generate trifluoromethyl radical (CF3 ), along with the
generation of reduced IrII. Next, CF3 undergoes a
•
radical addition to alkene 1 or 4 to deliver a transient α-
trifluoromethyl radical A or A´, which subsequently
undergoes a SET reduction by IrII, providing an α-
trifluoromethyl anion B or B´ with the concomitant
regeneration of photocatalyst IrIII. Finally, β-fluoride
elimination readily occurs to furnish the desired product
3 or 5.
General
procedures
for
the
defluorinative
trifluoromethylation of gem-difluoroalkenes
To an 8 mL sample vial, charged with [Ir(dF(CF3)ppy)2(5,5‘-
d(CF3)bpy)]PF6 (PC3) (7.0 mg, 0.006 mmol, 3 mol%),
LiClO4 (31.8 mg, 0.3 mmol, 1.5 equiv) and CF3SO2Na (62.4
mg, 0.4 mmol. 2.0 equiv) in acetone (1 mL) was added gem-
difluoroalkene (0.2 mmol,
1 equiv) under nitrogen
atmosphere at room temperature. The vial was sealed with
screw cap and stirred at room temperature under blue LEDs
for 36 h. The reaction mixture was diluted with EtOAc (10
mL), filtered through filter paper and concentrated under
vacuum. Purification by silica gel column chromatograph
using DCM and hexane as eluent afforded the target product.
Acknowledgements
We are grateful to Nanjing Tech University (Start-up Grant
39837118 and 39837101), SICAM Fellowship from Jiangsu
National Synergetic Innovation Center for Advanced Materials,
Nanyang Technological University, Singapore Ministry of
Education Academic Research Fund [Tier 1 grant (Reference No:
RG5/15 and RG111/16)] for generous financial support.
References
[1] a) S. Purser, P. R. Moore, S. Swallow, V. Gouverneur,
Chem. Soc. Rev. 2008, 37, 320-330; b) G. Theodoridis
in Advances in Fluorine Science, Vol. 2 (Eds.: T. Alain),
Elsevier, 2006, pp. 121–175; c) E. P. Gillis, K. J.
Eastman, M. D. Hill, D. J. Donnelly, N. A. Meanwell, J.
Med. Chem. 2015, 58, 8315–8359.
Scheme 3. Proposed mechanism for photoredox-catalyzed
trifluoromethylation of fluorinated alkenes through C(sp2 &
sp3)–F bond cleavage.
[2] a) H. Amii, K. Uneyama, Chem. Rev. 2009, 109, 2119–
2183; b) T. Ahrens, J. Kohlmann, M. Ahrens, T. Braun,
Chem. Rev. 2015, 115, 931−972; c) T. Stahl, H. F. T.
Klare, M. Oestreich, ACS Catal. 2013, 3, 1578−1587; d)
M. Janjetovic, A. M. Traff, G. Hilmersson, Chem. Eur.
J. 2015, 21, 3772–3777; e) O. Papaianina, K. Y.
Amsharov, Chem. Commun. 2016, 52, 1505–1508; f) N.
Suzuki, T. Fujita, K. Y. Amsharov, J. Ichikawa, Chem.
Commun. 2016, 52, 12948–12951; g) T. Nishimine, H.
Taira, E. Tokunaga, M. Shiro, N. Shibata, Angew. Chem.
Int. Ed. 2016, 55, 359–363; h) J. Tanaka, S. Suzuki, E.
Tokunaga, G. Haufe, N. Shibata, Angew. Chem. Int. Ed.
2016, 55, 9432–9436; i) S. Yoshida, K. Shimomori, Y.
Kim, T. Hosoya, Angew. Chem. Int. Ed. 2016, 55,
10406–10409; j) K. Kikushima, M. Grellier, M. Ohashi,
S. Ogoshi, Angew. Chem. Int. Ed. 2017, 56, 16191–
16196; k) D. Zell, U. Dhawa, V. Mꢀller, M. Bursch, S.
Grimme, L. Ackermann, ACS Catal. 2017, 7,
4209−4213; l) D. Zell, V. Meller, U. Dhawa, M. Bursch,
R. R. Presa, S. Grimme, L. Ackermann, Chem. Eur. J.
2017, 23, 12145–12148; m) K. Saito, T. Umi, T.
Yamada, T. Suga, T. Akiyama, Org. Biomol. Chem.
2017, 15, 1767–1770; n) Z. Zhang, Q. Zhou, W. Yu, T.
Li, G. Wu, Y. Zhang, J. Wang, Org. Lett. 2015, 17,
2474–2477; o) H. Luo, G. Wu, S. Xu, K. Wang, C. Wu,
Y. Zhang, J. Wang, Chem. Commun. 2015, 51, 13321-
13323; p) L. Zhang, W. Zhang, J. Liu, J. Hu, J. Org.
Chem. 2009, 74, 2850–2853; q) M. Hu, Z. He, B. Gao,
L. Li, C. Ni, J. Hu, J. Am. Chem. Soc. 2013, 135,
17302−17305.
In
summary,
an
efficient
defluorinative
trifluoromethylation of α-trifluoromethyl alkenes and
gem-difluoroalkenes via Ir photoredox catalyzed C–F
bond cleavage has been developed. This reaction
provides a convenient and efficient approach to
construct substituted difluoroalkenes, which is
compatible with various functional groups. Meanwhile,
the reaction exhibits excellent stereoselectivity with
gem-difluoroalkenes, which provides potential for
further
applications
in
pharmaceutical
and
agrochemical research.
Experimental Section
General
procedures
for
the
defluorinative
trifluoromethylation of α-trifluoromethyl alkenes
To
an
8
mL
sample
vial,
charged
with
[Ir(dF(CF3)ppy)2dtbpy]PF6 (PC2) (4.4 mg, 0.004 mmol, 2
mol%), and CF3SO2Na (46.8 mg, 0.3 mmol. 1.5 equiv) in
dimethylacetamide (1 mL) was added α-trifluoromethyl
alkene (0.2 mmol, 1 equiv) under nitrogen atmosphere at
room temperature. The vial was sealed with screw cap and
stirred at room temperature under blue LEDs for 12 h. The
reaction mixture was diluted with EtOAc (10 mL), washed
with water (2×20 mL), brine (20 mL), and concentrated under
[3] a) S. M. Senaweera, A. Singh, J. D. Weaver, J. Am.
Chem. Soc. 2014, 136, 3002−3005; b) J. Chen, K. Zhao,
B. Ge, C. Xu, D. Wang, Y. Ding, Chem. Asian J. 2015,
10, 468–473; c) A. Singh, J. J. Kubik, J. D. Weaver,
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800740
Advanced Synthesis & Catalysis
Chem. Sci. 2015, 6, 7206–7212; d) A. Singh, C. J.
Fennell, J. D. Weaver, Chem. Sci. 2016, 7, 6796–6802;
e) A. Arora, J. D. Weaver, Acc. Chem. Res. 2016, 49,
2273−2283; f) S. Senaweera, J. D. Weaver, J. Am. Chem.
Front. 2016, 3, 1163–1185; d) T. Koike, M. Akita, Acc.
Chem. Res. 2016, 49, 1937−1945; e) T. Chatterjee, N.
Iqbal, Y. You, E. J. Cho, Acc. Chem. Res. 2016, 49,
2284−2294.
Soc. 2016, 138, 2520−2523; g) J. Xie, M. Rudolph, F. [9] a) P. Tian, C. Feng, T.-P. Loh, Nat. Commun. 2015, 6,
Rominger, A. S. K. Hashmi, Angew. Chem. Int. Ed.
2017, 56, 7266–7270; h) K. A. Teegardin, J. D. Weaver,
Chem. Commun. 2017, 53, 4771–4774; i) K. Chen, N.
B. R. Gschwind, B. Kꢁnig, J. Am. Chem. Soc. 2017, 139,
18444–18447; j) H. Wang, N. T. Jui, J. Am. Chem. Soc.
2018, 140, 163−166; k) J. I. Day, J. D. Weaver, J. Org.
Chem. 2017, 82, 6801−6810.
7472; b) S.-H. Cai, L. Ye, D.-X. Wang, Y.-Q. Wang, L.-
J. Lai, C. Zhu, C. Feng, T.-P. Loh, Chem. Commun.
2017, 53, 8731–8734; c) C.-Q. Wang, L. Ye, C. Feng,
T.-P. Loh, J. Am. Chem. Soc. 2017, 139, 1762−1765; d)
L.-H. Wu, K. Zhao, Z.-L. Shen, T.-P. Loh, Org. Chem.
Front. 2017, 4, 1872−1875.
[10] a) C. Zhang, Adv. Synth. Catal. 2014, 356, 2895–2906;
b) Q. Lefebvre, N. Hoffmann, M. Rueping, Chem.
Commun. 2016, 52, 2493−2496; c) L. Zhu, L.-S. Wang,
B. Li, B. Fu, C.-P. Zhang, W. Li, Chem. Commun. 2016,
52, 6371−6374.
[4] a) T. Ichitsuka, T. Fujita, J. Ichikawa, ACS Catal. 2015,
5, 5947−5950; b) K. Fuchibe, H. Hatta, K. Oh, R. Oki,
J. Ichikawa, Angew. Chem. Int. Ed. 2017, 56, 5890–
5893; c) T. Fujita, M. Takazawa, K. Sugiyama, N.
Suzuki, J. Ichikawa, Org. Lett. 2017, 19, 588−591; d) X. [11] a) M. S. Lowry, J. I. Goldsmith, J. D. Slinker, R. Rohl,
Zhang, Y. Liu, G. Chen, G. Pei, S. Bi, Organometallics
2017, 36, 3739−3749; e) W. Dai, Y. Lin, Y. Wan, S. Cao,
Org. Chem. Front. 2018, 5, 55−58.
R. A. Pascal, G. G. Malliaras, S. Bernhard, Chem. Mater.
2005, 17, 5712−5719; b) Z. Zuo, D. T. Ahneman, L.
Chu, J. A. Terrett, A. G. Doyle, D. W. C. MacMillan,
Science 2014, 345, 437−440.
[5] a) T. Xiao, L. Li, L. Zhou, J. Org. Chem. 2016, 81,
7908−7916; b) H. Chen, T. Xiao, L. Li, D. Anand, Y. [12] a) J. Zoller, D. C. Fabry, M. A. Ronge, M. Rueping,
He, L. Zhou, Adv. Synth. Catal. 2017, 359, 3642–3647;
c) S. B. Lang, R. J. Wiles, C. B. Kelly, G. A. Molander,
Angew. Chem. Int. Ed. 2017, 56, 15073–15077; d) L. Li,
Angew. Chem. Int. Ed. 2014, 53, 13264 –13268; b) M.
Rueping, S. Zhu, R. M. Koenigs, Chem. Commun. 2011,
47, 12709–12711.
T. Xiao, H. Chen, L. Zhou, Chem. Eur. J. 2017, 23, [13] a) G. J. Choi, Q. Zhu, D. C. Miller, C. J. Gu, R. R.
2249–2254; e) G. Chelucci, Chem. Rev. 2012, 112,
1344–1462; f) X. Zhang, S. Cao, Tetrahedron Lett. 2017,
58, 375–392; g) J. Ichikawa, Chim. Oggi 2007, 25, 54–
57.
Knowles, Nature 2016, 539, 268–271; b) Q. Zhu, D. E.
Graff, R. R. Knowles, J. Am. Chem. Soc. 2018, 140,
741−747.
[14] M. Bergeron, T. Johnson, J.-F. Paquin, Angew. Chem.
Int. Ed. 2011, 50, 11112–11116.
[6] a) G. Jin, X. Zhang, D. Fu, W. Dai, S. Cao, Tetrahedron
2015, 71, 7892–7899; b) R. T. Thornbury, F. D. Toste, [15] Currently, the exact solvent effect is not clear in the
Angew. Chem. Int. Ed. 2016, 55, 11629–11632; c) J. Hu,
X. Han, Y. Yuan, Z. Shi, Angew. Chem. Int. Ed. 2017,
56, 13342–13346; d) L. Kong, B. Liu, X. Zhou, F. Wang,
X. Li, Chem. Commun. 2017, 53, 10326–10329; e) X.
presence of PC3. We surmised that less polar solvent
(acetone) might have an impact on redox potential of
PC3 and stabilize the formed intermediate in the SET
process.
Lu, Y. Wang, B. Zhang, J.-J. Pi, X.-X. Wang, T.-J. Gong, [16] a) V. G. Nenajdenko, V. N. Korotchenko, A. V. Shastin,
B. Xiao, Y. Fu, J. Am. Chem. Soc. 2017, 139,
12632−12637; f) B. Zhang, X. Zhang, J. Hao, C. Yang,
Org. Lett. 2017, 19, 1780−1783.
E. S. Balenkova, Russ. Chem. Bull. 2004, 53, 1034–
1064; b) A. A. Goldberg, V. M. Muzalevskiy, A. V.
Shastin, E. S. Balenkova, V. G. Nenajdenko, J. Fluor.
Chem. 2010, 131, 384–388; c) Y. Li, D.-H. Tu, Y.-J. Gu,
B. Wang, Y.-Y. Wang, Z.-T. Liu, Z.-W. Liu, J. Lu, Eur.
J. Org. Chem. 2015, 4340–4343.
[7] a) J. Xie, J. Yu, M. Rudolph, F. Rominger, A. S. K.
Hashmi, Angew. Chem. Int. Ed. 2016, 55, 9416–9421;
b) J. Li, Q. Lefebvre, H. Yang, Y. Zhao, H. Fu, Chem.
Commun. 2017, 53, 10299–10302.
[8] a) T. Liang, C. N. Neumann, T. Ritter, Angew. Chem.
Int. Ed. 2013, 52, 8214–8264; b) S. Barata-Vallejo, S.
M. Bonesi, A. Postigo, Org. Biomol. Chem. 2015, 13,
11153–11183; c) X. Pan, H. Xia, J. Wu, Org. Chem.
[17] A. Singh, S. J. Staig, J. D. Weaver, J. Am. Chem. Soc.
2014, 136, 5275−5278.
5
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10.1002/adsc.201800740
Advanced Synthesis & Catalysis
COMMUNICATION
Visible Light-Mediated Trifluoromethylation of
Fluorinated Alkenes via C–F Bond Cleavage
Adv. Synth. Catal. Year, Volume, Page – Page
L.-H. Wu, J.-K. Cheng, L. Shen, Z.-L. Shen,* and
T.-P. Loh*
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