Electrophotocatalytic SNAr Reactions of Unactivated Aryl Fluorides at Ambient Temperature and Without Base

Article abstract of DOI:10.1002/anie.201909983

The electrophotocatalytic S_NAr reaction of unactivated aryl fluorides at ambient temperature without strong base is demonstrated.

Full text of DOI:10.1002/anie.201909983

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: Electrophotocatalytic SNAr Reactions of Unactivated Aryl
Fluorides at Ambient Temperature and Without Base.
Authors: He Huang and Tristan Hayes Lambert
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201909983
Angew. Chem. 10.1002/ange.201909983
Link to VoR: http://dx.doi.org/10.1002/anie.201909983
http://dx.doi.org/10.1002/ange.201909983

10.1002/anie.201909983
Angewandte Chemie International Edition
COMMUNICATION
Electrophotocatalytic SNAr Reactions of Unactivated Aryl
Fluorides at Ambient Temperature and Without Base.
He Huang[a] and Tristan H. Lambert*[a]
Abstract: The electrophotocatalytic SNAr reaction of unactivated aryl
A. SNAr with aryl halides
fluorides at ambient temperature without strong base is demonstrated.
X
Nu
Nu–H
Nucleophilic aromatic substitution (SNAr) reactions have long
–H+
been an important strategic tool for organic synthesis, enabling
1
2
1, 2]
the direct arylation of nucleophilic substrates.[
Classically,
SNAr reactions operate on activated arenes 3 bearing strongly
electron-withdrawing functionality (EWG, Figure 1A).[3-8] While
such reactions have great utility, such substituents are often not
synthetically desirable and thus represent a significant limitation
for this reaction class. On the other hand, several reports have
described SNAr reactions with unactivated substrates 4 through
the use of strong bases and high reaction temperatures.[9-13]
Unfortunately, many complex substrates are not compatible with
such conditions, which thus precludes the broad adoption of these
methods. As such, the development of SNAr reactions that occur
on unactivated substrates at ambient temperature without the
need for strongly basic reagents has presented a significant
challenge.
X
F
F
EWG
activated
R
R
3
4
4
unactivated (this work)
unactivated (previous)
requires EWG,
strong base
requires high temp,
strong base
electrophotocatalytic →
room temp, no strong base
B. Photoredox-catalyzed SNAr of alkoxyarenes (Nicewicz 2017)
OMe
Acr+ Acr•
blue LEDs
oxidation
Acr+
OMe
OMe
Acr•
Nu
+
Nu–H
NuH
+
–MeOH
reduction /
5
6
7
2
rearomatization
C. Electrophotocatalytic C–H / N–H coupling (previous work)
In this regard, a new entry in the SNAr arena was recently
reported by Nicewicz, who found that alkoxy arenes could
undergo nucleophilic substitution via photoredox catalysis (Figure
1B).[ 14 ] Mechanistically, these reactions were thought to be
initiated by single-electron photooxidation of the alkoxyarene 5 to
generate a radical cation 6. Subsequent nucleophilic attack,
reduction of the resulting radical intermediate 7 (nominally by the
reduced acridinium photocatalyst, Acr•), and rearomatization with
expulsion of the alkoxy substituent then furnished the substitution
products 2. This method represented a notable new strategy for
SNAr reactions and expanded the scope of nucleofugal groups to
include alkoxy substituents. On the other hand, this substrate
expansion also represented a limitation, in that the electron-
donating alkoxy substituents were necessary to achieve the initial
8 mol%
TAC
Cl
CHO
Cl
N
+
Cl
N
N
light +
electricity
CHO
N
H
Cl
8
9
10
D. Electrophotocatalytic SNAr of unactivated aryl fluorides (this work)
CHO
CHO
F
catalyst
N
N
+
N
N
H
light +
electricity
Cl
Cl
11
9
12
Figure 1. SNAr reactions, including classic, photoredox-catalyzed, and
electrophotocatalytic variants.
oxidation event. It therefore remains a challenge to develop SNAr
methods of the Nicewicz type that accommodate unactivated
aromatics and a broader range of nucleofugal groups. However,
overcoming this challenge requires the identification of a catalyst
oxidizing enough to achieve the initial single-electron oxidation of
less electron-rich substrates while retaining the ability to reduce
[ 15 - 17 ]
the intermediate radical complex (cf. 7).
In this
Communication, we report that an electrophotocatalytic[ 18 ]
strategy solves this problem and enables SNAr reactions of
unactivated aryl fluorides at room temperature and without strong
base.
We recently described the oxidative coupling reactions of
strongly deactivated arenes, such as 1,4-dichlorobenzene (8),
using a trisaminocyclopropenium (TAC) ion electrophotocatalyst
(Figure 1C).[19] Unexpectedly, when we attempted the reaction of
1-chloro-4-fluorobenzene 11 under the same conditions, the
[a]
Dr. H. Huang, Prof. T. H. Lambert
Department of Chemistry and Chemical Biology
Cornell University, Ithaca, NY 14853, USA
E-mail: Tristan.lambert@cornell.edu
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201909983
Angewandte Chemie International Edition
COMMUNICATION
major product observed was not that of C–H/N–H coupling, but
rather ipso substitution of the fluoride (Figure 1D). For the
reasons discussed above, this transformation was notable in that
it occurred at room temperature under mildly acidic conditions
(AcOH) and on a (classically) unactivated substrate. Here, we
report on the further development of this electrophotocatalytic
SNAr method.
was detrimental (entry 3), but other electrolytes were more
effective (entries
4
and 5), with one equivalent of
tetrabutylammonium tetrafluoroborate (TBABF4) showing the
highest efficiency (entry 5). Blue LEDs were optimal, with a
compact fluorescent light (CFL) resulting in a greatly diminished
yield (entry 6). No conversion was observed in the dark (entry 7).
Interestingly, without current (but with irradiation), there was no
catalyst turnover (entry 8), and the same reaction without acid and
electrolyte produced similar results (entry 9). As expected, without
catalyst no reaction occurred (entry 10). Meanwhile, 1.0 and 2.0
V both led to catalytic turnover (entries 11 and 12), but the yield
using 1.5 V was superior. Finally, we found that the use of 20
mol% catalyst furnished a higher yield (entry 13), and 15 mol%
DDQ added in two portions was equally effective (entry 14).
Table 1. Catalyst optimization studies.[a]
CHO
electrophotocatalyst
constant voltage
F
CHO
+
N
N
N
AcOH, electrolyte
N
H
Cl
C (+) | Pt (–)
blue LED
CH3CN
Cl
11
9
12
We next examined the scope of this reaction (Table 2). Using
4-fluorochlorobenzene (11), pyrazoles bearing carbonyl
functionality furnished products 12-16 in good yield (entries 1-3),
while halogenated pyrazoles also participated efficiently (entries
4-6). 1,2,3-triazoles were productive as well, leading to adducts
entry catalyst (mol%) Ecell (V) electrolyte (equiv.)
other
yield (%)b
1c
2
3
4
5
6
7
8
9
13 (8)
14 (10)
14 (10)
14 (10)
14 (10)
14 (10)
14 (10)
14 (10)
14 (10)
–
1.5
1.5
1.5
1.5
1.5
1.5
1.5
–
LiClO4 (6)
LiClO4 (6)
LiClO4 (1)
TBAPF6 (1)
TBABF4 (1)
TBABF4 (1)
TBABF4 (1)
TBABF4 (1)
–
CFL
25
60
23
45
60
18
0
–
20 and 21 (entries
7
and 8).
The reaction of 6-
–
bromobenzotriazole led to 22 in good yield and with a 1:1
regioselectivity for arylation of the two nitrogens. Both 1,3,5-
triazoles (entries 10 and 11) and tetrazole (entry 12) could be
arylated as well, although yields were modest in these cases.
–
–
CFL
no light
In terms of the fluoroarene component, we found 1,4-
difluorobenzene to be particularly effective as an arylating
reactant, giving rise to adduct 26 in 90% yield (entry 13).
Interestingly, it also proved possible to utilize 1,4-difluoro-2-
methylbenzene to generate the product 27 (entry 14), in which the
1-fluoro group was substituted selectively. We speculate that the
adjacent methyl group might support greater cationic character at
the 1-position of the intermediate radical cation, leading to this
surprising selectivity. The use of 1-bromo-4-fluorobenzene led to
product 28 (entry 15), while, 4-tert-butyl-1-fluorobenzene was
also productive to form 29 (entry 16). Additionally, the use of 1,2-
difluorobenzenes led to products 30 and 31 (entries 17 and 18) in
modest yields. On the other hand, 1,3-difluorobenzene was not
an effective participant in this method (entry 19). Remarkably,
however, fluorobenzene gave rise to the phenylated adduct 33 in
45% yield (entry 14), albeit with the production of a significant
amount of C–H / N–H coupled product as well. Fluoroarenes
bearing strongly electron-withdrawing groups did not lead to
arylated products (e.g. entry 21).
no current
12
11
0
–
no current, no acid
10
1.5
1.0
2.0
1.5
1.5
TBABF4 (1)
TBABF4 (1)
TBABF4 (1)
TBABF4 (1)
TBABF4 (1)
no catalyst
11
12
13
14
14 (10)
14 (10)
14 (20)
14 (15)d
–
–
–
32
50
75
75
e
(73)
–
ClO4
O
Me
Me
N
Me
Me
NC
NC
Cl
Cl
N
N
O
Me
Me
13
Ered(radical dication) = 3.33 V vs SCE
DDQ (14)
Ered (excited) = 3.18 V vs SCE
[a] Reaction conditions: 11 (2.0 mmol, 5.0 equiv), 9 (0.4 mmol, 1.0 equiv),
electrophotocatalyst (0.04 mmol, 0.1 equiv), MeCN (6.0 mL), AcOH (4.0 mmol,
10 equiv), TBABF4 (0.4 mmol, 1.0 equiv), N2, carbon felt anode, Pt cathode.
Reactions performed under constant voltage conditions with irradiation for 24 h
at rt. [b] Yields determined by 1H NMR. [c] 2.0 ml 11 was used. [d] 15% catalyst
added in two portions, 36 h reaction time. [e] Yield of isolated product.
To illustrate the applicability of this method to the synthesis of
more complex molecules, we also synthesized the products
shown in entries 22-28. Thus, a variety of halogenated purines
(entries 22-25), a steroidal ester-fused pyrazole (entry 26), and a-
aminoester-fused pyrazoles (entries 27 and 28) could be N-
arylated. Notably, the ester moieties of adducts 40-42 are
representative of functional groups that could be labile under the
strongly basic conditions of classic SNAr reactions, but which are
compatible with the current method.
In terms of optimization (Table 1), the original reaction was
performed in the presence of 8 mol% TAC 13 in an undivided cell
(Ecell = 1.5 V) under irradiation by white light with LiClO4 and AcOH
in acetonitrile (Table 1, entry 1). Despite extensive screening, we
were unable to achieve higher yields with catalyst 13. Alternatively,
2,3-dichloro-5,6-dicyanoquinone (DDQ, 14), which has a similar
excited state reduction potential [20-26], has also been used for
arene photooxidations.[23] Using 10 mol% DDQ and blue light-
emitting diodes (LEDs) but otherwise identical conditions, the
product 12 was generated in 60% yield. The use of less LiClO4
This article is protected by copyright. All rights reserved.

10.1002/anie.201909983
Angewandte Chemie International Edition
COMMUNICATION
Other nucleophiles can also participate (Table 3). For
example, simple alcohols reacted with 1,4-difluorobenzene to
furnish aryl ethers 43 and 44 in good yields (entries 1 and 2).
Cyclopropyl- and cyclopentylmethanol were also viable
nucleophiles (entries 3 and 4), as was menthol (entry 5). The
more functionalized 4-pentyn-1-ol led to 48 in serviceable yield
ethanol to furnish ether 50 (entry 8), while 4-tert-butyl-1-
fluorobenzene and methanol led to 51 in 50% yield (entry 9).
Interestingly, we found that water was also capable of serving as
a nucleophile (entry 10), although the yield of 4-fluorophenol (52)
was low. In terms of nitrogen nucleophiles, O-tert-butylcarbamate
led to the formation of N-Boc-4-fluoroaniline (53) in 35% yield
Table 2. Scope of the electrophotocatalytic arylation of heteroaromatics.[a]
15 mol% DDQ
AcOH, TBABF4
F
heteroarene
R
+
R
C (+) | Pt (–), blue LED
Ecell = 1.5 V, CH3CN
Heteroarene scope
(1)
O
(2)
(3)
(4)
(5)
(6)
O
CO2Et
Br
I
Br
Me
H
Me
N
N
N
N
N
N
N
N
N
N
N
N
Cl
Cl
Cl
Cl
Cl
Cl
12
73% yield
15
60% yield
16
78% yield
17
63% yield
18
53% yield
19
52% yield
Br
(7)
(8)
(9)
(10)
Cl
(11)
(12)
O
H
N
N
N
N
N
N
CO2Me
N
N
N
N
N
N
N
N
3
N
1 N
N
N
N
Cl
Cl
Cl
Cl
Cl
20
41% yield
21
56% yield
22
23
40% yield
24
32% yield
25
31% yield
58% yieldb (N1:N3 = 1:1)
Arene scope
(13)
O
N
(14)
(15)
O
N
(16)
(17)
(18)
Me
O
O
O
N
O
H
H
H
H
H
H
F
Me
N
F
1
N
N
N
N
N
N
N
N
4
Br
F
F
26
28
29
30
31
27
57% yield
C1:C4 = 10:1
90% yield
O
50% yield (5%)
62% yield (9%)
Bioactive molecule derivatives
(22) (23)
43% yield (12%)
41% yield (18%)
Cl
N
(19)
F
(20)
(21)
(24)
F
Cl
N
O
H
O
N
Cl
H
Cl
H
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Cl
NC
X
Cl
32
34
0% yield
37
38
56% yield
33
35
36
X = Cl, 61% yield
X = Br, 40% yield
<10% yield (25%)
58% yieldb
45% yield (21%)
(25)
(26)
(27)
Cl
(28)
O
O
I
N
Cl
N
O
COOEt
Me
CO2Me
n-Bu
O
O
Cl
N
N
N
H
HN
H
N
N
Boc
N
N
O
H
H
F
O
Cl
N
N
39
39% yield
40
50% yield
41
42
55% yieldb
53% yieldb
[a] See SI for detailed procedures. Reactions performed with 5 equiv. aryl fluoride and 1 equiv. nucleophile under constant voltage and irradiation for 36 h at rt.
Percentages in parentheses indicate yield of C-H/N–H coupling products. [b] 2.0 ml CH2Cl2 used as co-solvent.
(entry 6), and a protected sugar could be engaged despite
concerns of oxidative destruction of the acetal moiety (entry 7).
Meanwhile, reaction of some alternative aryl fluorides was also
productive. For example, 1-chloro-4-fluorobenzene reacted with
(entry 11). We found that an unprotected amine like i-propylamine
was not viable, however (entry 12).
A mechanistic rationale for this chemistry is shown in Figure
2. Photoexcitation of DDQ (14) produces an excited state species
This article is protected by copyright. All rights reserved.

10.1002/anie.201909983
Angewandte Chemie International Edition
COMMUNICATION
55 which is potent enough (Ered = 3.18 V vs SCE)[22] to oxidize
fluoroarene 11. Nucleophilic attack by pyrazole 9 to the resulting
radical cation 57 then produces radical 58. We presume that 58
must undergo a one-electron reduction to furnish anion 59 in order
to expel the fluoride leaving group to form product 21. However,
because DDQ radical anion 56 is a poor reductant,[15-22, 27] the
catalytic cycle likely cannot be closed by transfer of an electron
from 56 to 58, but rather the reduction of 58 and the reoxidation
of 56 must be accomplished by the electrotrodes. Additional
support for this mechanistic rationale is provided in the supporting
information.
anode
cathode
CHO
N
N
Cl
12
DDQ
14
photon
e–
F–
F
F
DDQ*
55
N
–
N
N
back
electron
transfer
59
CHO
e–
F
Cl
DDQ●–
Cl
56
X
DDQ●–
11
Table 3. Electrophotocatalytic SNAr reactions with various nucleophiles. [a]
56
F
N
+
F
Nu
20 mol% DDQ
Cl
Cl
H
N
H+
+
57
Nu–H
58
CHO
AcOH, TBABF4
C (+) | Pt (–)
Ecell = 1.5 V
N
R
R
CHO
9
blue LED
CH3CN
Figure 2. Proposed mechanism for electrophotocatalytic SNAr reaction.
(1)
(2)
(3)
O
O
O
Me
Et
For the reactions shown in Table 3, the products have lower
oxidation potentials than the starting materials, and so it is
perhaps remarkable that the products remain intact. Indeed, we
have found that alkoxybenzenes do not undergo any reaction
(Scheme S1 in SI), either with pyrazoles or alcohols as might be
expected from the mechanistic proposal and the precedent of
Nicewicz. We propose that, although the single-electron oxidation
event is facile, the back-electron transfer is very rapid and thus
outcompetes nucleophilic attack to the transient radical cation
intermediate. Indeed, a similar rationale has been advanced in the
DDQ photoxidation of benzene to phenol.[22]
F
F
F
43
63% yieldb
44
45
65% yieldb
43% yield
(5)
(8)
i-Pr
(6)
(4)
(7)
O
O
O
F
F
F
Me
46
66% yield
47
41% yield
48
53% yield
Me
O
(9)
Me
O
O
O
O
Et
Me
O
Cl
O
The ability to achieve SNAr reactions on unactivated
substrates under mild conditions offers unique possibilities for
O
F
Me
Me
49
46% yield
50
51
52% yieldc
50% yieldc
chemoselective reactions (Scheme 1).
For example, we
(10)
(11)
(12)
subjected pyrazole 9 and a 1:1 mixture 1-chloro-4-fluorobenzene
(11) and 1-fluoro-2,4-dinitrobenzene (60) to our standard reaction
conditions, under which adduct 12 was formed in 65% yield as the
only observable product. Aryl fluoride 60 was left untouched by
these conditions. Meanwhile, 1-chloro-4-fluorobenzene (11) was
also selectively converted to 12 in the presence of 4-fluoroanisole
(43), with the latter left intact.
H
H
OH
N
O
N
Me
Me
O
F
F
F
52
53
35% yield
54
28% yieldb
no reaction
[a] Reactions performed with 5 equiv. aryl fluoride and 1 equiv. nucleophile
under constant voltage and irradiation at rt for 24-36 h. [b] Yield determined by
UPLC. [c] Yield determined by 1H NMR.
This article is protected by copyright. All rights reserved.

10.1002/anie.201909983
Angewandte Chemie International Edition
COMMUNICATION
F
O
N
15 mol% DDQ
Cl
H
In conclusion, we have developed an electrophotocatalytic
method for SNAr reactions of unactivated fluorides that occurs at
room temperature and without the use of strong base. This
method offers an arylation technology complementary to existing
SNAr methods. Furthermore, this work advances the nascent
area of electrophotocatalysis by demonstrating how the
combination of light and electrical energy can be used to promote
redox neutral reactions.
blue LED
CHO
11
Ecell = 1.5 V
N
N
+
N
H
C (+) | Pt (–)
NO2
AcOH, CH3CN
F
F
Cl
9
12
65% yield
(96% 60)
O2N
60
O
30 mol% DDQ
blue LED
H
Cl
CHO
11
43
Acknowledgements
Ecell = 1.5 V
N
N
+
N
F
N
H
C (+) | Pt (–)
AcOH, CH3CN
Research reported in this publication was supported by the National
Institutes of Health under R35 GM127135.
Cl
9
MeO
12
61% yield
(95% 43)
Keywords: Electrophotocatalysis • SNAr • arylation •
Scheme 1. Demonstration of chemoselectivity.
electrochemistry • photochemistry
[1]
[2]
H. Amii, K. Uneyama, Chem. Rev. 2009, 109, 2119-2183.
[15] N. A. Romero, D. A. Nicewicz, Chem. Rev. 2016, 116, 10075-10166.
[16] S. Fukuzumi, K. Ohkubo, Org. Biomol. Chem. 2014, 12, 6059-6071.
[17] C. K. Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013, 113,
5322-5363.
M. Smith, J. March, March’s Advanced Organic Chemistry: Reactions,
Mechanisms, and Structure, Wiley-Interscience, Hoboken, 2007, pp. 853
– 933.
[3]
[4]
R. Jitchati, A. S. Batsanov, M. R. Bryce,Tetrahedron 2009, 65, 855-861.
A. Huang, F. Liu, C. Zhan, Y. Liu, C. Ma, Org. Biomol. Chem. 2011, 9,
7351-7357.
[18] For examples of electrophotocatalysis or photoelectrocatalysis, see: (a)
J.-C. Moutet, G. Reverdy, J. Chem. Soc., Chem. Commun. 1982, 654-
655. (b) R. Scheffold, R. Orlinski, J. Am. Chem. Soc. 1983, 105, 7200-
7202. (c) H. Yan, Z.-W. Hou, H.-C. Xu, Angew. Chem. Int. Ed. 2019, 58,
4592-4595; Angew. Chem. 2019, 131, 4640–4643. See also: (d) F.
Wang, S. S. Stahl, Angew. Chem. Int. Ed. 2019, 58, 6385–6390; Angew.
Chem. 2019, 131, 6451–6456.
[5]
[6]
[7]
[8]
M. Bella, S. Kobbelgaard, K. A. Jorgensen, J. Am. Chem. Soc. 2005, 127,
3670-3671.
G. Lautrette, F. Touti, H. G. Lee, P. Dai, B. L. Pentelute, J. Am. Chem.
Soc. 2016, 138, 8340-8343.
X. Wang, Y. Tang, C. Y. Long, W. K. Dong, C. C. Li, X. H. Xu, W. X. Zhao,
X. Q. Wang, Org. Lett. 2018, 20, 4749-4753.
[19] H. Huang, Z. M. Strater, M. Rauch, J. Shee, T. Sisto, C. Nuckolls, T. H.
Lambert, Angew. Chem. Int. Ed. 2019, 58, 13318-13322; Angew. Chem.
2019, 131, 13452-13456.
R. Travieso-Puente, S. Budzak, J. Chen, P. Stacko, J. T. B. H.
Jastrzebski, D. Jacquemin, E. Otten, J. Am. Chem. Soc. 2017, 139,
3328-3331
[20] A. E. Wendlandt, S. S. Stahl, Angew. Chem. Int. Ed. 2015, 54, 14638-
14658; Angew. Chem. 2015, 127, 14848-14868..
[9]
F. Diness, D. P. Fairlie, Angew. Chem. Int. Ed. 2012, 51, 8012-8016;
Angew. Chem. 2012, 124, 8136-8140.
[21] D. Walker, J. D. Hiebert, Chem. Rev. 1967, 67, 153-195.
[22] K. Ohkubo, A. Fujimoto, S. Fukuzumi, J. Am. Chem. Soc. 2013, 135,
5368-5371.
[10] Y. Zheng, A. S. Batsanov, V. Jankus, F. B. Dias, M. R. Bryce, A. P.
Monkman, J. Org. Chem. 2011, 76, 8300-8310.
[23] S. Das, P. Natarajan, B. Konig, Chem. Eur. J. 2017, 23, 18161-18165.
[24] C. Song, H. Yi, B. Dou, Y. Li, A. K. Singh, A. Lei, Chem. Commun. 2017,
53, 3689-3692.
[11] C. Borch Jacobsen, M. Meldal, F. Diness, Chem. Eur. J. 2017, 23, 846-
851.
[12] Y. Y. Lin, M. Li, X. F. Ji, J. J. Wu, S. Cao, Tetrahedron 2017, 73, 1466-
1472.
[25] K. Ohkubo, K. Hirose, S. Fukuzumi, Chem. Asian. J. 2016, 11, 2255-
2259.
[13] J. Mao, Z. Wang, X. Xu, G. Liu, R. Jiang, H. Guan, Z. Zheng, P. J. Walsh,
Angew. Chem. Int. Ed. 2019, 58, 11033-11038; Angew. Chem. 2019, 131,
11149-11154.
[26] F. Rusch, J.-C. Schober, M. Brasholz, Chem. Cat. Chem 2016, 8, 2881-
2884.
[27] M. T. Huynh, C. W. Anson, A. C. Cavell, S. S. Stahl, S. Hammes-Schiffer,
J. Am. Chem. Soc. 2016, 138, 15903-15910.
[14] N. E. S. Tay, D. A. Nicewicz, J. Am. Chem. Soc. 2017, 139, 16100-16104.
This article is protected by copyright. All rights reserved.

10.1002/anie.201909983
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
catalytic
DDQ
F
Nu
Unactivated aryl
fluorides engage in SNAr
reactions at room
temperature and without
the strong base using
DDQ as an
He Huang, Tristan H.
Lambert
R
+
Nu–H
R
blue LEDs
Ecell = 1.5 V
Page No. – Page No.
electrophotocatalysis
Title
electrophotocatalyst.
This article is protected by copyright. All rights reserved.