OrthoC-H arylation of arenes at room temperature using visible light ruthenium C-H activation

Article abstract of DOI:10.1039/d0sc01289k

A ruthenium-catalyzedorthoC-H arylation process is described using visible light. Using the readily available catalyst [RuCl₂(p-cymene)]₂, visible light irradiation was found to enable arylation of 2-aryl-pyridines at room temperature for a range of aryl bromides and iodides.

Full text of DOI:10.1039/d0sc01289k

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ARTICLE
ortho C-H Arylation of Arenes at Room Temperature
Using Visible Light Ruthenium C-H Activation
Received 00th January 20xx,
Accepted 00th January 20xx
Arunachalam Sagadevan, Anastasios Charitou, Fen Wang, Maria Ivanova, Martin Vuagnat, and Michael F. Greaney*
DOI: 10.1039/x0xx00000x
A ruthenium-catalyzed ortho C-H arylation process is described using visible light. Using the readily available catalyst
[RuCl2(p-cymene)]2, visible light irradiation was found to enable arylation of 2-aryl-pyridines at room temperature for a
range of aryl bromides and iodides.
alkylation and ortho-arylation, operate through very different
frameworks in the thermal regime, with the former thought to
involve discrete 2o and 3o carbon-centered radicals adding to
Ru(III) metallacycles (Scheme 1A),8 and the latter involving
more typical oxidative additions of aryl halides to a Ru(II)
center.9 The role of photoexcitation on a putative arylation
process was thus interesting to examine in light of this
dichotomy; as the photoreductive formation of highly reactive
aryl radicals in analogy to Ru-meta alkylation chemistry was
unlikely to be a significant factor.
Introduction
The integration of visible light photoredox catalysis with
transition metal C-H activation catalysis creates new pathways
for bond formation, that frequently operate under mild
conditions. The two catalysis regimes can be meshed via two
separate catalyst entities, with two corresponding catalysis
cycles;1 or alternatively, a single dual-function catalyst system
can be used.2 We are interested in this latter approach to
exploit the facility of some Ru catalysts to absorb visible light,
such that their native C-H activation function is enhanced in
terms of improved rates, substrate scope, and environmental
impact. We, along with the Ackermann group, recently
demonstrated this concept for the Ru-catalysed meta-
alkylation reaction (Scheme 1).3 The tert-butylation of 2-
phenylpyridine 1, typically carried out under thermal
conditions (ca. 100 °C), could proceed at room temperature
under blue-light irradiation using the widely employed catalyst
[RuCl2(p-cymene)]2 to give the alkylated product 3 in good
yield.
A. Photo meta-Alkylation
N
[RuCl2(p-cymene)]2
(10 mol%)
N
I
+
KOAc (2.0 equiv)
RT
2
3
1
, 82%
via radical C-C bond formation
L
L
RuIII
L
RuIII
N
L
N
We were interested in exploring this concept of photo-Ru C-H
activation in the arylation regime. Ru-catalysed ortho-arylation
is a powerful approach to C-C bond formation that has seen
extensive development in recent years.4 Proceeding via Ru(II) /
Ru(IV) catalytic cycles, the process has excellent scope for aryl
halides (including aryl chlorides), is very tolerant of water and
air, and the cost of Ru compares favorably with the far more
expensive alternatives of Pd and Rh that are frequently used
for ortho C-H arylation. High reaction temperatures are
standard, however, when using [RuCl2(p-cymene)]2 as
catalyst.5,6 A photo Ru arylation reaction could activate
alternative mechanistic paths and offer the possibilty of room
temperature reaction.7 The two Ru-catalyzed processes, meta-
B. Proposed Ru-catalyzed arylation
X
N
N
[RuCl2(p-cymene)]2 (cat)
Ar
+
Ar
RT
1
4
5
typically via oxidative addition
N
N
ArBr
L
Ar
RuII
L
RuIV
Br
N
N
School of Chemistry, The University of Manchester, Oxford Road, Manchester,
M13 9PL, United Kingdom.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Scheme 1 Ruthenium photocatalysis for meta-alkylation and proposed ortho-arylation.
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derivative gave slightly improved yields and wasVireewtAaritnicleedOnflioner
substrate screening (entry 7). Common solvents such as
Results and Discussion
Photoarylation of 2-arylazines with aryl halides
DOI: 10.1039/D0SC01289K
MeOH, DCM, MeCN, or DMF were not effective (entry 8), nor
were the simple Ru(II) salts shown in entries 9-11. Control
experiments established that both light and catalyst were
essential for reaction at room temp (entries 13-15), and as
with our previous Ru meta systems,10 the reaction was found
to be air sensitive and require inert atmospheres to proceed.
We began by examining the archetypal arylation system of 2-
phenylpyridine 1a with bromoanisole 4a (Table 1). Using
[RuCl2(p-cymene)]2 as catalyst in the presence of KOAc, under
blue LED irradiation, we were pleased to observe successful
arylation at room temperature to give a good 70% combined
conversion to mono and di-ortho-arylated products 5a and
5aa. As is typical for Ru ortho-arylations of 2-phenyl pyridine,
the monoarylated product is a superior substrate than the
starting material, giving the diarylated material as the major
product.
Scheme 2 Photoarylation of 2-arylazines with p-bromoanisole (Anis = 4-BrC6H4).
R2
R2
R2
Br
(10 mol %)
[RuCl2(p-cymene)]2
N
N
N
N-Ac-L-Ile (10 mol %)
+
+
Ar
Ar
Ar
KOAc, 2-MeTHF, 5.0 eq H2O
OMe
4a
blue LEDs
, RT, N2, 24 h
R1
R1
Table 1 Development of Ru photoarylation
R1
1
5-mono
5-di
N
Br
(10 mol %)
[RuCl2(p-cymene)]2
N
N
N
N
N
KOAc, solvent, additives
N
+
+
Ar
Ar
Ar
Anis
Anis
Anis
Anis
Anis
blue LEDs
, RT, N2, 24 h
Anis
Anis
OMe
4a
1a
5a
5aa
OMe
5bb
t-Bu
47%
Me
5d
5aa
5cc
58%
53%
40%
(13% mono)[a]
(34% di)[a][b]
(16% mono)
(15% mono)
entry
catalyst
additives
MesCO2H
MesCO2H
MesCO2H
MesCO2H
N-Ac-l-
isoleu
N-Ac-l-
isoleu
N-Ac-l-
solvent
1,4-dioxane
DME
yield [%][a]
(70)
1
2
3
4
5
[RuCl2(p-cymene)]2
[RuCl2(p-cymene)]2
[RuCl2(p-cymene)]2
[RuCl2(p-cymene)]2
[RuCl2(p-cymene)]2
N
N
N
N
60
65
(72)
(74)
Anis
Anis
Anis
Anis
THF
Anis
Anis
2MeTHF
2MeTHF
MeO
Me
CO2Me
5ff
Ph
5ee
5g
5h
67%
66%
61%
79%
Me
6
7
[RuCl2(p-cymene)]2
[RuCl2(p-cymene)]2
2MeTHF
2MeTHF
(78)
(80)
Me
N
N
N
N
Anis
Anis
Anis
Anis
Anis
Anis
isoleu / H2O
none/H2O
N-Ac-l-
Cl
5i
8
9
[RuCl2(p-cymene)]2
[RuCl2(p-cymene)]2
2MeTHF
MeOH,
MeCN,
DCM, or
DMF
(80)
trace
5j
60%
5kk
5ll
65%
(20% mono)
65%
(15% mono)
68%
Me
isoleu
N
N
N
N
N
N
10
11
RuCl3·H2O
Ru(PPh3)4Cl2
none
N-Ac-l-
2MeTHF
2MeTHF
0
0
Anis
Anis
Anis
Anis
Anis
Anis
Anis
S
isoleu / H2O
None
N-Ac-l-
isoleu / H2O
N-Ac-l-
isoleu
N-Ac-l-
isoleu / H2O
N-Ac-l-
OMe
5mm
12
13
Ru(bpy)3Cl2
[RuCl2(p-cymene)]2
(5 mol%)
2MeTHF
2MeTHF
0
(72)
[b][c]
5n
5q
32%
67%
71%
5pp
52%
5o
63%
(16% mono)[a][b][c]
14
15
16
no catalyst
2MeTHF
2MeTHF
2MeTHF
0
0
0
Unless otherwise noted, reaction conditions were as follows: 1 (1.0 eq, 0.3 mmol), 4a
(1.5 eq, 0.6 mmol), [Ru] catalyst (10 mol %), additive (10 mol %), base (2.0 eq), solvent
(1 mL), H2O (5 eq). The mixture was irradiated with blue LEDs (40-90 W power) for 24 h
under N2 (1 atm). The yields refer to isolated yields after purification by column
chromatography on silica gel (major product illustrated). [a] Reaction performed using
0.250 mmol of 1 (1.0 eq) and 0.375 mmol of 4a (1.5 eq). [b] Reaction performed
without the addition of N-Ac-L-Ile. [c] Reaction run for 40 h.
[RuCl2(p-cymene)]2
dark
[RuCl2(p-cymene)]2
with air
isoleu / H2O
Reaction conditions: 1a (0.3 mmol), 4a (0.6 mmol), [Ru] catalyst (10 mol%),
additive (10 mol%), base 2.0 equiv, solvent (1 mL). The mixture was irradiated
with blue LEDs (40-90 W power) for 24 h under N2 atmosphere. [a] Yields in
brackets refer to combined 1H NMR yield using 1,3,5-trimethylbenzene
(mesitylene) as the internal standard, unbracketed yields are isolated. THF =
With these conditions in hand, we established the scope of the
reaction with respect to the C-H component using p-
bromoanisole as the arylating agent. Alkyl, alkoxy, carboxy,
and phenyl substitution was tolerated in the 4-position of the
tetrahydrofuran, 2-MeTHF
=
2-methyl tetrahydrofuran, DME
=
1,2-
arene, favoring the disubstituted product (5aa
– 5ff).
dimethoxyethane, DMF = dimethyl formaldehyde, DCM = dichloromethane.
Substitution in the 3-position with MeO, Me, Cl, and fused ring
of the naphthyl group acted as a steric control element,
suppressing the second ortho ruthenation step and yielding
mono-arylated products exclusively (5g – 5j). Some alterations
The reaction worked well in ethereal solvents (entries 1-4),
and a screen of carboxylate and amino acid additives did not
yield substantial improvements, although the acetylisoleucine
2 | J. Name., 2012, 00, 1-3
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to the directing group were possible, with alkylated pyridines generally effective in this protocol, althoughVie1w-Abrrtioclme Oon-li2ne-
DOI: 10.1039/D0SC01289K
being effective in the reaction, along with bicyclic quinoline methoxybenzene did react successfully to give 6k in 50% yield.
and isoquinoline directing groups (5kk – 5o). Finally, changing This ortho substitution pattern is known to favour an oxidative
the arene C-H to the 5-membered heteroarene thiophene C-H dimerization pathway for aryl halide substrates.11
was partially successful in the photoarylation, affording the
novel pyridyl thiophene 5q but in diminished yield.
Mechanistic studies
The exclusive formation of ortho-arylated products, allied with
the high reduction potential of aryl halides (ca. -2.5 eV)12
would likely preclude any discrete aryl radical generation
through SET from a Ru(II) catalytic species in the reaction. This
was supported with radical quenching experiments, where the
reaction proceeded to reasonable conversion in the presence
of both BHT and 1,1-diphenylethene (DHP), although TEMPO
was observed to completely inhibit the reaction forming an
Scheme 3 Photoarylation of 2-arylpyridines with various aryl halides.
[RuCl2(p-cymene)]2
X
N
N
N
(10 mol %)
R
R
+
or
Ar
Ar
Ar
2-MeTHF, KOAc
R2
blue LEDs
5.0 eq H2O,
RT, N2, 24h
1a
4
6-mono
Ph
6-di
R = H,
1b
R = Me,
insoluble black suspension.
A competition experiment
N
tBu
N
Me
N
Ph
Me
Me
between the electron-rich bromoanisole 4a and electron-poor
bromo-benzoate afforded a 3:1 ratio of products in favour of
the benzoate 6i, in line with what is commonly observed in
high-temperature Ru ortho-arylation through an oxidative
addition mechanism.13
[a]
[b]
6a
81%
X = Br
6b
6cc
47%
70%
X = Br
X = I
Recent investigations from Larrosa and co-workers into the
mechanism of Ru(II)-ortho arylation have identified the
inhibitory role of the cymene ligand in [RuCl2(p-cymene)]2
catalysis.5,14 While this ligand affords an air-stable, easy to use
catalyst, it retards activity in catalytic cycles, and must de-
complex to enable the formation of the active bis-
cycloruthenated complex C (Scheme 4E). We analysed the free
cymene formed in the reaction under room temperature blue
light irradiation against an ambient light control.
Decomplexation was observed in both cases, but with a clear
rate increase under blue LED irradiation (Scheme 4C). Photo-
decomplexation of 6-arenes such as cymene is well known,
and has been used as a triggering mechanism for both
chemical and biological activity in Ru(II) complexes.15 However,
a light / dark experiment (Scheme 4D) demonstrated that
continuous irradiation was necessary for complete conversion.
This suggests that either reversible cymene re-complexation
can inhibit the reaction, or there is an additional role for visible
light in the catalytic cycle (e.g. photoexcitation of complexes C
or D to facilitate either oxidative addition or reductive
elimination, respectively). Stern-Volmer experiments with
stoichiometric pre-catalyst A and aryl halides did not show
clear evidence of photoluminescence quenching, but we
cannot rule out an additional role for visible light in
subsequent steps in the catalytic cycle at this time.
N
N
Cl
N
Br
Me
Me
S
S
[b]
2
6dd
6e
6f
=
52%
58%
X = Br
R
Br, 65%
X = I
X = I
F
N
F
N
Ac
N
CO2Et
Me
Me
[b]
6gg
77%
[c]
6i
71%
X = Br
6h
62%
X = I
X = Br
N
OMe
N
Me
Me
OMe
79%[b]
X = Br
6j
6k
50%
X = Br
Unless otherwise noted, reaction conditions were as follows: 1 (1.0 eq, 0.25 – 0.30
mmol), 4 (1.5 eq, 0.375 – 0.45 mmol), [Ru] catalyst (10 mol %), base (2.0 eq), solvent (1
mL), H2O (5 eq). The mixture was irradiated with blue LEDs (40-90 W power) for 24 h in
N2 (1 atm). The yields refer to isolated yields after purification by column
chromatography on silica gel. [a] Reaction run for 72 h. [b] Reaction performed using
0.3 mmol of 1 (1.0 eq) and 0.6 mmol of 4 (2.0 eq) in the presence of N-Ac-L-Ile (10 mol
%). [c] Reaction run for 40 h.
We then turned our attention to the aryl halide coupling
partner, and were pleased to find broad substrate scope
across a variety of aryl bromides and iodides (Scheme 3). We
Conclusions
used 3-methyl-2-phenylpyridine (1b) as the substrate in the We have established
a room temperature, ruthenium
majority of cases, to simplify the reaction pathway for catalysed ortho-arylation reaction that proceeds at room
monoarylation. We observed good efficiencies for 4-alkyl and temperature under the agency of visible light irradiation. The
moderate efficiencies for 4-phenyl aryl halides (6a - 6cc), reaction encompasses a wide selection of aryl halides,
along with the 2-thienyliodide substrate (6dd). Halogens were producing C-H arylated products that are typically accessed at
well tolerated (6e – 6gg). Electron poor (4-keto and 4-carboxy temperatures in excess of 100 °C. Initial observations point to
ester groups) along with electron rich (4-methoxy) reacted a photo-decomplexation of the cymene ligand from the
smoothly in each case. Ortho-substituted aryl halides were not ruthenium pre-catalyst as playing a key role in the catalytic
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Scheme 4 Mechanistic investigations and proposed pathway. Conversion in part C
cycle. Future work will extend the photoarylation to new C-H
substrate classes, and further delineate the role of visible light
in the mechanism.
View Article Online
refers to amount of p-cymene produced.
DOI: 10.1039/D0SC01289K
Conflicts of interest
A. Competition between aryl halides
There are no conflicts to declare.
[RuCl2(p-cymene)]2
(10 mol %)
Br
R
N
CO2Et
N
OMe
N
Me
Me
Me
+
+
2-MeTHF, KOAc
5.0 eq H2O, blue LEDs
RT, N2, 24h
Acknowledgements
This work was supported by the EPSRC, The Royal Society, and
the EU. We thank Dr Louise Natrajan (University of
Manchester) for helpful discussions.
1b
4a
4b
6i
53%
6j
18%
R = 4-OMe,
R = 4-CO2Et,
6i : 6i
3 : 1
71% combined NMR yield
B. Radical inhibitors
[RuCl2(p-cymene)]2
KOAc, 2-MeTHF,
H2O
Br
Ar
N
N
OMe
Me
Me
+
Radical Scavenger
blue LEDs
RT, N2, 24h
Notes and references
OMe
4a
6j
1b
TEMPO = 0% (black suspension)
BHT = 54%
1,1-Diphenylethylene = 34%
C. p-Cymene production
1
Reviews: a) M. D. Levin, S. Kim and F. D. Toste, ACS Cent. Sci.
2016, 2, 293. b) J. Twilton, C. Le, P. Zhang, M. H. Shaw, R. W.
Evans and D. W. C. MacMillan, Nat. Rev. Chem. 2017, 1, 0052; c)
J. A. Milligan, J. P. Phelan, S. O. Badir and G. A. Molander,
Angew. Chem. Int. Ed. 2019, 58, 6152; d) M. Parasram, V.
Gevorgyan, Chem. Soc. Rev. 2017, 46, 6227.
D. Light on / off
Br
Ar
[RuCl2(p-cymene)]2
(10 mol %)
N
N
N
2
Selected recent examples: a) W. Ding, L.-Q. Lu, Q. Q. Zhou, Y.
+
+
Ar
Ar
Ar
KOAc (2.0 eq)
Wei, J. –R. Chen and W. –J. Xiao, J. Am. Chem. Soc. 2017, 139,
63. b) Y. Li, K. Zhou, Z. Wen, S. Cao, X. Shen, M. Lei and L. Gong,
J. Am. Chem. Soc. 2018, 140, 15850. c) Q. M. Kainz, C. D. Matier,
A. Bartoszewicz, S. L. Zultanski, J. C. Peters, G. C. Fu, Science,
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J. C. Peters, J. Am. Chem. Soc. 2017, 139, 12716. e) D. B. Bagal, G.
Kachkovskyi, M. Knorn, T. Rawner, B. M. Bhanage, O. Reiser,
Angew. Chem. Int. Ed. 2015, 54, 6999. f) A. Sagadevan, A.
Ragupathi and K. C. Hwang, Angew. Chem. Int. Ed. 2015, 54,
13896. g) H. Huo, X. Shen, C. Wang, L. Zhang, P. Röse, L. –A.
Chen, K. Harms, M. Marsch, G. Hilt and E. Meggers, Nature 2014,
515, 100. h) L. Zhang and E. Meggers, Acc. Chem. Res. 2017, 50,
320. i) J. Thongpaen, R. Manguin, V. Dorcet, T. Vives, C.
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58, 15244. j) S. Witzel, J. Xie, M. Rudolph and A. S. K. Hashmi,
Adv. Synth. Catal. 2017, 359, 1522. k) I. Abdiaj, A. Fontana, M.
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Maity, C. Zhu, P. E. Krach, L. Cavallo and M. Rueping, Angew.
Chem. Int. Ed. 2019, 58, 3412.
2-MeTHF, 5.0 eq H2
O
OMe
2a
blue LEDs, RT, N2
1a
5a
5aa
light on up to 5 h = 48% (5a+5aa)
light off after 5h to 24h = 53% (5a+ 5aa)
E. Proposed pathway
Me
iPr
N
RuII
Cl
H
1a
KOAc
N
A
[RuCl2(p-cymene)]2
p-cymene
N
N
L
Ru
H
N
X
1a
Ar
5a
B
reductive
elimination
3
a) A. Sagadevan and M. F. Greaney, Angew. Chem. Int. Ed.
N
N
2019, 58, 9826; b) P. Gandeepan, J. Koeller, K. Korvorapun, J.
Mohr and L. Ackermann, Angew. Chem. Int. Ed. 2019, 58, 9820.
L
L
RuII
Ar
RuIV
X
N
4
Reviews: a) P. Nareddy, F. Jordan and M. Szostak, ACS Catal.
N
D
C
2017, 7, 5721. b) L. Ackermann, Org. Proc. Res. Dev. 2015, 19,
260. c) P. B. Arockiam, C. Bruneau, and P. H. Dixneuf, Chem. Rev.
2012, 112, 5879.
oxidative
addition
Ar
X
5
Selected examples: a) M. Drev, U. Grošelj, B. Ledinek, F.
4 | J. Name., 2012, 00, 1-3
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View Article Online
DOI: 10.1039/D0SC01289K
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6
For a recent mild Ru-catalyzed arylation using cyclometallated
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8
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