Micellar Catalysis for Ruthenium(II)-Catalyzed C?H Arylation: Weak-Coordination-Enabled C?H Activation in H2O

Article abstract of DOI:10.1002/anie.201901856

Chemoselective C?H arylations were accomplished through micellar catalysis by a versatile single-component ruthenium catalyst. The strategy provided expedient access to C?H-arylated ferrocenes with wide functional-group tolerance and ample scope through weak chelation assistance. The sustainability of the C?H arylation was demonstrated by outstanding atom-economy and recycling studies. Detailed computational studies provided support for a facile C?H activation through thioketone assistance.

Full text of DOI:10.1002/anie.201901856

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Accepted Article
Title: Micellar Catalysis for Ruthenium(II)-Catalyzed C−H Arylation:
Weak-Coordination-Enabled C−H Activation in H2O
Authors: Santhivardhana Reddy Yetra, Torben Rogge, Svenja
Warratz, Julia Struwe, Wentao Peng, Philipp Vana, and Lutz
Ackermann
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201901856
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Angewandte Chemie International Edition
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COMMUNICATION
Micellar Catalysis for Ruthenium(II)-Catalyzed C−H Arylation:
Weak-Coordination-Enabled C−H Activation in H O
2
[
a]
[a]
[a]
[a]
[b]
Santhivardhana Reddy Yetra, Torben Rogge, Svenja Warratz, Julia Struwe, Wentao Peng,
[
b]
[a]
Philipp Vana, and Lutz Ackermann*
Abstract: Chemoselective C–H arylations were accomplished in
terms of micellar catalysis by versatile single-component
user-friendly single-component ruthenium catalyst for ferrocene
C–H arylations and (iii) computational insights into the nature of
weak thiocarbonyl coordination for C−H activation.
a
ruthenium catalyst. The strategy provided expedient access to C–H
arylated ferrocenes with wide functional group tolerance and ample
scope through weak chelation assistance. The sustainability of the
C–H arylation was demonstrated by an outstanding atom-economy
and recycling studies. Detailed computational studies provided
support for a facile C–H activation through thioketone assistance.
Transition metal-catalyzed C–H activations have surfaced as a
[
1]
powerful tool for molecular syntheses, with transformative
[2]
applications to inter alia material sciences and pharmaceutical
[3]
industries. The sustainability of the C–H activation strategy
could be improved when using water as a nonflammable,
Figure 1. Micellar catalysis for ruthenium-catalyzed C–H arylation.
[
4]
nontoxic,
environmentally-friendly
reaction
medium.
Unfortunately, the organic compounds and catalysts of interest
are usually not soluble in water, leading to limited
We commenced our studies by probing the envisioned C–H
[
5]
heterogeneous catalysis not in, but rather on water. In sharp
contrast, specific surfactants have been identified as
increasingly viable tools for realizing homogeneous metal
arylation of ferrocene 1a by 4-bromo anisole (2a) with [RuCl
2
(p-
cymene)] as the catalyst in TPGS-750M/H O (Table 1 and
2
2
Table S–1-S–3). Notably, additive-free conditions provided
unsatisfactory results (entry 1). Instead, the addition of acetic
acid afforded the desired arylated ferrocene 3aa in 62% yield
[6]
[7]
catalysis in water. Thus, pioneering studies by Lipshutz,
[
8]
[9]
[10]
Gallou, Tan, and Handa, among others, have indicated the
major potential of designer surfactants for palladium-catalyzed
coupling chemistry in terms of trace metal impurities,
homogenous catalysis and improved selectivities. Despite of
these indisputable advances, micellar C–H functionalization
(
entry 2). Among various carboxylic acid additives,
adamantylcarboxylic acid gave the best performance (entry 5).
Moreover, single-component ruthenium catalysts were found to
be more efficient in furnishing the desired arylated product 3aa,
[
11]
[12]
continues to be scarce,
while sustainable ruthenium
even at reduced reaction temperatures of 50 to 70 °C (entries
micellar C–H activation catalysis has thus far proven elusive.
Within our program on ruthenium-catalyzed C–H arylations,
[16]
6-9). Likewise, arene-free ruthenium catalysts
proved also
[
13]
effective (entries 10 and 11), while unsatisfactory results were
obtained with a cationic ruthenium complex (entry 12). Variation
of the surfactants did not lead to superior results (entries 13-19).
Importantly, when water was used as the reaction medium we
observed only trace amounts of product 3aa, which indicates the
key role of the micellar regime (entry 20). The unique catalytic
performance and water tolerance of the ruthenium(II) micellar
catalysis were mirrored by palladium, rhodium, cobalt and
manganese complexes falling short in delivering the desired C–
H arylation (entries 21-24).
we have now devised C–H arylations assisted by weakly-
coordinating thiocarbonyls, allowing the first micellar-enabled C–
[
14]
H activation on substituted ferrocenes
– key structural motifs
in organocatalysts and versatile ligands for stereoselective
[
15]
catalysis.
Salient features of our approach include (i)
ruthenium-catalyzed C–H activation by micellar catalysis, (ii) a
[
a]
b]
Dr. S. R. Yetra, T. Rogge, Dr. S. Warratz, J. Struwe
Prof. Dr. L. Ackermann
Institut für Organische und Biomolekulare Chemie
Georg-August-Universität Göttingen
Tammannstrasse 2, 37077 Göttingen, Germany
E-mail: Lutz.Ackermann@chemie.uni-goettingen.de
Homepage:http://www.ackermann.chemie.uni-goettingen.de/
W. Peng, Prof. Dr. P. Vana
[
Institut für Physikalische Chemie
Georg-August-Universität Göttingen
Tammannstrasse 6, 37077 Göttingen, Germany
Supporting information for this article is given via a link at the end of the
document.((Please delete this text if not appropriate))
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Angewandte Chemie International Edition
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COMMUNICATION
[
a]
Table 1. Thiocarbonyl-assisted C−H arylation.
dibromoarenes selective mono C–Br cleavage was observed,
while both C–Br bonds could be functionalized when an
excess of ferrocene 1a was employed (3aj, 3ak). The
outstanding chemoselectivity of the versatile ruthenium(II)
catalyst was reflected by fully tolerating valuable functional
groups, such as chloro, bromo, ester, ketone and aldehyde
substituents. Further, heteroaryl (3ar), and peptide-substituted
(
3as) ferrocenes were obtained in a chemoselective manner.
Entry
[TM]
Additive
Micelle
Yield
%)
(
1
2
3
4
5
6
7
8
9
[RuCl
[RuCl
[RuCl
[RuCl
[RuCl
2
2
2
2
2
(p-cymene)]
(p-cymene)]
(p-cymene)]
(p-cymene)]
(p-cymene)]
2
2
2
2
2
---
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
2
2
2
2
2
O
O
O
O
O
O
O
O
O
O
O
O
-
AcOH
62
64
65
76
69
80
51
69
70
67
10
65
27
66
70
55
71
73
CF
3
CO
2
H
MesCO
2
H
AdCO
---
---
---
---
---
---
AdCO
---
---
---
---
---
---
---
-
2
H
[Ru(O
2
CMes)
2
(p-cymene)]
2
2
2
2
2
2
2
[Ru(O
2
CAd) (p-cymene)]
2
[
b]
c]
[Ru(O
[Ru(O
2
CAd)
2
(p-cymene)]
(p-cymene)]
[
2
CAd)
2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
[Ru(OAc)
2
(PPh
3
)
2
]
[Ru(O CAd)
2
2
(PPh
3
)
2
]
[Ru(NCCH
3
)
6
][SbF
6
]
2
2
H
[Ru(O
[Ru(O
[Ru(O
[Ru(O
[Ru(O
[Ru(O
[Ru(O
[Ru(O
2
2
2
2
2
2
2
2
CAd)
2
(p-cymene)]
2
(p-cymene)]
2
(p-cymene)]
2
(p-cymene)]
2
(p-cymene)]
2
(p-cymene)]
2
(p-cymene)]
2
(p-cymene)]
SPGS-550M/H
PTS/H
Triton X-100/H
2
O
CAd)
CAd)
CAd)
CAd)
CAd)
CAd)
CAd)
2
O
2
O
2
SDS/H O
Scheme 1. C–H arylations with aryl bromides 2. [a] 1a (2.0 equiv), 2j (1.0
Tween 20/H
2
O
equiv), 24 h.
Brij 35/H
Brij 93/H
2
O
O
The versatile ruthenium-catalyzed C–H arylation was not
limited to mono-substituted ferrocenes. Indeed the ferrocenes
2
2
H O
<5
1b-c were likewise identified as viable substrates to obtain the
arylated products (Scheme 2a). Moreover, differently
3
Pd(OAc)
[Cp*RhCl
Cp*Co(CO)I
MnBr(CO)
2
-
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
TPGS-750M/H
2
2
2
2
O
O
O
O
-
-
-
-
substituted arenes 4 were found to be arylated within the
ruthenium-catalyzed C–H activation manifold (Scheme 2b).
2
]
2
-
2
-
5
-
[
[
a] Reaction conditions: 1a (0.20 mmol), 2a (0.24 mmol), additive (30 mol %),
TM] (10 mol %), micelle/H O (1.0 mL), 100 °C, 12 h, under N . Yields of
2
2
isolated product, TM: transition metal. [b] With NaCl (3M) at 50 °C.
[
17]
[
c] 70 °C.
With these optimized reaction conditions in hand, we then
examined the substrate scope of the ruthenium-catalyzed C–H
arylation with micelle TPGS-750M/H O (Scheme 1). First, we
2
evaluated various aryl bromides 2. Electron-donating and
electron-withdrawing substitutents were well tolerated, leading
to arylated ferrocenes with high efficacy (3aa-3ai). With
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Scheme 4. Key mechanistic studies.
Next, intermolecular competition experiments with differently
substituted aryl bromides 2 revealed the more electron-deficient
aryl bromide 2f to react preferentially (Scheme 5).
Scheme 2. a) C–H arylations of ferrocenes 1. b) Micellar C–H arylations of
arenes.
Next, we probed the versatility of the arene ligand-free-catalyst
[
2 3 2
Ru(OAc) (PPh ) ] in micellar catalysis. Various aryl bromides 2
as well as heteroaryl electrophiles were well accepted here
likewise (Scheme 3).
Scheme 5. Intermolecular competition experiment.
We were further pleased that the designer surfactant could be
recycled up to four times without affecting the catalytic
performance. Based on the organic solvent employed during the
workup procedures, the parent reaction resulted in a very low E
factor value of 5.6, thus indicating the sustainability of the
present reaction (Scheme 6).
Scheme 3. C–H arylation with arene-free ruthenium catalyst.
Given the versatility of the ruthenium-catalyzed C–H arylation,
we became intrigued to delineate its mode of action. To this end,
C–H arylations in the presence of isotopically labeled cosolvents
led to H/D scrambling in proximity to the thiocarbonyl group
Scheme 6. Measure of sustainability by E factor and recycling study.
(
Scheme 4). Furthermore, we observed a negligible kinetic
isotopic effect (KIE) of k /k = 1.2. These findings are indicative
of a fast organometallic C–H ruthenation.
Furthermore, nano micelles of TPGS-750M played a crucial role
in the catalysis. A dynamic light scattering (DLS) experiment
revealed the existence of micelles with an average diameter of
H
D
52 nm (Figure 2). After full conversion, the particle size of the
surfactant solution significantly increased to 130 nm, indicating
the accommodation of the organic compounds and catalyst in
the micelles.
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COMMUNICATION
In summary, we have developed an unprecedented
ruthenium(II)-catalyzed C–H arylation by a micellar regime. Thus,
the single-component complex [Ru(O
arene-ligand-free [Ru(OAc) (PPh
homogeneous C–H arylations in H
ruthenium-catalyzed C–H activation features full tolerance of
sensitive functional groups and H O by an organometallic C–H
2
CAd)
set the stage for
O. The first micellar-enabled
2
(p-cymene)] and the
2
3 2
) ]
2
2
activation manifold as well as a strategy for effective micelle
recovery and reuse. The facile C–H activation by weak
thioketone assistance was rationalized by experimental and
computational studies.
Figure 2. DLS studies of the micelles.
Acknowledgements
To gain further insights into the nature of the thioketone weak
coordination, we explored the key C–H activation step by means
of density functional theory (DFT) studies. Calculations at the
PW6B95-D3(BJ)/def2-TZVP+COSMO//TPPS-D3(BJ)/def2-TZVP
level of theory revealed the C–H activation to proceed via the
formation of agostic intermediate B with an energy barrier of
Generous support by the DFG (Gottfried-Wilhelm-Leibniz-Preis
to LA and SPP1807) is gratefully acknowledged.
Keywords: C–H activation • micellar catalysis • thioketone •
ruthenium • arylation
-1
[17]
10.9 kcal mol (Figure 3 and Figure S2). A comparison with
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COMMUNICATION
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[
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This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201901856
COMMUNICATION
COMMUNICATION
Santhivardhana Reddy Yetra, Torben
Rogge, Svenja Warratz, Julia Struwe,
Wentao Peng, Philipp Vana, and Lutz
Ackermann*
Page No. – Page No.
Micellar Catalysis for Ruthenium(II)-
Catalyzed C−H Arylation: Weak-
Coordination-Enabled C−H Activation
2
in H O
Micelle: Weak-coordination enabled versatile ruthenium-catalyzed C−H arylations by micellar catalysis in H O.
2
This article is protected by copyright. All rights reserved.