Rhodium-Catalyzed Dealkenylative Arylation of Alkenes with Arylboronic Compounds

Article abstract of DOI:10.1002/anie.202105355

The C?C bond formation reaction represents a fundamental and important transformation in synthetic chemistry, and exploring new types of C?C bond formation reactions is recognized as appealing, yet challenging. Herein, we disclose the first example of rhodium-catalyzed dealkenylative arylation of alkenes with arylboronic compounds, thereby providing an unconventional access to bi(hetero)aryls with excellent chemoselectivity. In this method, C(aryl)?C(alkenyl) and C(alkenyl)?C(alkenyl) bonds in various alkenes and 1,3-dienes can be cleaved via a hydrometalation and followed by β-carbon elimination pathway for Suzuki–Miyaura reactions. Furthermore, a series of novel organic fluorescent molecules with excellent photophysical properties has been efficiently constructed with this protocol.

Full text of DOI:10.1002/anie.202105355

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Rhodium-Catalyzed Dealkenylative Arylation of Alkenes with
Arylboronic Compounds
Authors: Guangying Tan, Mowpriya Das, Iván Maisuls, Cristian A.
Strassert, and Frank Glorius
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202105355
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10.1002/anie.202105355
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RESEARCH ARTICLE
Rhodium-Catalyzed Dealkenylative Arylation of Alkenes with
Arylboronic Compounds
Guangying Tan, Mowpriya Das, Iván Maisuls, Cristian A. Strassert, and Frank Glorius*
Dedicated to Prof. Christian Bruneau
Abstract: The C–C bond formation reaction represents
a
challenging than the direct Heck arylation and hydroarylation
because of the thermodynamic and kinetic stability of most C–C
bonds (Scheme 1c).[6,7] In this work, C(aryl)–C(alkenyl) and
C(alkenyl)–C(alkenyl) bonds in various alkenes and 1,3-dienes
could be cleaved for Suzuki-Miyaura reaction with arylboronic
compounds under the help of chelation group, thereby providing
a rapid and unconventional access to bi(hetero)aryls. To the
best of our knowledge, there are only three reported examples
on transition-metal catalyzed C(aryl)–C(alkenyl) bond cleavage,
namely: 1) Youn’s Pd-catalyzed cascade reactions between 2-
alkenylphenyl beta-ketoesters and alkenes via aromatization-
driven beta-carbon elimination;[8] 2) Lautens’ Pd-catalyzed
remote C−H alkylation and C−C bond cleavage;[9] and 3)
Kakiuchi’s Rh-catalyzed olefin extrusion–reinsertion of
styrenes.[10] Notably, the cleavage of C(alkenyl)–C(alkenyl) bond
in 1,3-dienes remains unknown to date.
fundamental and important transformation in synthetic chemistry,
and exploring new types of C–C bond formation reactions is
recognized as appealing, yet challenging. Herein, we disclose the
first example of rhodium-catalyzed dealkenylative arylation of
alkenes with arylboronic compounds, thereby providing an
unconventional access to bi(hetero)aryls with excellent chemo-
selectivity. In this method, C(aryl)–C(alkenyl) and C(alkenyl)–
C(alkenyl) bonds in various alkenes and 1,3-dienes can be cleaved
via a hydrometalation and followed by beta-carbon elimination
pathway for Suzuki-Miyaura reaction. Furthermore, a series of novel
organic fluorescent molecules with excellent photophysical
properties has been efficiently constructed with this protocol.
Introduction
Transition-metal catalyzed cross-coupling reactions of alkenes
with arylboronic compounds have emerged as a rapid and
efficient C–C bond forming transformation that utilize of
abundant and/or commercially available feedstocks to produce
various value-added alkenylarenes as well as alkylarenes,[1]
thereby has received increasing attention from the synthetic
community. According to the difference of the products, these
reactions could be categorized into two main types. The first
type is Heck-type arylation of alkenes via transition-metal
catalysis,[2,3] the pathway involves the formation of an
alkylmetallic intermediate via an intermolecular carbometalation
of alkenes and a subsequent beta–H elimination to give
alkenylarenes (Scheme 1a). Another type refers to the
hydroarylation of alkenes.[4,5] In this type, transition-metal
catalyst reacts firstly with hydride reagents to generate an active
catalyst species [TM]–H. Then, [TM]–H interacts with alkenes
and arylboronic compounds through a hydrometalation and
transmetalation process in sequence to form an arylalkylmetallic
intermediate, which further undergoes a reductive elimination to
deliver a hydroarylated product (Scheme 1b). Beyond the above
two types, herein we disclose a new type of coupling reaction
between alkene and arylboronic compound via rhodium-
catalyzed dealkenylative arylation, which is much more
[]
Dr. G. Tan, M. Das, and Prof. Dr. F. Glorius
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität
Münster
Corrensstraße 40, 48149 Münster (Germany)
E-mail: glorius@uni-muenster.de,
Scheme 1. Transition-metal catalyzed coupling reactions between alkenes
and arylboronic compounds. [TM] = transition-metal. DG = directing group.
Dr. I. Maisuls and Prof. Dr. C. A. Strassert
Institut für Anorganische und Analytische Chemie, CeNTech, CiMIC,
SoN, Westfälische Wilhelms-Universität Münster
Heisenbergstraße 11, 48149 Münster (Germany)
Supporting information for this article is given via a link at the end of
the document.
Results and Discussion
1
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10.1002/anie.202105355
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Optimization of the Reaction Conditions. Inspired by
Kakiuchi’s work,[10] we began our study with the reaction
between 1-(2-methyl-6-(prop-1-en-2-yl)phenyl)-1H-pyrazole (1a)
and (4-methoxyphenyl)boronic acid (2a) in the presence of a
Cp*Rh(III) catalyst (see Supporting Information for the details,
Table S1). To our delight, the best yield for the desired product
3a reached 69% under the optimal catalytic system composed of
[RhCp*(MeCN)3][SbF6]2 (10 mol%) and Ag2O (2.0 equiv) in EtOH
(0.2 M) at 100 oC for 20 h, and only a trace amount of by-product
3aa resulting from the direct oxidative Heck arylation of 1a with
2a was observed (Table S1, entry 1). The control experiments
showed that both [RhCp*(MeCN)3][SbF6]2 and Ag2O were
indispensable for this reaction (Table S1, entries 2 and 3).
Catalysts played a crucial role in the chemoselectivity of
dealkenylative arylation over Heck arylation. Replacing
stage modification of natural products. For example, arylboronic
compounds 2y and 2z, which are derivatives from estrone and
tyrosine, reacted smoothly with 1e under the standard reaction
conditions, producing the desired products 4m and 4n in 65%
and 57% yields respectively.
Table 1: Scope of (hetero)arylboronic acids.[a,b]
[RhCp*(MeCN)3][SbF6]2
with
[RhCp*Cl2]2/AgSbF6,
the
chemoselectivity of this reaction switched completely and 3aa
was obtained as main product in 36% yield (Table S1, entry 4).
In addition, [IrCp*Cl2]2 and [CoCp*(CO)I2]2, the congeners of
[RhCp*Cl2]2, showcased negligible catalytic activity for this
transformation (Table S1, entries 5 and 6). When Ag2O was
replaced with Ag2CO3 as oxidant, 3a was delivered in a slightly
decreased yield (Table S1, entry 7) and the reaction was shut
down completely when employing AgOAc and Cu(OAc)2 as
oxidant (Table S1, entries 8 and 9). Moreover, solvents also
significantly affect the chemoselectivity (Table S1, entries 10-15).
For example, CF3CH2OH gave a moderate yield of 3a along with
a trace amount of the by-product 3aa. However, the undesired
Heck arylation were more favored when employing other
solvents such as MeOH, tBuOH, DCE, 1,4-dioxane, and toluene.
Furthermore, sensitivity screening revealed that this reaction
was relatively robust (Table S2),[11] only suffering from
diminished yields with water addition or at larger scales.
Substrate Scope. With the optimized conditions in hand, the
scope of (hetero)arylboronic acids was tested firstly in the
reaction with 1a. As shown in Table 1,
(hetero)arylboronic acids smoothly underwent
a
series of
this
transformation, producing a variety of bi(hetero)aryl skeletons in
moderate to good yields (3a-3x). Phenylboronic acids with
electron donating or electron withdrawing groups such as
methoxyl, methyl, tert-butyl, iso-butyl, trimethylsilyl, phenyl, vinyl,
fluoro, chloro, trifluromethyl, and ester at the para- or meta-
position of the phenyl ring could react with 1a in good yields (3a-
3s). Moreover, naphthalen-1-ylboronic acid, naphthalen-2-
ylboronic acid, and (5-bromobenzo[b]thiophen-2-yl)boronic acid
were suitable for this transformation (3t-3v). Furthermore, the
carbazolye and triphenylamine containing boronic acids could
also undergo this dealkenylative arylation (3w and 3x).
Subsequently, the reactivity of different types of alkenes was
inspected (Table 2). To our delight, 1-(5-methyl-2-(1-
phenylvinyl)phenyl)-1H-pyrazole (1b) and 1,2-disubstituted
internal alkenes such as (E)-1-(5-methyl-2-styrylphenyl)-1H-
pyrazole (1c) and (E)-1-(5-methyl-2-(pent-1-en-1-yl)phenyl)-1H-
pyrazole (1d) could be cleaved for the dealkenylative arylation
with (4-methoxyphenyl)boronic acid (2a) in moderate yields.
Then, the scope with respect to directing group-containing
alkene substrates (1) was investigated. As summarized in Table
2, various pyrazole or pyridine containing alkenes could undergo
this dealkenylative arylation, delievering the corresponding
biaryls in moderate to good yields (4a-4l). To highlight the
synthetic usefulness, this method was examined in the late-
[a] Reaction conditions: 1a (0.2 mmol), 2 (0.4 mmol), [RhCp*(MeCN)3][SbF6]2
(10 mol%), and Ag2O (2.0 equiv) in EtOH (1.0 mL) at 100 oC under Ar for 20 h.
[b] Isolated yields.
To our delight, our protocol could also be extended to the
dealkenylative arylation of 1,3-dienes with the aid of pyridine unit
as directing group (Table 3). It needs to be noted that the
cleavage of C(alkenyl)–C(alkenyl) bond in 1,3-dienes is
unknown to date. First, arylboronic compounds with either
electron-donating or electron-withdrawing groups engaged in
this reaction with 2-((2Z,4E)-3-methyl-5-phenylpenta-2,4-dien-2-
yl)pyridine (5a) in moderate yields (6a-6i). Subsequently, the
scope of 1,3-dienes was examined by using arylboronic
compounds 2z as the coupling partner. As summarized in Table
3, various 2-pyridyl-containing 1,3-dienes underwent this method,
delivering the corresponding products in moderate yields (6j-6r).
In addition, 2-((1Z,3E)-4-phenylbuta-1,3-dien-1-yl)pyridine and
2-((2Z,4E)-5-phenylpenta-2,4-dien-2-yl)pyridine failed to give the
desired products.
Considering the synthetic usefulness of this protocol, we
further illustrated the transformation of the directing group. As
shown in Scheme 2a, the pyrazolyl group could be easily
transformed into an amino group. To gain some insight into the
reaction mechanism,
a set of control experiments were
conducted. First, treating 1e under the standard reaction
2
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10.1002/anie.202105355
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RESEARCH ARTICLE
Table 3: Scope of 2-pyridyl-containing 1,3-dienes.[a,b]
conditions delivered the direct dealkenylatived product 8 in 76%
yield. Moreover, the direct dealkenylation reaction of 1e was
also observed in the absence of Ag2O by using EtOH or PrOH
i
as solvent. The above alcohol-mediated dealkenylation
reactions of 1e suggested that the dealkenylative product 8
might be an intermediate of this dealkenylation reaction. To
corroborate this possibility, two parallel competition experiments
of 1e or 8 with 2a under the standard reaction conditions for 3 h
were conducted, and the desired product 4a was obtained in 52%
and 37% yields individually. Furthermore, an intermolecular
competition experiment was also performed, treating of 1 equiv
each of 1e, 9, and 2a in one pot under the standard reaction
conditions for 3 h. As shown in Scheme 2c and 2d, the results
evidenced that the arylation reaction from C−C cleavage was
much faster than that from C−H activation. Therefore, the direct
dealkenylative arylation reaction of 1e is more favored than the
cascade dealkenylation and rhodium-catalyzed ortho C−H
arylation.[12-13] However, at this stage, this possibility cannot be
completely ruled out.
Table 2: Scope of directing group-containing alkenes.[a,b]
[a] Reaction conditions: 5 (0.2 mmol), 2 (0.4 mmol), [RhCp*(MeCN)3][SbF6]2
(10 mol%), and Ag2O (2.0 equiv) in EtOH (1.0 mL) at 100 oC under Ar for 36 h.
[b] Isolated yields.
Based on the above observations and relevant literature,[10,14,
a plausible mechanistic pathway is proposed as illustrated in
15]
Scheme 3. Firstly, the reaction of [RhCp*(MeCN)3][SbF6]2 with
EtOH forms an active catalyst species [Cp*RhIIIX]–H (X = SbF6
or OEt) along with CH3CHO (CH3CHO was detected by GCMS
after the reaction of 1e and 2a, see Supporting Information).[14]
The resulting rhodium hydride species interacts with substrate 1
to give the intermediate IM1, followed by a hydrometalation of
alkene units to generate the intermediate IM2. Then,
intermediate IM2 goes through a beta–carbon elimination to
deliver an alkene coordinated intermediate IM3, which further
providing the intermediate IM4 through the release of an alkene.
Subsequently, intermediate IM4 reacts with arylboronic acids to
give intermediate IM5 via a transmetalation process. Since the
direct dealkenylative product was observed after the reaction
(Scheme 2b and 2d), intermediate IM4 suffers from a reversible
dealkenylation reaction in the presence of hydrogen ion at the
same time. Finally, intermediate IM5 undergoes a reductive
elimination to provide the desired products 3 along with the
release of Cp*RhI species. The later one will be further re-
oxidized to Cp*RhIII species by Ag2O to close the catalytic cycle.
[a] Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), [RhCp*(MeCN)3][SbF6]2
(10 mol%), and Ag2O (2.0 equiv) in EtOH (1.0 mL) at 100 oC under Ar for 20 h.
[b] Isolated yields. [c] The diarylated product 4b' was obtained in 12% yield. [c]
The diarylated product 4e' was obtained in 13% yield.
3
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10.1002/anie.202105355
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RESEARCH ARTICLE
Scheme 4. Synthesis of organic fluorescent molecules 10, 11, and 12 through
programmed arylations (for detailed reaction conditions, see supporting
information). Conditions: 1) [RhCp*(MeCN)3][SbF6]2 and Ag2O in EtOH at 100
oC. 2) [RhCp*Cl2]2/AgSbF6 and Ag2O in dioxane at 120 oC. 3) Pd(PPh3)4,
Na2CO3 in a mixture of toluene, EtOH and H2O at 100 oC. [a] Total yields. [b]
Emission maximum and ΦF (± 2%, toluene, RT). [c] ΦF in a glassy matrix (±
4%, 2-Me-THF,77 K). [d] Emission maximum and ΦF in solid state (± 2%, RT).
Following the above studies, we devoted our efforts on the
strategic application of this protocol. As it is widely known,
organic fluorescent molecules have broad applications in
chemosensors, organic light-emitting diodes, field-effect
transistors, memory devices, and bioprobes etc.[16] In addition,
triphenylamine (TPA) derivatives are considered versatile
materials because they possess nonplanar characteristic,
excellent electron-donating property, and hole-transporting
capability.[17] Therefore, we designed and synthesized three
triphenylamine (TPA) derivatives containing organic fluorescent
molecules (10-12) through a programmed rhodium-catalyzed
dealkenylative arylation and C–H arylation, and palladium-
catalyzed Suzuki-Miyama reaction of 1h with different
arylboronic acids (Scheme 4, see also Supporting Information
for details).
Scheme 2. a) Removal of directing group. b) Alcohol-mediated direct
dealkenylation of 1e. c) Two parallel competition experiment. d) Intermolecular
competition experiment.
Figure 1. (a) Normalized absorption spectra of compounds 10, 11, and 12 in
fluid toluene at RT. (b) Photoluminescence spectra of compounds 10, 11, and
12 in fluid toluene (10-5 M) and in the solid state at RT. Inset: Photographs of
compounds 10, 11, and 12 in toluene at RT (10-5 M), while photoexcited with a
UV lamp. Further photophysical data and photoluminescence spectra at 77 K
are found in the Supporting Information.
Finally, the photophysical properties of the newly synthesized
organic fluorophores (10-12) were measured, including
absorption and photoluminescence spectra, fluorescence
quantum yields (ΦF) and excited singlet state lifetimes (t) in fluid
Scheme 3. Plausible mechanistic pathway.
4
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10.1002/anie.202105355
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RESEARCH ARTICLE
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solution and in the solid state at room temperature (RT) as well
as in glassy matrices at 77 K (see Supporting Information for
details). As shown in Scheme 4 and in Figure 1, the absorption
and emission maxima in toluene (10-5 M) are centered at
around 345 nm and 400 nm, respectively. Surprisingly high ΦF
around 44% was observed in fluid toluene (Scheme 4). Notably,
this value further increased to roughly 75% at low temperature
(77 K), where also a slight blue-shift is observed. Contrastingly,
a significant red-shift of the photoluminescence (around 30 nm)
was observed in the solid state, if compared with fluid solutions,
which is attributed to an enhanced dielectric constant favoring
the charge-transfer character while dropping the ΦF to 20%,
13%, and 21%, respectively. Clearly, these compounds display
a bright and intense blue fluorescence both in solution and in the
solid state (Figure 1). Based on the obtained ΦF and  values
(Tables S3-S4), we calculated the fluorescence (kF) and non-
radiative (knr) deactivation rate constants (Table S5). The
comparably high value of kF for the three species implies a
predominant π-πcharacter of the fluorescent S1 states. In
frozen matrices at 77 K and in apolar solvents at RT, the π-π
character is increased while boosting kr, whereas in the more
polar solid state the charge-transfer character is enhanced with
generally lower radiative and higher radiationless deactivation
rates. At 77 K, radiationless processes are suppressed due to
reduced rotovibrational degrees of freedom while providing the
intrinsically high fluorescence rate constant due to a maximized
π-π character in the absence of solvent stabilization of the
photoexcited states.
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[5]
Conclusion
In summary, we have demonstrated the first example of
rhodium(III)-catalyzed dealkenylative arylation of alkenes with
arylboronic compounds, thereby providing an unconventional
access to bi(hetero)aryls with excellent chemo-selectivity. In
addition, this transformation was also amenable to 1,3-dienes. In
this method, C(aryl)–C(alkenyl) and C(alkenyl)–C(alkenyl) bonds
in various alkenes and 1,3-dienes can be cleaved via a
hydrometalation and followed by beta-carbon elimination
pathway for Suzuki-Miyaura reaction. Furthermore, a new class
of bright fluorophores was made accessible providing a blue
luminescence with lifetimes in the ns range and up to 75%
quantum yields.
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Acknowledgements
This work was support by the Alexander von Humboldt
Foundation
(G.T.
and
I.M.)
and
the
Deutsche
Forschungsgemeinschaft (Leibniz Award and SFB 858 for F.G.
and INST 211/915-1 for C.A.S.).
Keywords: rhodium catalysis • dealkenylation arylation •
alkenes • C–C bond cleavage • organic fluorescent molecules
[2]
For selected examples on oxidative Heck reactions, see: a) E. J.
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RESEARCH ARTICLE
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10.1002/anie.202105355
Angewandte Chemie International Edition
RESEARCH ARTICLE
Guangying Tan, Mowpriya Das, Iván
Maisuls, Cristian A. Strassert, and Frank
Glorius*
Page No. – Page No.
Rhodium-Catalyzed Dealkenylative
Arylation of Alkenes with Arylboronic
Compounds
A rhodium(III)-catalyzed dealkenylation arylation of alkenes and 1,3-dienes with
arylboronic compounds has been developed for the first time to provide an
unconventional access to bi(hetero)aryls with excellent chemo-selectivity.
7
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