Pd-Catalyzed Vinylation of Aryl Halides with Inexpensive Organosilicon Reagents Under Mild Conditions

Article abstract of DOI:10.1002/chem.201802573

Pd-catalyzed Hiyama vinylation reaction of non-activated aryl chlorides and bromides under mild conditions was developed. The use of efficient vinyl donors and electron-rich sterically hindered phosphine ligands was critical for the success of the reaction. The products of this transformation can be used for Am/Cm separation, an important challenge in nuclear fuel reprocessing. The substituent effect on Am/Cm separating selectivity was also achieved, which could contribute to the development of new chromatographic materials for the separation of Am and Cm.

Full text of DOI:10.1002/chem.201802573

A Journal of
Accepted Article
Title: Pd-Catalyzed Vinylation of Aryl Halides with Inexpensive
Organosilicon Reagents Under Mild Conditions
Authors: Chu-Ting Yang, Jun Han, Jun Liu, Yi Li, Fan Zhang, Hai-Zhu
Yu, Sheng Hu, and Xiaolin Wang
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To be cited as: Chem. Eur. J. 10.1002/chem.201802573
Link to VoR: http://dx.doi.org/10.1002/chem.201802573
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10.1002/chem.201802573
Chemistry - A European Journal
COMMUNICATION
Pd-Catalyzed Vinylation of Aryl Halides with Inexpensive
Organosilicon Reagents Under Mild Conditions
Chu-Ting Yang,*[a] Jun Han,[a] Jun Liu,[a] Yi Li,[a] Fan Zhang,[a] Hai-Zhu Yu,*[b] Sheng Hu[a], and Xiaolin
Wang*[a]
More importantly, the substituent effect on separating selectivity
for pyridine resins was achieved. Hence, this work not only
provides a convenient method for the synthesis of substituted
styrenes but also contributes to the development of new
chromatographic materials for the separation of Am and Cm.
Our study began with an examination of the reaction of 2-
chloronaphthalene (1a) with an inexpensive, readily available
and efficient vinyl donors (1,3,5,7-tetravinyl-1,3,5,7-tetramethyl-
cyclotetrasiloxane, D4V, 2).[11e] We initially used Pd(OAc)2 as the
catalyst and tetrabutylammonium fluoride trihydrate (TBAF) as
the activating agent. The electron-rich sterically hindered
phosphine ligands were used to activate aryl chlorides (Table 1,
entries 1–7).[15] We were delighted to find that X-phos provided
excellent yield (86%, entry 7). The observation is expected,
because according to the recent studies, Pd(OAc)2/X-phos is
capable to activate aryl chlorides under mild conditions. The
coordination of the aromatic ring in X-phos could increase the
electron density of metal center (Pd) and promote the oxidative-
addition step, which is rate-determining step in this vinylation
reaction.[11k,16] Reducing the amount of catalyst (1 mol%)
generated a lower yield (68%, entry 8). Other Pd catalysts,
including PdBr2 and Pd(dba)2, also promoted the reaction but
gave lower yields (entries 9 and 10). By contrast, the reaction
did not occur in the absence of a Pd catalyst (entry 11). In a test
Abstract: Pd-catalyzed Hiyama vinylation reaction of non-activated
aryl chlorides and bromides under mild conditions was developed.
The use of efficient vinyl donors and electron-rich sterically hindered
phosphine ligands was critical for the success of the reaction. The
products of this transformation can be used for Am/Cm separation,
an important challenge in nuclear fuel reprocessing. The substituent
effect on Am/Cm separating selectivity was also achieved, which
contributes to the development of new chromatographic materials for
the separation of Am and Cm.
Substituted styrenes are one of the most important building
blocks for the synthesis of fine chemicals and polymers.[1] In
addition, styrenes are used ubiquitously in modern organic
reactions,
such
as
cross-metathesis,[2]
asymmetric
dihydroxylation,[3]
aminohydroxylation,[4] and epoxidation.[5]
Classical methods for the synthesis of functionalized styrene
derivatives involve dehydration of alcohols, dehydrohalogenation
of alkyl halides, carbonyl olefination, and the reduction of
terminal alkynes.[6] However, these methods suffer from harsh
reaction conditions and limited scope of substrates. Thus, recent
attention has been given to developing transition-metal-
catalyzed methods for the preparation of styrene derivatives.
One of the most important examples is Pd-catalyzed vinylation
of aryl halides with organometallic vinyl donors,[7] including tin-,[8]
boron-,[9] magnesium-,[10] and silicon-based reagents.[11] Among
these vinyl donors, organosilicon reagents offer numerous
advantages, such as low toxicity, ease of synthesis, low cost,
and high chemical stability.[12] Since the pioneering study of
Hiyama and co-workers,[11a] a variety of palladium catalytic
systems, organosilicon-based vinyl donors, and activating
reagents are now used to promote the vinylation reaction under
milder conditions.[11,12] Nevertheless, to date, the substrate
scope has been predominantly limited to aryl iodides and
bromides.[13,14] Moreover, the reaction at room temperature was
limited to aryl iodides and activated bromides.[11e,11g] It remains
challenging to develop vinylation reactions of aryl bromides and
chlorides under milder conditions, especially at room
temperature. Such transformations are desirable because they
would be amenable to large-scale reactions.
V
of various organosilicon-based vinyl donors (entries 12–17), D4
generated the best yield. The decrease of reaction temperature
to 40°C lowered the yield to 38% (entry 18). The product was not
obtained at room temperature (entry 19). Finally, aryl bromide
and iodide were also good substrates (entries 21 and 22), but
the present conditions were not effective for the coupling of an
aryl tosylate (entriy 20).
Table 1. Pd-catalyzed vinylation of 1-chloronaphthalene under various
conditions.
Catalyst
Ligand
Vinyl
Temp.
(°C)
67
Time Yield
Entry
(0.01 mmol) (0.02 mmol)
donor
(h)
24
24
24
24
24
24
(%)[a]
V
1
2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdBr2
PCy3
DPPF
D4
6
Herein, Pd-catalyzed vinylation of aryl chlorides and
bromides, using inexpensive organosilicon reagents and milder
reaction conditions, was achieved. The vinylation reactions of
non- activated aryl bromides were carried out at room
temperature. Moreover, gram-scale reactions were conducted to
synthesize vinyl pyridines, which can be used for Am/Cm
separation as polyvinyl pyridine (PVP) through polymerization.
V
D4
67
Trace
Trace
10
V
3
PtBu3
D4
67
V
4
JohnPhos
RuPhos
S-phos
X-phos
X-phos
X-phos
X-phos
X-phos
X-phos
X-phos
X-phos
X-phos
D4
67
V
5
D4
67
33
V
6
D4
67
17
V
7
D4
67
24 90(86)[b]
V
8[c]
D4
67
24
24
24
24
24
24
24
24
68
76
[a]
C.-T. Yang, J. Han, J. Liu, Y. Li, F. Zhang, S. Hu, X.-L. Wang
Institute of Nuclear Physics and Chemistry
China Academy of Engineering Physics
Mianyang 621900 (P. R. China)
E-mail: yangchuting@caep.cn
V
9
D4
67
V
10
11
12
13
14
15
Pd(dba)2
-
D4
67
59
V
D4
67
Trace
73
xlwang@caep.cn
V
[b]
Prof.Dr. H. -Z. Yu
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
D3
67
Department of Chemistry and Center for Atomic Engineering of
Advanced Materials
Anhui University
Hefei 230026 (P. R. China)
E-mail: yuhaizhu@ahu.edu.cn
HVDS
DVDS
67
45
67
64
VS(OMe)3
67
32
Supporting information for this article is available on the WWW under http://
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10.1002/chem.201802573
Chemistry - A European Journal
COMMUNICATION
(DVDS). This catalyst was not only effective for the activated
aryl bromides (electron withdrawing groups, 3p-3s, 3u) but also
provided good yields for the non-activated substrates (3a, 3t, 3v-
3y). Interestingly, an aldehyde moiety (3p) can survive under
these mild reaction conditions, indicating good functional group
compatibility of the transformation. It is important to note that in
most previous Pd-catalyzed Hiyama vinylation reactions, only
aryl iodides and activated bromides could react at room
temperature.[11e,11g] This new method, therefore, provides the
first example of a Pd-catalyzed Hiyama vinylation reaction of
non-activated aryl bromides at room temperature.
16
17
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
X-phos
X-phos
X-phos
X-phos
X-phos
X-phos
X-phos
VS(OEt)3
VS(OiPr)3
67
67
40
25
67
67
67
24
24
24
24
24
24
24
36
81
V
18
D4
38
V
19
D4
Trace
Trace
93
20[d]
21[e]
22[f]
D4
V
V
D4
V
D4
91
V
[a] Reaction conditions: 2-chloronaphthalene (0.5 mmol), D4 (0.25 mmol),
TBAF (1 mol/L in THF, 1 mL), catalyst (0.01 mmol), ligand (0.02 mmol), GC
yields after 24 h (average of two runs). [b] Isolated yields, TON (turn over
number) =45. [c] 0.005 mmol of Pd catalyst was added, TON=68. [d] R-OTs
(0.5 mmol) was used. [e] R-Br (0.5 mmol) was used. [f] R-I (0.5 mmol) was
used. D3V=2,4,6-trimethyl-2,4,6-trivinyl-1,3,5,2,4,6-trioxatrisilinane, HVDS=
Table 3. Pd-catalyzed vinylation of aryl bromides at room temperature.[a]
hexavinyldisiloxane,
methoxy(vinyl)silane,
isopropoxy(vinyl)silane.
DVDS=divinyltetramethyldisiloxane,
VS(OEt)3=triethoxy(vinyl)silane,
VS(OMe)3=tri-
VS(OiPr)3=tri-
The results of the current study indicate that Pd(OAc)2/X-phos
is a suitable catalyst for the vinylation reaction of aryl chlorides.
In regard to the scope of this method (Table 2), aryl chlorides
with different substituent groups can participate in the reaction.
Both electron-donating (3b, 3h, 3m) and electron-withdrawing
(3c−g, 3l) aryl chlorides are good substrates. However, the latter
showed better reactive activity and were obtained in good to
excellent yields. More importantly, a variety of synthetically
useful functional groups, including ether (3b, 3h), ester (3c, 3o),
nitryl (3d, 3i), cyano (3e), carbonyl (3f), amide (3g), and
sulfoxide (3l) can be tolerated in this reaction. Furthermore, the
heteroaryl chlorides such as pyridine (3i, 3o), thiophene (3j),
furan (3k), and bipyridyl (3n) worked well, affording the
corresponding styrenes in 73-77% yields.
Table 2. Pd-catalyzed vinylation of aryl chlorides.[a]
[a] Reactions were carried out at 25°C for 24 h on a 0.5 mmol scale using 0.01
mmol Pd(OAc)2 and 0.02 mmol 6. For details about each substrate please see
the Supporting Information. Yields were determined through the isolation of
the desired products.
Further tests showed the present catalyst (Pd(OAc)2/6)
cannot promote vinylation of aryl chlorides at room temperature,
suggesting good chemoselectivity of the reaction. As shown in
Scheme 1, we found that for substrates with both aryl-Br and
aryl-Cl sites, the former was much more reactive under the
present catalytic conditions. In the reaction of compound 7 and
DVDS, mono-vinyl compound (3z) was the only product, while
aryl-Cl remained intact and was capable of undergoing further
functionalization.
Scheme 1. Selectivity between aryl bromides and chlorides.
Additionally, gram-scale reactions (Table 4) were conducted
to evaluate the efficiency of the new catalyst system in
preparative organic synthesis. In the experiments, the Pd-
catalyzed vinylation reaction proceeded equally well, in
comparison to the smaller scale experiments, and the reaction
afforded vinyl pyridines with good isolated yields and high
functional-group tolerance. The products were important
monomers for polyvinyl pyridine (PVP), which can be can be
used as a paper reinforcing agent, surface modifier, support for
metal catalyst, template for nanostructure, and pyridine resin.[17]
Specifically, pyridine resins have become promising materials
[a] Reactions were carried out at 67°C for 24 h on a 0.5 mmol scale using 0.01
mmol Pd(OAc)2 and 0.02 mmol X-phos. For details about each substrate
please see the Supporting Information. Yields were determined through the
isolation of the desired products.
The vinylation of 2-bromonaphthalene provided 93% yield
with the present condition but gave only 21% yield at room
temperature. Thus, we continued to improve the reaction at
room temperature. Through optimizing multiple reaction
parameters(see the Supporting Information), we found room
temperature Pd-catalyzed vinylation of aryl bromides can be
realized with phosphine ligand (6, Table 3) and vinyl donor
for Am/Cm separation,[18] addressing an important challenge in
actinides separation chemistry and nuclear fuel reprocessing.[19]
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10.1002/chem.201802573
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However, the reported resins frequently suffer from the poor
Am/Cm selectivity. In order to improve the selectivity, a series of
pyridine resins with different substituents embedded in silica
beads were synthesized (see the Supporting Information). We
To summarize, we have developed a Pd-catalyzed cross-
coupling reaction of aryl halides with organosilicon vinyl
reagents. This reaction represents the rare example of a Pd-
catalyzed Hiyama vinylation reaction of non-activated aryl
chlorides and bromides under mild conditions, in particular, at
found that: 1) The Am/Cm separation factors (SFAm/cm
)
V
decreased with electron-donating groups (Me, OMe), and this
was probably due to the enhanced basic and complexing ability
of the nitrogen atom. 2) By contrast, the resin with the CF3 group
revealed the best Am/Cm selectivity (SFAm/cm=4.2), due to the
softer nitrogen atom. 3) Interestingly, the resins with Cl groups
exhibited high Cm selectivity. The separation factors were
calculated as SFCm/Am = 2 and 5 with mono-Cl and di-Cl
substituents, respectively.
room temperature. The use of efficient vinyl donors (D4 or
DVDS) and electron-rich sterically hindered phosphine ligands is
crucial. The reaction tolerates a number of synthetically relevant
functional groups, including esters, amides, nitryl, cyano,
carbonyl, aldehyde, and heteroaryl halides are also good
substrates. Furthermore, we also demonstrate that the Pd-
catalyzed method is amenable to gram-scale preparative
organic synthesis, and the products were used to synthesize
pyridine resins, which are promising materials for Am/Cm
separation. Finally, we preliminarily evaluated the substituent
effect on Am/Cm separating selectivity for pyridine resins. The
resin with the electron-withdrawing group (CF3) exhibited the
best selectivity for Am and that with the Cl group showed high
selectivity for Cm. The results of this study contribute to the
development of new chromatographic materials for the
separation of Am and Cm. Follow-up studies are underway in
our laboratory.
Table 4. Gram-scale vinylation of halogenated pyridines.
Experimental Section
Representative procedure (3a, Table 2): In air, Pd(OAc)2( 0.01 mmol),
and X-phos (0.02 mmol) were added to a Schlenk tube equipped with a
stir bar. The vessel was evacuated and filled with argon (three cycles).
[a] Reactions were carried out at 25°C for 24 h on a 20 mmol scale using 0.4
mmol Pd(OAc)2, 0.8 mmol 6, 20 mmol bromides and 20 mmol DVDS. [b]
Reactions were carried out at 67°C for 24 h on a 20 mmol scale using 0.4
mmol Pd(OAc)2, 0.8 mmol X-phos, 20 mmol chlorides and 10 mmol D4V. For
details about each substrate please see the Supporting Information. Yields
were determined through the isolation of the desired products.
V
TBAF (1 mol/L in THF, 1 mL), 2-chloronaphthalene (0.5 mmol), and D4
(0.25 mmol) were added in turn under Argon atmosphere at room
temperature. The reaction mixture was stirred at 67 ºC for 24 h, then
quenched with H2O (10 mL). The resulting solution mixture was then
extracted with CH2Cl2 (3 times, 10 mL each), dried over Mg2SO4, filtered
through silica gel with copious washings (CH2Cl2), concentrated, and
purified by column chromatography. The product was dried under high
vacuum for at least 0.5 h before it was weighed and characterized by
NMR spectroscopy.
Acknowledgements
Our study was supported by the Science Challenge Project
(TZ2016004), and the National Natural Science Foundation of
China (Nos. 91426302, 21672001).
Figure 1. The optimized structures formed by 2-Cl-Py and Am (Cm).
We further analyzed the Cm-selectivity through density
functional theory calculations of the optimized structure, formed
by the simplified ligand model (2-Cl-Py) and metal centers (Am,
Cm). The Am-N bond length was longer than Cm-N bond length
in the optimized structures (Figure 1, 2.843 Å versus 2.832 Å),
indicating a weaker interaction between Am and the pyridine
ligand. Furthermore, frontier molecular orbital analysis revealed
comprehensive interactions between Cl(p) orbital and the Cm(f)
orbital, which was significantly weaker in the Am-system (See
the Supporting Information). In addition, the corresponding
frontier orbital energy of the Cm complex was significantly lower
than that of the Am-complex, and the HOMO-LUMO energy gap
of the Cm system was greater, which helped to improve the
stability of the Cm complex.
Keywords: palladium • silicon• cross-coupling • Am/Cm
separation • substituent effect
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COMMUNICATION
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10.1002/chem.201802573
Chemistry - A European Journal
COMMUNICATION
COMMUNICATION
Pd-catalyzed Hiyama vinylation
reaction of non-activated aryl
chlorides and bromides under mild
conditions was achieved. The
products of this transformation can
be used for Am/Cm separation, an
important challenge in nuclear fuel
reprocessing.
C.-T. Yang,* J. Han, J. Liu, Y. Li, F.
Zhang, S. Hu, H.-Z. Yu,* X.-L. Wang*
Page No. – Page No.
Pd-Catalyzed Vinylation of Aryl
Halides
with
Inexpensive
Organosilicon Reagents Under Mild
Conditions
This article is protected by copyright. All rights reserved.