B(C6F5)3-Catalyzed Tandem Friedel-Crafts and C?H/C?O Coupling Reactions of Dialkylanilines

Article abstract of DOI:10.1002/asia.202000763

Tandem Friedel-Crafts (FC) and C?H/C?O coupling reactions catalyzed by tris(pentafluorophenyl) borane (B(C₆F₅)₃) were achieved without using any other additive in the absence of solvent. This process can be used for the reactions between a series of dialkylanilines and vinyl ethers with good isolated yields of bis(4-dialkylaminophenyl) compounds. Based on combined theoretical and experimental studies, the possible reaction mechanism was proposed. B(C₆F₅)₃ can activate the C=C and C?O bond for FC and C?H/C?O coupling reactions respectively. The FC reaction is slow, which is followed by a fast C?H/C?O coupling.

Full text of DOI:10.1002/asia.202000763

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: B(C6F5)3-Catalyzed Tandem Friedel-Crafts and C-H/C-O
Coupling Reactions of Dialkylanilines
Authors: Gaowen Zhai, Xueting Liu, Wentao Ma, Guoqiang Wang, Liu
Yang, Shuhua Li, Youting Wu, and Xingbang Hu
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10.1002/asia.202000763
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B(C6F5)3-Catalyzed Tandem Friedel-Crafts and C-H/C-O Coupling
Reactions of Dialkylanilines
Gaowen Zhai+, Xueting Liu+, Wentao Ma, Guoqiang Wang, Liu Yang, Shuhua Li*, Youting Wu* and
Xingbang Hu*
Abstract: Tandem Friedel-Crafts (FC) and C-H/C-O coupling
reactions catalyzed by tris(pentafluorophenyl) borane (B(C6F5)3)
were achieved without using any other additive in the absence of
solvent. This process can be used for the reactions between a series
of dialkylanilines and vinyl ethers with good isolated yields of bis(4-
dialkylaminophenyl) compounds. Based on combined theoretical and
experimental studies, the possible reaction mechanism was
proposed. B(C6F5)3 can activate the C=C and C-O bond for FC and
C-H/C-O coupling reactions respectively. The FC reaction is slow,
which is followed by a fast C-H/C-O coupling.
specifity of the catalysts. Besides, comparing with the abundant
achievements on metal-catalyzed C-C bond formation,
processes promoted by metal-free catalyst are still rare and full
of challenges. [1, 2]
Tris(pentafluorophenyl)borane (B(C6F5)3) is known as excellent
Lewis acid which can interact with electron-donor and act as
catalyst for some reactions, such as hydrogenation,
dehydrogenation, carboboration, isomerization, C-C formation,
cross-metathesis, et al. [15, 16] Herein, we reported an unexpected
one-pot FC and C-H/C-O coupling reaction between
dialkylanilines and vinyl ethers catalyzed by metal-free B(C6F5)3.
The mechanism of this new process has also been elucidated
based on experimental and theoretical investigations.
[1-14]
Constructing C-C bond is one of the most important topics in
both academic laboratories and industrial production. Many
famous reactions have been developed for the C-C bond
formation. [1] Among them, C-H/C-O coupling and Friedel-Crafts
(FC) reactions are two effective strategies. [2-13]
Table 1 Optimization of reaction conditions. [a]
Both C-H and C-O bonds are quite inert. Hence, the C−H/C−O
coupling to produce C-C bond is full of challenges. Until now,
effectively accessing this coupling reaction still requires metal-
based catalysts, [2] such as compounds containing Ni, [3] Fe, [4] Co,
[5] Mn [6] , Rh, [7] Ir, [8] or Pd [9]. It is worth noticing that, besides the
use of highly active metal-based catalysts, some of these
reported C-H/C-O coupling reactions also require pre-active
substrates, such as Grignard reagent, [3a, 3m, 3n, 4] organolithium
Entry
Solvent
Cat.
conversion(%)[b]
1
2
3
Benzene
Toluene
THF
DMF
B(C6F5)3
B(C6F5)3
B(C6F5)3
B(C6F5)3
B(C6F5)3
B(C6F5)3
BPh3
B(C2H5)3
B(C6F5)3
-
66
54
58
37
87
96
0
0
88
0
4
5
-
-
-
-
-
-
-
6[c]
7
reagent, [3i, 3q] or organoboron compound [3b, 3j, 3r, 9]
.
8
Though FC reactions have been widely used to introduce C-C
bond on aromatic ring [10], this reaction is usually unsuitable for
alkalinous substrates due to the coordination of the amines to
these reported acid catalysts. Classical textbook especially
emphasizes the incompatibility of FC reactions to amines. [11] For
N-containing substrates, great achievements have been
obtained for the FC reactions of indole and pyrrole because of
9d
10
11e
B(C6F5)3
82
[a] Standard reaction conditions: 2-Methoxypropene (0.25mmol), N,N-
Diethylaniline (2mmol), catalyst (0.05mmol), solvent (0.5ml), 110°C for 18
h. [b] The conversions of 2a were determined by GC. [c] 1b (2mmol) was
used instead of 1a, produces 3c. [d] 1a and 2a were dried over MgSO4. [e]
2a (3mmol), 1a (24mmol), B(C6F5)3 (0.6mmol).
[12]
the extremely weak alkalinity of these two compounds.
However, the FC reactions become challenging for substrates
with enhanced alkalinity, such as dialkylanilines. Recently,
We began the experiments by investigating the reaction
between N,N-Diethylaniline (1a) and 2-Methoxypropene (2a) in
the presence of B(C6F5)3 without using any other additive. It is
interesting to find that 3g can be produced with good conversion
(Entries 1-5, Table 1). When N,N-Dimethylaniline (1b) was used
as substrate, 96% conversion can be obtained (Entry 6).
Obviously, the producing of 3g requires two equivalents of 1a
and one equivalent of 2a. There are two new C-C bonds formed
accompanied by the C-O bond cleavage. It is reasonable to
deduce that 3g was produced by FC reaction between 1a and
2a, followed by the C-H/C-O coupling between 1a and the
intermediate. Methanol was detected in the experiment, which
may be the byproduct of the C-H/C-O coupling. Previous study
had revealed a C-alkylation reaction between aniline and
Bertrand and we achieved the FC reaction of dialkylanilines by
[13]
using carbene-gold (I) as catalyst.
Now, more and more
substrates with alkalinity have been successfully used for FC
reactions. [14]
It is worth noticing that the reported catalysts of the C-H/C-O
[10-14]
couplings [3-9] are quite different from those of FC reactions
due to the difference of their reaction mechanisms and the
[*]
G. Zhai, X. Liu, W. Ma, G. Wang, L. Yang, Prof. S. Li, Prof. Y. Wu,
Prof. X. Hu
School of Chemistry and Chemical Engineering
Nanjing University
Nanjing 210093 (P. R. China)
E-mail: shuhua@nju.edu.cn; ytwu@nju.edu.cn; huxb@nju.edu.cn
These authors contributed equally to this work.
benzylic alcohols catalyzed by B(C6F5)3 in the presence of
[+]
[15r]
1,1,1,3,3,3-hexafluoro-2-propanol.
No similar C-alkylations
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
reaction between methanol and N,N-Dialkylanilines were
observed in our experiment.
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Solvents have nonnegligible influence on the reactions. It is
fantastic that the best conversion was obtained in the absence
of additional solvent (Entries 1-5, Table 1). The catalytic ability of
different Lewis acids had been investigated. Triphenylboron
(BPh3) and triethylboron (BEt3) cannot catalyze the reaction due
to weak Lewis acidity (Entry 7, 8). No reaction was observed in
the blank experiment without any catalyst (Entry 10).
R5 group on vinyl ethers is vital for C-O bond cleavage
(Scheme 2). The n-Bu substitution gave worse conversion than
the ethyl substitution. The steric hindrance of t-Bu obviously
declined the reaction rate. Though the carboxyl (AcO) is a better
leaving group comparing with EtO or n-BuO,[3s] the electron
delocalization between vinyl and carboxyl may stabilize the C-O
bond. As a result, there is no reaction at all when R5 is acetyl
(Ac).
Scheme 1. Reactions between N,N-Dialkylanilines and Vinyl Ethers. Isolated
yields were reported. For 3c, 3g, 3k, and 3o, R5=Me; For the other products,
R5=Et.
Scheme 2. The influence of leaving group on the reaction. Conversions of 2
were reported.
Scheme 3. Reactions between N,N-Dialkylanilines and cyclic Vinyl Ethers.
Isolated yields were reported.
Using B(C6F5)3 as catalyst without any other additive in the
absence of solvent, we explored the scope of this
unprecedented one-pot FC and C-H/C-O coupling reactions
(Scheme 1). The reactions performed quite well with a variety of
substrates. Good to excellent isolated yields can be obtained for
most of the investigated reactions (3a to 3n, and 3p). The
experiment has also been performed in gram-level and the
conversion is only slightly declined (Entries 5 and 11, Table
1).However, products 3h an 3q have low yields because of low
When cyclic vinyl ethers (4) were used as substrates (Scheme
3), two kinds of products can be obtained depending on the
reaction condition. Reactions performed under the standard
condition gave products containing an oxygen heterocycles (5a’-
h’) with good to excellent isolated yields. 5a’-h’ can be
hydrolyzed to products containing hydroxyl group (5a-h) with
excellent isolated yields in the presence of water. Reaction
between 5a and furan gave 5a’ as product (yield: 97%) in the
presence of B(C6F5)3, indicating that 5a-h are the intermediates
during the formation of 5a’-h’. The transformations between 5a-
h and 5a’-h’ are easy to be controlled.
To understand the mechanism of this new process, the
density functional theory (DFT) calculations with M06-2X
functional were performed (see the ESI for computational
details).[17] The reaction between N,N-Dimethylaniline (1b) and
ethyl vinyl ether (2b) was chosen as the model reaction. The
corresponding free-energy profile is shown in Figure 1. As seen
from Figure 1, this reaction may proceed in the following steps.
First, the coordination of B(C6F5)3 to the C=C double bond of 2b
[15d] produces the intermediate Int1, which is slightly endergonic
by 0.3 kcal/mol. The C=C bond length in Int1 is 0.075 Å longer
than that in 2b, indicating that the C=C double bond is
conversion of the substrates. Because B(C6F5)3 has the ability to
[15, 16]
bind with the nitrogen of Lewis base,
it is necessary to
check the influence of this binding to the reaction. For this
purpose, N,N-Dialkylanilines with methyl, ethyl and propyl on the
nitrogen atome were investigated. Being different from N,N-
Dimethylaniline and N,N-Diethylaniline, the interaction between
N,N-Dipropylaniline and B(C6F5)3 is quite weak due to the steric
hindrance, [15a] which can be confirmed by the 11B NMR of N,N-
Dialkylaniline-B(C6F5)3 solution (Table S1 in ESI). The satisfied
yields of 3i to 3l suggest that the reaction did not go through the
intermediate containing nitrogen-B(C6F5)3 interaction. Methyl
substitution on the meta-position of 1b can introduce steric
hindrance. In this case, when there is no obvious repulsion
between 1 and 2, the reactions still perform quite well (3m, 3n,
and 3p). Otherwise, the reaction cannot happen (3o).
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Figure 1. The energy profile for the one-pot FC and C-H/C-O coupling process. The values shown above are Gibbs free energies in kcal/mol. The optimized
structures can be found in Figure S5.
reaction occurred at 110oC and the best conversion was
somewhat activated. Subsequent electrophilic addition of Int1 to
1b produces the dearomatized intermediate Int2, which involves
a free energy barrier of 12.5 kcal/mol (via TS1-2) and is
endergonic by 9.5 kcal/mol. TS1-2 involves attack by the boron-
anion at the para-carbon, which is similar to that reported for the
obtained in the absence of extra solvent (Entries 1-5, Table 1).
According to our calculations, the whole reaction was
presented in Scheme 4. To verify this reaction mechanism, we
have also carried out some control experiments. First, the FC
reaction can happen alone with excellent yield in the presence of
[18]
hydrogenation of N-phenyl amines catalyzed by B(C6F5)3.
B(C6F5)3 rather than carbene-Au reported in our previous work
[13a]
Then, rearomatization of Int2 with the assistance of another 1b
molecule forms the intermediate Int3 via TS2-3 with a barrier of
15.2 kcal/mol (relative to the reactants). After that, a proton
transfer from the ammonium ion to the C atom bonded to
B(C6F5)3 produces Int4 via TS3-4. The free energy barrier of this
step is 28.7 kcal/mol (relative to Int3). Reaction between 1b and
2b to produce Int4 corresponds to the FC reaction. In the
second stage, the reaction proceeds via the C-H/C-O coupling to
produce the final product 3a. This stage starts by the
coordination of B(C6F5)3 to the O atom of Int4 to produce the
species Int5. The C1-O bond length in Int5 is 0.096 Å longer
than that in Int4, indicating the activation of C-O bond by
B(C6F5)3. Then, electrophilic attack of Int5 to another 1b
molecule provides Int6 via TS5-6, with a barrier of 13.5 kcal/mol
(Scheme 5a).
We also synthesized a compound 7 by
Grignard reaction, which has a similar structure as Int4 in the
theoretical calculation. was used to react with N,N-
7
Dialkylanilines for direct C-H/C-O coupling (Scheme 5b). As
expected, the reaction between 6 and 1b gave the product 3a
with 91% isolated yield. When 1a was used as substrate to react
with 7, the reaction produced a new compound 8, which
contains both N,N-dimethyl-phenylamino and N,N-diethyl-
phenylamino. Being different from the one pot reaction between
1b and 2b, the C-H/C-O coupling between 7 and 1b occurred at
room temperature (Figure S1 in ESI). This phenomenon is in
accord with the calculation results that the C-H/C-O coupling
involves a barrier of only 13.5 kcal/mol, which is easier to
happen comparing with the FC reaction (Figure 1). Second,
when a mixture of 1a and 1b (1:1 in mole ratio) was used as
substrate to react with 2b, the reaction produced 3a, 8 and 3e in
the ratio of 7:44:49 (Scheme 5c), which further support the
appearing of Int4 as the intermediate in the one-pot process.
Changing the mole ratio of 1a and 1b, the distribution of the
products can be well controlled (Figure S3 in ESI). In addition, a
proton trapping experiment was also performed (Scheme 5d).
When proton trapping agent (NEt3) was added into the reaction
system, the reaction cannot happen at all.
(relative to Int4). Finally,
a
proton transfer leads to
rearomatization of Int6, giving the final product 3a and C2H5OH
as a by-product. At the same time, B(C6F5)3 was regenerated.
The generation of 3a is exergonic by 17.2 kcal/mol. The rate-
determining step of the whole process is the proton transfer in
the FC reaction with
a barrier of 28.7 kcal/mol. N,N-
Dimethylaniline (1b)-assisted proton transfer plays an important
role in the reaction. This result is consistent with the fact that the
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10.1002/asia.202000763
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This work was supported by National Natural Science
Foundation of China (No. 21676134, 21878141, and 21576129).
Conflict of interest
The authors declare no conflict of interest.
Keywords: Friedel-Crafts • C-H/C-O Coupling • B(C6F5)3 • Lewis
acid • Density functional calculation
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(a) Independent FC reaction
(b) Direct C-H/C-O coupling of the intermediate 7
(c) Intermediate verification
(d) Proton trapping experiment
Scheme 5. Experimental results on the mechanism study. Isolated yields were
reported.
In conclusion, a simple and easily accessed metal-free one-pot
Friedel-Crafts and C-H/C-O coupling reaction catalyzed by
B(C6F5)3 was reported. This new process is suitable for the
reactions between dialkylanilines and vinyl ethers. No other
additives and solvent are required. Good isolated yields were
obtained for most of substrates. The mechanism of this new
process has also been elucidated based on experimental and
theoretical investigations. The catalyst B(C6F5)3 is found to
activate the C=C and C-O bond for FC and C-H/C-O coupling
reactions respectively. We believe that the metal-free strategy
reported here could be applicable for constructing other kinds of
C-C bonds.
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10.1002/asia.202000763
Chemistry - An Asian Journal
COMMUNICATION
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COMMUNICATION
One-pot Friedel-Crafts and C-H/C-O
coupling reactions catalyzed by
B(C6F5)3 were achieved for the
reactions between a series of
dialkylanilines and vinyl ethers with
good isolated yields. The possible
reaction mechanism was proposed
based on theoretical and experimental
studies.
Gaowen Zhai+, Xueting Liu+, Wentao
Ma, Guoqiang Wang, Liu Yang, Shuhua
Li*, Youting Wu* and Xingbang Hu*
B(C6F5)3-Catalyzed Tandem Friedel-
Crafts and C-H/C-O Coupling
Reactions of Dialkylanilines
This article is protected by copyright. All rights reserved.