B(C6F5)3-Catalyzed cyclization of alkynes: direct synthesis of 3-silyl heterocyclic compounds

Article abstract of DOI:10.1039/d0cc04314a

An efficient one-pot strategy for easy access to 3-silyl heterocyclic compounds was developedviaa B(C₆F₅)₃-catalyzed cycloaddition reaction ofo-(1-alkynyl)(thio)anisoles oro-(1-alkynyl)-N-methylaniline. In this reaction, benzenethiophene, benzofuran or indole skeletons could be constructed by an intermolecular cyclization with diphenylsilane. This protocol elicited moderate-to-good yields with metal-free reaction systems.

Full text of DOI:10.1039/d0cc04314a

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DOI: 10.1039/D0CC04314A
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B(C6F5)3-Catalyzed Cyclization of alkynes: Direct Synthesis of 3-
Silyl Hetero Cyclic Compounds
Received 00th January 20xx,
Accepted 00th January 20xx
Mengxing Li, Ting Wang, Zhenyu An, Rulong Yan*
DOI: 10.1039/x0xx00000x
www.rsc.org/
(a) General strategies for the synthesis of heteroarylsilanes
An efficient one-pot strategy for easy access to 3-silyl hetero cyclic
compounds has been developed via B(C6F5)3-catalyzed
R
a
Si LG
cycloaddition reaction of o-(1-alkynyl)(thio)anisoles or o-(1-alkynyl)-
N-methylaniline. In this reaction, benzenethiophene, benzofuran
or indole skeleton can be constructed by the intermolecular
cycliazation with diphenylsilane. This protocol features moderate
to good yields with metal-free reaction systems.
Si
X
Si
cat.
Rh, Au
Path. B
X
X
Path. A
Si
LG = H, CF3 etc.
Cat. = Rh, Ru, Ir, KOtBu, CsF, RbF, B(C6F5)3 etc.
X
Si
(b) One-pot synthesis of heteroarylsilanes (this work)
Heteroarylsilanes are stable and find widespread use in
medical imaging applications, polymer synthesis, and drug
discovery.1 As a consequence, the exploitation of efficient
methods to construct heteroarylsilanes has become one of the
hot-topic areas in modern organic synthesis. Reports to today,
many researches have been reported for the synthesis of
R
R
Ar
R
X
B(C6F5)3 (15 mol %)
PhCI, N2, 120 oC, 24 h
X= S, O
Si
Si
H
+
Ar
Me
X
X= S, O, NH
N
Me
substituted heteroarylsilanes.2, 3 As depicted in Scheme 1 ， Scheme 1 Approaches for the synthesis of heteroarylsilanes
these synthetic strategies can be divided into two pathways: (a)
reported the effective C-H silylation of a series of electron-rich
direct silylation of heterocyclic compounds catalyzed by the Rh,
aromatic compounds such as N,N-disubstituted anilines with a
Ru , Ir etc,4 and (b) construction of heteroarylsilanes by the
variety of hydrosilanes using B(C6F5)3 as a catalyst.8b Later,
cyclizations from the aryne precursors containing the silicon
Zhang and co-workers showed that B(C6F5)3 -catalyzed
groups.5 In the developing pathway B, the obvious features of
convergent disproportionation reaction of indoles with
the substrates were already containing the silicon groups, and
hydrosilanes.8c On the other hand, 2-alkynylthioanisoles have
suffering the tedious and difficult synthesis operation.
been widely used in cyclization process for the construction of
Therefore, the intermolecular strategy to construct the hetero
benzothiophenes owing to the very stable and readily available
cyclic compounds with silanes to afford heteroarylsilanes is
properties.9 In order to develop the method of intermolecular
still highly desirable for its simple and easy operation.
cyclization and silylation to achieve silyl hetero cyclic
The C-Si bond formation has constantly attracted
compounds, herein, we envisaged the feasibility of using
tremendous interest in the organic and material chemistry.6
B(C6F5)3 as a catalyst to generate silylbenzo[b]thiophenes with
Recently, the B(C6F5)3 have often been served as powerful
2-alkynylthioanisoles and diphenylsilane.
metal-free catalyst for the C-Si bond formation. Several studies
Initially, methyl(2-alkynylphenyl)sulfanes (1a) and
on the B(C6F5)3-catalyzed the C-Si bond formation have been
diphenylsilane were chose as starting materials to explore the
developed.7,8 The group of Piers reported the B(C6F5)3-
reaction conditions. The product (2a) was successfully
catalyzed reactions between hydrosilane and the aromatic
obtained in 34% yield with B(C6F5)3 (5 mol %) in toluene at
aldehydes, ketones, and esters.8a In 2016, Hou’s group
120°C under nitrogen atmosphere (Table 1, entry 1). Among
the various solvents examined, chlorobenzene was superior
than toluene, dimethylformamide (DMF), ethanol, and 1,2-
dichloromethane (DCM) (Table 1, entries 2-5). When the
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and
reaction was carried out under air, a slightly lower yield was
obtained (Table 1, entry 6). The amount of B(C6F5)3 was also
evaluated and 15 mol % of B(C6F5)3 showed the best catalytic
Chemical Engineering, Lanzhou University, Lanzhou, Gansu, China.
Fax: 0931-8912596 E-mail: yanrl@lzu.edu.cn
† Electronic Supplementary Information (ESI) available: Experimental procedures
spectroscopic data. See DOI: 10.1039/c000000x/
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1

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Table 2 Scope of 3-silylbenzo[b]thiophenes a
Table 1 Optimization of the reaction conditions a
View Article Online
DOI: 10.1039/D0CC04314A
R
Ph
SiPh2H
Si
B(C6F5)3
B(C6F5)3 (15 mol %)
Ph2SiH2
Si
Ar
R
Ph
Ar
PhCI (2 mL),120 o
24 h, N2
C
solvent, 120 oC, 24 h, N2
Me
Me
S
S
S
S
1a-1s
SiPh2H
Silicon
sources
Catalyst
(mol %)
2a-2s
Entry
Solvent
Yield (%)
SiPh2H
SiPh2H
Me
Et
1
2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
HMD
5
5
Toluene
PhCl
DMF
EtOH
DCM
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
34
62
S
S
S
2b, 90%
2c, 95%
2a, 88%
SiPh2H
SiPh2H
SiPh2H
3
5
n.d.
n.d.
25
nPr
Ph
tBu
S
S
S
4
5
2f, 57%
2d, 68%
2e, 65%
5
5
SiPh2H
SiPh2H
SiPh2H
Cl
6c
7
5
55
Br
O
S
S
S
2g, 43%
2i, 52%
2h, 77%
10
15
0
70
SiPh2H
SiPh2H
SiPh2H
Me
8
88
Me
S
S
S
9
n.d.
n.d.
n.d.
68
Me
Cl
2j, 80%
2k, 49%
2l, 56%
10b
11
12
13
14
15
15
15
15
15
SiPh2H
SiPh2H
SiPh2H
S
Ph3SiH
S
S
S
Cl
PhSiH3
2m, 78%
2n, 67%
2o, 56%
SiPh2H
SiPh2H
SiPh2H
Et3SiH
44
Me
Et
S
S
S
Ph2MeSiH
trace
2r, 41%
SiPh2H
2q, 50%
2p, 0%
a Reaction conditions: 1a (0.2 mmol), Ph2SiH2 (0.4 mmol), B(C6F5)3,
solvent (2 mL), 120 °C, N2, 24 h. Isolated yield based on 1a. b HMD
= Hexamethyldisilane. c Under air.
SiPh2H
SiPh2H
Me
Br
S
S
S
Me
efficiency, giving the desired product 2a in 88% yield (Table 1,
entries 7-9). Other silicon sources were also investigated and
no corresponding products were detected when
hexamethyldisilane(HMD) and triphenylsilane served as silicon
sources (Table 1, entries 10-11). Phenylsilane and triethylsilane
were employed for this reaction system, giving the
corresponding desired products 5 and 6 in 68% and 44% yields
respectively (Table 1, entries 12-13). But Ph2MeSiH only gave a
trace amount of the desired product (Table 1, entry 14).
Having optimized the reaction conditions in hand, we
explored the generality of this cycloadditions reaction for the
generation of 3-silylbenzo[b]thiophenes with methyl(2-
alkynylphenyl)sulfanes and diphenylsilane as substrates. The
results were summarized in table 2. It was found that reactions
of methyl(2-alkynylphenyl)sulfanes with various groups work
smoothly to provide the corresponding products in moderate
to good yields. With electron-donating substituents on the
aromatic ring at the terminal alkyne, such as methyl, ethyl,
propyl, tertiary butyl, pentyloxy, and phenyl groups, desired
2t, 59%
2u, 72%
2s, 75%
a Reaction conditions: 1 (0.2 mmol), Ph2SiH2 (0.4 mmol), B(C6F5)3 (15
mol %), solvent (2 mL), 120 °C, N2, 24 h.
products were obtained in 43-95% yields. Electron-
withdrawing groups such as chloro and bromo were also
tolerated with the optimized reaction conditions, affording the
corresponding products in moderate yields (2h, 2i, 2l, 2m). The
substrate 2k with substituent at the ortho position of the
phenyl ring slightly lowered the reactivity may cause by the
steric hindrance. Additionally, the substrates with R as the
naphthyl group (1n) and thienyl group (1o) were employed for
this reaction system, giving the desired products in 67% and 56%
yields, respectively. Notably, no desired product 2p was
obtained and starting material 1p almost all was recovered in
this reaction system, this result demonstrated that the
terminal active hydrogen of acetylene affected this
transformation severely. Moreover, the reaction system is also
2 | J. Name., 2012, 00, 1-3
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COMMUNICATION
SiPh2H
Ph
Table 3 Scope of 3-silylbenzo[b]furans and 3-silylindoles a
PhI
View Article Online
Pd(OAc)2, Xantphos
R
DOI: 10.1039/D0CC04314A
SiPh2H
Ph
Ph
B(C6F5)3 (15 mol %)
KOH, p-xylene
S
S
Ph2SiH2
R
PhCI (2 mL),120 o
24 h, N2
C
2a
Me
7, 56%
X
X
X
SiPh2H
Me
4a-4o
3a-3o
The scope of benzofuran silanes
Br
Br
NXS, CH2Cl2
r.t., 4h
Ph
Ph
S
S
8, 92% (X= Br)
9 ,80% (X= I)
2u
SiPh2H
SiPh2H
SiPh2H
Me
SiPh2H
Me
Et
Scheme 2 Further transformation of the heteroarylsilanes
O
O
O
O
heterocyclic compounds by the 3-silylbenzo[b]thiophenes. For
example, the silylated compound 2a reacted with PhI to
produce compound 7 in 56% yield through the Pd-catalyzed
cross-coupling process.10a Similarly, the corresponding
halogenated products 8 and 9 were obtained in high yields
when the compound 2u was employed as substrate through
4a, 70%
SiPh2H
4b, 77%
4c, 68%
4d, 67%
SiPh2H
Me
SiPh2H
SiPh2H
S
nBu
Me
O
O
O
O
F
4e, 73%
4f, 78%
4g, 54%
4h, 67%
The scope of N-methylindole silanes
8b
the bromination and iodination under mild conditions
SiPh2H
SiPh2H
SiPh2H
SiPh2H
(Scheme 2).
nBu
Me
Me
N
N
N
N
Ph
Me
Me
Me
F
Me
B(C6F5)3 (15 mol %)
Ph
4i, 62%
4j, 67%
4k, 58%
4l, 71%
1
2
PhCI (2 mL),120 o
C
S
Me
S
SiPh2H
24 h, N2
SiPh2H
SiPh2H
10, 40%
S
1a
Cl
Me
N
N
Ph2SiH2
N
SiPh2H
Ph
Me
Me
Me
B(C6F5)3 (15 mol %)
4m, 72%
Ph
4n, 61%
4o, 43%
PhCI (2 mL),120 o
24 h, N2
C
S
a
S
Reaction conditions: 3 (0.2 mmol), Ph2SiH2 (0.4 mmol), B(C6F5)3
(15 mol%), solvent (2 mL), 120 °C, N2, 24 h.
2a, 0%
10
Scheme 3 Control experiments
To gain insight into the reaction mechanism, several
mechanistic experiments were carried out. First, we
performed the reaction with 1a in the absence of
diphenylsilane and the benzothiophene 10 was obtained in 40%
yield. (Scheme 3, entry 1). The benzothiophene 10 and
diphenylsilane were also subjected to the standard conditions
and no corresponding desired product 2a was obtained
(Scheme 3, entry 2). This result could rule out that the reaction
is proceeded by the sequence of formation of heterocycles and
C3 site C-H silylation.
suitable for the more challenging substrates carrying alkyl
group on the terminal alkyne (2q-2r). Furthermore, the
substrates with methyl or bromo group on the aromatic ring
also generated the corresponding products 2s, 2t and 2u in
moderate yields.
To further explore the scope of this protocol, we turned our
attention to synthesize of various 3-silylbenzofurans and 3-
silylindoles. As shown in table 3, a series of 1-methoxy-2-
(phenylethynyl)benzenes underwent efficiently through
cyclization to produce the desired 3-silylbenzofurans
successfully with satisfactory yields. When the substrates with
alkyl on the aromatic ring at the terminal alkyne (3a-3f), the
reaction worked well, delivering the desired products (4a-4f) in
67-77% yields. In the case of substrates with strong electron-
withdrawing F group (3g), lower yields of the desired products
were afforded. In addition, we find that the substrate with
thienyl group (3h) was also worked smoothly through this
transformation. Similarly, the 3-silylindoles were also can be
synthesized from N-methyl-2(phenylethynyl)anilines with this
reaction system. With this transformation, a variety of
different substituted 3-silylindoles were furnished in
acceptable yields. Various substitutions on the aromatic ring at
the terminal alkyne were well tolerated with the reaction
conditions and the expected products were obtained in
moderate yields (4i-4m). As expected, the substrate with a
thienyl group at the terminal alkyne also reacted with
diphenylsilane to give the product 4o in 43% yield.
2a CH
+
B(C6F5)3
4
Ph
Si
H
H
Ph
SiPh2H
Ph
S
Me
B
Ph
Si
H
H
B(C6F5)3
Ph
H
B(C6F5)3
A
Ph
Ph
Si
Me
S
Ph
H
1a
Scheme 4 Proposed mechanism
A plausible reaction mechanism for the present B(C6F5)3-
To demonstrate the synthetic value of this method, we
investigated the further derivation potential to form diverse
catalyzed silylation is depicted in Scheme 4 on the basis of
7,8,11
these experimental results and previous reports
Initially,
the hydrosilane could be activated by B(C6F5)3 through a B-H
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Y. Han, S. Zhang, J. He and Y. Zhang, ACS Catal. 2018, 8,
interaction to form the weak adduct A. Subsequently, the
resulting cationic Ph2SiH+ species selectively attacks the triple
bond of methyl(2-alkynylphenyl)sulfanes 1a to generate the
intermediate B with the forming of C-S bond. Finally,
demethylation provides 3-silylbenzo[b]thiophene 2a, along
with the B-(C6F5)3H converting to B(C6F5)3.
In summary, we have developed a metal-free electrophilic
silylation and cyclization of alkynes. The electrophilic silylation
reagent diphenylsilane with B(C6F5)3 catalyst proceeds
smoothly cycloaddition reaction with alkynes to form various
silylation heterocyclic compounds.
View Article Online
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DOI: 10.1039/D0CC04314A
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This work was supported by National Natural Science
Foundation of China (21672086).
Conflicts of interest
There are no conflicts to declare.
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DOI: 10.1039/D0CC04314A
Si
R
B(C6F5)3 (15 mol %)
PhCI, N2, 120 oC, 24 h
Si
H
R
X Me
X
X= S, O, NCH3
X= S, O, NH
One-pot synthesis
High chemoselectivity (C3 position)
High functional group compatibility
Transition-Metal free conditions