Construction of Six-Membered Silacyclic Skeletons via Platinum-Catalyzed Tandem Hydrosilylation/Cyclization with Dihydrosilanes

Article abstract of DOI:10.1002/adsc.201800456

Catalytic silicon-carbon or silicon-heteroatom bond-forming hydrosilylation has become increasingly important in synthetic chemistry, catalysis and organosilicon chemistry. Herein we report a platinum-catalyzed one-pot and tandem hydrosilylation/cyclization of OH-containing alkynes with dihydrosilanes, allowing for facile synthesis of six-membered organosilicon compounds, including silyloxycycles and cyclic siloxanes in high yields and with good stereoselectivities. (Figure presented.).

Full text of DOI:10.1002/adsc.201800456

Title: Construction of Six-Membered Silacyclic Skeletons via
Platinum-Catalyzed Tandem Hydrosilylation/Cyclization with
Dihydrosilanes
Authors: Peng-Wei Long, Xing-Feng Bai, Fei Ye, Li Li, Zheng Xu, Ke-
Fang Yang, yuming cui, Zhan-Jiang Zheng, and Li-Wen Xu
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800456
Link to VoR: http://dx.doi.org/10.1002/adsc.201800456

10.1002/adsc.201800456
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Construction of Six-Membered Silacyclic Skeletons via
Platinum-Catalyzed Tandem Hydrosilylation/Cyclization with
Dihydrosilanes
Peng-Wei Longa, Xing-Feng Baia,b, Fei Yea, Li Lia, Zheng Xu a*, Ke-Fang Yanga, Yu-
Ming Cuia, Zhan-Jiang Zhenga, Li-Wen Xua,b*
a
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal
University, Hangzhou 311121, P. R. China.
[Fax: 86 2886 5135; Tel: 86 2886 8720; E-mail: liwenxu@hznu.edu.cn]
Suzhou Research Institute and State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of
b
Chemical Physics, Chinese Academy of Sciences, Lanzhou, P. R. China
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
(a) Previous work
Abstract. Catalytic siliconcarbon or siliconheteroatom
bond-forming hydrosilylation has become increasingly
Ph
Ph
Si
Pd(OAc)2 (5 mol %)
PCy3-HBF4 (10 mol %)
t-Bu
t-Bu
O Si
important in synthetic chemistry, catalysis and
organosilicon chemistry. Herein we report a platinum-
catalyzed one-pot and tandem hydrosilylation/cyclization
of OH-containing alkynes with dihydrosilanes, allowing for
facile synthesis of six-membered organosilicon compounds,
including silyloxycycles and cyclic siloxanes in high yields
and with good stereoselectivities.
O
(1)
PivOH, Cs2CO3
Br
R
R
3 A MS, p-xylene,
140 o
C
X
X
[Rh(OH)(coe)2]2 ( 8 mol % Rh)
(S,S)-Me-Duphos ( 6 mol %)
O
OH
SiRAr2
(2)
(3)
(4)
Si
R
ethyl acrylate (1.2 equiv)
THF, 65 oC, 24 h
Ar
Keywords: Cyclization; platinum; organosilicon;
homogeneous catalysis; silacycle.
Y
Y
i-Pr
i-Pr
Pd(OAc)2 (10 mol %)
Ligand (20 mol %)
i-Pr
O
The siliconcarbon or siliconheteroatom bond-forming
hydrosilylation of unsaturated compounds, including
olefins, alkynes, carbonyl compounds, and imines, is a
fundamental and synthetically valuable reaction that has
found wide applications in the synthesis of structurally
diverse organosilicon compounds.[1] In this context, the
catalytic hydrosilylation of carboncarbon multiple bonds
is arguably one of the most powerful and useful methods
for the synthesis of substituted silanes and their
derivatives.[2] In particular, transition metal-catalyzed
hydrosilylation of internal alkynes has received
considerable attention in the past years, and rapid progress
has been made in this field.[1-3] However, due to the low
reactivity and difficulty in controlling stereoselectivity, the
hydrosilylation of internal alkynes with hydrosilanes is
challenging.[4] In this context, Tomooka et al.[5] reported an
elegant platinum-catalyzed hydrosilyation of internal
Si
I
Si
O
R2
i-Pr
R2
DIPEA (2.2 equiv)
PhMe, 75 oC, 5-12 h
ii) [Rh(nbd)Cl]2
(0.4 mol %)
P(4-OMePh)3P
(2.4 mol %)
R
i) [Ir(coe)2Cl]2
(0.1 mol %)
H2SiR2 (2. 5 equiv)
R
Si
O
O
nbe (2 equiv)
R1
R1
R2
R2
DCM, 80 oC, 2 d THF, 120 o
C
(b) This work
R1
Z
Z
O
R1
Pt2(dba)3 (1 mol %)
OH
(5)
Si
RuPhos (2 mol %)
Ph
Ph
+
Si
H2
DCM, 80 oC, 12 h
Z = CH2 or SiR2
R2
R2
alkynes in which
a catalytic desymmetrization of
dihydrosilanes was developed. Meanwhile, methods for
selective and tandem hydrosilylation of internal alkynes
and alcohols with dihydrosilanes remained scarce.
Furthermore, to the best of our knowledge, there are no
reports on transition metal-catalyzed synthesis of six-
membered silacycles via one-pot hydrosilylation of
alcohol/silanol-containing alkynes with dihydrosilanes.
Figure 1. The synthesis of oxygen-containing silacycles
through transition-metal-catalyzed cyclization.
Recently, construction of oxygen-containing silacyclic
skeletons via transition metal catalysis has drawn much
attention from synthetic community.[6] For example,
Gevorgyan and co-workers[7] reported
a
palladium-
1
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10.1002/adsc.201800456
Advanced Synthesis & Catalysis
catalyzed intramolecular arylation of TBDPS-protected
dimethyl(2-(phenylethynyl)phenyl)silanol
(1a)
and
phenols for the synthesis of silyloxycycles (Figure 1, eq. 1). methylphenylsilane (2a) was also an important factor
In 2012, Shintani and Hayashi[8] developed an interesting
synthesis of silicon-stereogenic dibenzooxasilines via a
rhodium-catalyzed transmetalation of hydroxyl-tethered
tetraorganosilanes (Figure 1, eq. 2). Moreover, palladium-
catalyzed silyl methyl Heck reaction of iodomethylsilyl
ethers of phenols with aliphatic alkenols was also proven
to be a facile approach to access oxygen-containing
silacyclic skeletons (Figure 1, eq. 3) [9]. In 2015, Jeon and
co-workers[10] reported a modular approach towards
catalytic synthesis of silyloxycycles by reductive C(sp2)-H
and C(sp3)-H silylation through sequential transition metal
catalysis (Ir(I)/Rh(I) or Rh(I)/Rh(I), see Figure 1, eq. 4), in
which the first step was iridium or rhodium-catalyzed
hydrosilylation of ketones, and subsequent Rh/(4-
MeOPh)3P-catalyzed arene C-H silylation and competitive
alkene hydrosilylation of norbornene (nbe) were the key
steps. Very recently, we reported a facile catalytic
synthesis of cyclic siloxanes through iridium-catalyzed
intramolecular C–H silylation of siloxane-tethered arenes
and hydrosilanes.[11] Apparently, development of a simple
reaction with general and excellent control in
stereoselectivity is highly desirable. It is thus of great
importance to design new strategy to access structurally
diverse silacyclic compounds.
(Table S4 of Supporting Information).
Table 1. Optimization of reaction conditions.[a]
"Standard conditions"
O
Pt (dba) (1 mol %)
RuPhos (2 mol %)
2
3
OH
Si
Ph
Ph
+
Si
2
o
H
DCM, 80 C, 12 h
2a
1a
3a
RuPhos =
i-PrO
PCy
2
Oi-Pr
Entry Derivation from standard conditions
Yield
(%)[b]
none
83[c]
30
26
43
27
13
26
66
1
2
3
4
5
6
7
8
TBSO-MOP instead of RuPhos at rt
Xantphos instead of RuPhos at rt
SPhos instead of RuPhos at rt
Johnphos instead of RuPhos at rt
PPh3 instead of RuPhos at rt
DPEphos instead of RuPhos at rt
Inspired by previous reported platinum catalysis,[12] and
built upon our recent findings on multicomponent reaction
with dihydrosilanes, alkynes, and alcohols,[13] we herein
document
a chemoselective synthesis of silacycles,
including oxasilines and cyclic siloxanes, via a platinum-
catalyzed tandem silylation/hydrosilylation of internal
alkynes bearing an alcohol or silanol group with
dihydrosilanes (Figure 1, eq. 5).
We started our investigation by examining catalytic effects
of phosphine ligands, such as Xantphos, SPhos, DPEphos,
Johnphos, Betettphos, Ruphos, in the tandem
hydrosilylation/cyclization of OH-containing acetylene 1a
with methylphenylsilane 2a in the presence of 1 mol%
Pt2(dba)3. After extensive screenings of phosphine ligands
(see Table S1-S4 of Supporting Information), including the
TBS-monoprotected TBSO-MOP that has excellent
activity in platinum-catalyzed multicomponent silylation of
alkynes and alcohols with dihydrosilanes,[13] the best
ligand and the optimized reaction conditions were
identified, which were used for the synthesis of the desired
silacycle 3a in 83% yield (Table 1, entry 1). The choice of
Pt catalyst and RuPhos was crucial for the tandem
hydrosilylation/cyclization reaction, evidenced by the
drastically decreased reaction yield in the control
experiment when triphenylphosphine was employed as the
ligand (Table 1, entry 6). Other phosphine ligands, such as
Xantphos, Sphos, DPEphos, Xphos, Johnphos, and
Btettphos were found to be less effective for this
transformation and led to inferior results (see Table S1 in
Supporting Information). Solvent screening revealed that
toluene was the best solvent (Table 1, entries 8 and 9, also
see Table S2 in Supporting Information for detail). In
addition, room temperature and increasing reaction
1,2-dichlorobenzene instead of DCM at
rt
DCE instead of DCM at rt
31
66
71
25
40
<5
NR
9
at rt instead of 80 oC
10
11
12
13
14
15
at 100 oC instead of 80 oC
Pd2(dba)3 instead of Pt2(dba)3
[Rh(COD)Cl]2 instead of Pt2(dba)3
[Ir(COD)Cl]2 instead of Pt2(dba)3
[Ru(p-cymene)Cl]2 instead of Pt2(dba)3
[a] Unless otherwise noted, the reaction conditions were as
follows: (2-(phenylethynyl)phenyl)methanol (0.4 mmol),
platinum complex (1 mol %), ligand (2 mol%). Reaction time is
12 hours for every case. [b] Yield was determined by 1H NMR. [c]
The isolated yield is 55% in this case.
o
temperature to 100 C led to lower yield (Entries 10 and
11). Notably, the reaction promoted by the other transition
metal complexes, such as Pd2(dba)3, [Rh(COD)Cl]2,
[Ir(COD)Cl]2, and [Ru(p-cymene)Cl]2, resulted into poorer
or no conversion (Entries 12-15). And the ratio of
2
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10.1002/adsc.201800456
Advanced Synthesis & Catalysis
With the established optimal conditions in hand, we
investigated the substrate scope of this tandem
hydrosilylation/cyclization of OH-containing alkynes, and
the results are summarized in Scheme 1. The reaction was
applicable to various OH-containing alkynes 1 (11
examples) bearing different substituents on the phenyl ring,
tolerated, leading to the formation of a wide range of
siloxanes 5 in high yields (65-94%). In addition, diethyl
dihydrosilane and tert-butylphenylsilane were also found
to be suitable reaction partners, and siloxanes 5o and 5p
were obtained in good yields.
R
R
R
R
Si
O
Pt2(dba)3 (1 mol %)
RuPhos (2 mol %)
Si
R3
R4
R1
and
the
corresponding
silylether-containing
OH
R3
R2
R4
R1
Si
+
Si
benzo[d][1,2]oxasilines 3 were obtained in good yields.
Notably, the reaction conversions were excellent, but the
isolated yields slightly decreased due to the SiO bond
cleavage of benzo[d][1,2]oxasilines 3 during the column
chromatographic purification.
Toluene, 100 oC, 12 h
H2
2
R2
4
RuPhos =
i-PrO
5
PCy2
Oi-Pr
O
Si
Cl
Si
MeO
Si
O
1
Pt (dba) (1 mol %)
RuPhos (2 mol %)
2
3
R
O
Si
Si
OH
1
Ph
O
O
R
Ph
Si
Si
+
Si
Ph
Ph
Si
o
H
Si
2
DCM, 80 C, 12 h
Ph
Ph
2
Ph
R
Ph
2
R
Ph
Ph
1
5d
80% yield
5c
91% yield
3
RuPhos =
i-PrO
5b
90% yield
PCy
5a
86% yield
2
Oi-Pr
Si
O
Si
O
F
Si
Si
O
O
Si
O
O
Si
MeO
Ph
O
Ph
Si
Si
O
Ph
O
O
Ph
F3C
Ph
Si
Si
Si
Si
t-Bu
Ph
n-Bu
Ph
Ph
Ph
Ph
5g
Ph
5h
70% yield
Ph
3b
60% yield
Ph
5f
Ph
3c
60% yield
5e
73% yield
74% yield
73% yield
3a
3d
55% yield
55% yield
Si
Si
Si
O
O
Si
O
O
O
O
MeO
MeO
Cl
Si
Si
O
O
Si
Si
Si
Ph
Ph
Si
Ph
Ph
Ph
Ph
Si
Si
Ph
Ph
Ph
Ph
F
MeO
F
5l
5k
66% yield
3e
5j
3g
3h
3f
5i
83% yield
85% yield
68% yield
43% yield
24% yield
62% yield
55% yield
Si
O
O
O
Si
O
Si
O
Si
O
O
Si
Si
Si
Si
Et
Ph
Ph
Ph
t-Bu
Si
Ph
Si
Si
Ph
Et
Ph
Ph
Ph
n-Bu
Cl
Prn
F3C
Bu
5p
65% yield
3k
5o
98% yield
5n
81% yield
3j
5m
88% yield
3i
45% yield
50% yield
46% yield
Ph Ph
i-Pr i-Pr
Si
O
Si
Scheme 1. Pt-catalyzed tandem hydrosilylation/cyclization
of (2-(arylethynyl)phenyl)methanols with
methylphenylsilane 2a.
O
Si
Si
1
Ph
Ph
Ph
Ph
5q
5r
32% yield
75% yield
Built upon the above successful construction of silacycles
via platinum-catalyzed tandem hydrosilylation/cyclization
reaction, we next aimed at the synthesis of cyclic siloxanes
using the same method. A silanol-containing alkyne 4a
was then prepared and tested in the Pt-catalyzed tandem
hydrosilylation/cyclization reaction (Table S5 of
Supporting Information). To our delight, silacycle 5a was
obtained in 41% yield under the standard reaction
conditions. Running the reaction at 100 oC led to an
increased yield of 94%. Moreover, the loading of platinum
catalyst could be reduced to 0.1 mol %, with a slightly
decreased yield of 82% (Table S5).
Scheme 2. Pt-catalyzed tandem hydrosilylation/cyclization
of
dimethyl(2-(arylethynyl)phenyl)silanols
4
with
dihydrosilanes 2.
O
OH
TBAF (1 eq)
THF
Si
(1)
Ph
Ph
Ph
6
3a
Si
O
TBAF (1 eq)
THF
(2)
Si
Ph
With the optimal reaction conditions (Table S5, entry 6),
various substituted silanol-containing alkynes 4 were
Ph
Ph
7
5a
examined
hydrosilylation/cyclization
for
the
platinum-catalyzed
reaction
tandem
with
Scheme 3. The standard TBAF desilylation of product 3a
or 5a: The confirmation of (Z)-selectivity in platinum-
catalyzed hydrosilylation/cyclization.
methylphenylsilane 2a. As summarized in Scheme 2,
alkynes bearing electron-donating or electron-
withdrawing substituents on the phenyl rings were well
4
3
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10.1002/adsc.201800456
Advanced Synthesis & Catalysis
The stereoselectivity of platinum-catalyzed tandem
hydrosilylation/cyclization was confirmed by desilylation
reactions of 3a or 5a (Scheme 3), through which the
formation of known (Z)-alkenes indicated the (Z)-
stereoselectivity for the tandem hydrosilylation/cyclization.
To test the possibility of an enantioselective variant of this
reaction, we performed preliminary studies by employing a
range of chiral phosphine ligands, including HZNU-Phos,
Tao-Phos, and Xing-Phos developed by our group (see
Scheme S1)[14] under the standard reaction conditions
(Table S6 and Table S7 in Supporting Information).
However, it is difficult to control the desymmetrization of
MePhSiH2 by chiral P-ligands at present. It was found that
only the Fei-Phos[15] and its analogues exhibited the best
asymmetric induction, and led to products with up to 32%
ee (Scheme 4), potentially useful for enantioselective
construction of silicon-stereogenic oxasiline.[16]
ESI-MS, see Figure S1-S4, and for NMR analysis, see
Figure S5-S7, in Supporting Information) of possible
platinum species in the presence of RuPhos ligand[18], a
plausible mechanism for this platinum-catalyzed tandem
hydrosilylation/cyclization reaction was proposed (Figure
2). The addition of methylphenylsilane to platinum
intermediate (species I), followed by hydrosilated
alcoholysis or silanolysis, is a fast step to form etherified
platinum species IV. Subsequent intramolecular
hydrosilylation then gives the corresponding product 3 or 5.
Therefore, the mechanistic process gave important
information that the desymmetrization of dihydrosilane is
not an easy task because the stereoselective insertion of the
platinum complex to Si-H bond is quite difficult. Although
the origin of the observed stereoselectivity induced by
RuPhos or Fei-Phos is not clear at this stage, we believe
steric repulsion of P-ligand plays an important role during
the insertion of platinum to methylphenylsilane
(MePhSiH2) and subsequent transmetalation and reductive
elimination.
O
Pt2(dba)3 (1 mol %)
OH
Si

Ligand (2 mol %)
Ph
Ph
+
Si
H2
In summary, we have successfully developed a novel
platinum-catalyzed tandem hydrosilylation/cyclization of
OH-containing internal alkynes with dihydrosilanes. The
employment of a monophosphine ligand RuPhos led to the
facile construction of silacycles, silyloxycycles and cyclic
siloxanes in high yields and stereoselectivities. Preliminary
studies suggested that construction of silicon-stereogenic
DCM, rt, 12 h
2a
1a
3a
R = Ph, 30% yield, 25% ee
R = 4-methoxyphenyl,
45% yield, 32% ee
Me
R2P
N
N Me
PR2
Ligand =
R = Cy, 23% yield, 0% ee
silacycles
hydrosilylation/cyclization is feasible by employing chiral
ligands. Further mechanistic investigations and
development of an enantioselective variant of this reaction
are underway and will be reported in due course.
via
this
platinum-catalyzed
tandem
Fei-Phos and its analogues
Scheme 4. Stereoselective construction of silicon-
stereogenic center: Preliminary results for platinum-
catalyzed tandem hydrosilylation/cyclization of 1a with 2a.
Experimental Section
Ph
SiH2
General procedure for platinum-catalyzed tandem
hydrosilylation/cyclization. To a solution of Pt2(dba)3
L = RuPhos
Pt2(L0)3
L0 = dba
H
[Pt]
H
L
Si
Pt(0)
L
L0
(4.4 mg, 0.004 mmol,
1
mol%) in anhydrous
II
I
dichloromethane (4 mL) was added Ruphos (3.7 mg, 0.008
mmol, 2 mol %). The mixture was stirred at room
Z
OH
Z
temperature
(phenylethynyl)phenyl)methanol
methylphenylsilane (0.48 mmol) were added. After the
reaction was stirred at 80 C for 12 h in a sealed tube (25
for
30
minutes,
(0.4
and
then
mmol)
(2-
and
O
Ph
Si
Ar
Ph
H
R
3a, Z = CH2,
5a, Z = SiMe2
H
O
Pt
L
o
Si
H
mL), the reaction mixture was cooled down, diluted with
Et2O and filtered through Celite. The organic phase was
dried over Na2SO4 and concentrated under reduced
pressure. Purification by silica gel chromatography
(petroleum ether: ethyl acetate = 50:1) afforded the desired
product. All the products 3 have been analyzed by GC-MS,
NMR, and HRMS (see Supporting Information).
II
III
Ph
SiH2
Ar
Z
OR
O
Pt
L
Si
L
Si
Pt
H
H
IV
VI
Z
Ar
O
L
Si Pt
Acknowledgments
H
V
The authors gratefully thank the financial support of the National
Natural Science Foundation of China (No. 21472031, 21703051,
21702211, and 21773051), and Zhejiang Provincial Natural
Science Foundation of China (LZ18B020001, LY16E030009,
LY17B030005, and LY17E030003) is appreciated. The authors
also thank Dr. J. Cao, Dr. Y.M. Cui, Dr. F. Ye, Dr. K.Z. Jiang, Dr.
C.Q. Sheng, and Dr. G.W. Yin (all at HZNU) for their technical
and analytical support, and XLW thanks to Profs. Shibasaki and
Yixin Lu for their help in the past years.
Figure 2. Proposed mechanism for the platinum-catalyzed
tandem hydrosilylation/cyclization reaction of OH-
containing internal alkyne with methylphenylsilane.
On the basis of platinum-catalyzed hydrosilylation
reaction[17] and the experimental results on the electrospray
ionization mass spectrometry (ESI) and NMR analysis (for
4
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10.1002/adsc.201800456
Advanced Synthesis & Catalysis
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5
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10.1002/adsc.201800456
Advanced Synthesis & Catalysis
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[18] The experimental results on the electrospray
ionization mass spectrometry (ESI) and NMR analysis
gave useful information for this platinum-catalyzed
tandem hydrosilyation/cyclization reaction. For
example, the NMR analysis of the platinum complex
with RuPhos showed that there are possibly at least
three different intermediates, as evidence with the
presence of 67.36, 55.07, and 42.81 ppm (Figure S5 in
Supporting Information). And there is only one new
peak (47.75 ppm) of platinum/RuPhos complex in the
presence of MePhSiH2, which supported the formation
of new platinum intermediate II is a favorable
possibility. In addition, there is no change for
platinum/RuPhos complex with or without OH-
containing alkyne substrate 1a. Furthermore, the NMR
analysis of the reaction mixtures supported the
proposed mechanism showed in Figure 2 is reasonable.
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6
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10.1002/adsc.201800456
Advanced Synthesis & Catalysis
COMMUNICATION
Construction of Six-Membered Silacyclic
Skeletons via Platinum-Catalyzed Tandem
Hydrosilylation/Cyclization with Dihydrosilanes
1
R
Z
Pt (dba) (1 mol %)
RuPhos (2 mol %)
2
3
O
Z
1
3
3
4
R
R
R
R
Si

OH
Si
4
Adv. Synth. Catal. Year, Volume, Page – Page
o
R
+
H
DCM, 80 C, 12 h
2
Z = CH or SiR
2
2
2
R
>29 examples
up to 94% yield
Peng-Wei Long, Xing-Feng Bai, Fei Ye, Li Li,
Zheng Xu*, Ke-Fang Yang, Yu-Ming Cui, Zhan-
Jiang Zheng, and Li-Wen Xu*
2
R
7
This article is protected by copyright. All rights reserved.