Copper-catalyzed silylation reactions of propargyl epoxides: Easy access to 2,3-allenols and stereodefined alkenes

Article abstract of DOI:10.1039/c7cc04588c

Efficient silylation reactions of propargyl epoxides catalyzed by copper catalysts have been developed. Under mild reaction conditions, tri- and tetra-substituted functionalized allenols and alkenes could be selectively obtained in moderate to high yields

Full text of DOI:10.1039/c7cc04588c

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Copper-Catalyzed Silylation Reactions of Propargyl Epoxides: Easy
Access to 2,3-Allenols and Stereodefined Alkenes
Xi-Hao Chang,a Zheng-Li Liu,a Yun-Cheng Luo,a Chao Yang,a Xiao-Wei Liu,a Bing-Chao Da,a Jie-Jun
Li,a Tanveer Ahmad,a Teck-Peng Loh*a,b,c and Yun-He Xu*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
organometallic reagents have attracted much attention.[11]
Nevertheless, the use of expensive transition-metal catalysts or/and
sensitive organometallic reagents limited their wide application.
Efficient silylation reactions of propargyl epoxides catalyzed by
copper catalyst have been developed. Under mild reaction
conditions, the tri- and tetrasubstituted functionalized allenols
and alkenes could be selectively obtained in moderate to high
yields via tuning the bases and solvents used in the reactions. This
work provides straightforward and efficient approaches to the
synthesis of multifunctionalized 2,3-allenols and stereodefined
alkenes from the same starting material of propargyl epoxides.
R2
O
R1
PhMe2Si-Bpin
+
1
2
[Cu]
A
B
C
R2
PhMe2Si
OH
R2
PhMe2Si
R1
Multifunctionalized alkenes are fundamental building blocks for
the construction of complex molecules.[1,2,] Although numerous
methods have been developed for the preparation of these
compounds, the need to control the stereoselectivity as well as to
access structural diversity is still a challenging task.[3] Therefore,
methods such as carbometallation of alkynes and direct
functionalization of diverse allenes have been developed.[4,5]
However, the difficulty in controlling the stereochemistry as well as
limited substrate scope encourage us to develop versatile methods
to access a wide variety of polyfunctionalized alkenyl compounds
via formation of 2,3-allenols as precursors. In conjunction with our
continuous interests in the preparation of multifunctionalized
alkenes[6] and allenes,[7] herein we report copper-catalyzed silylation
reactions of propargyl epoxides for the synthesis of silyl-substituted
2,3-allenols and alkenes. The product distributions can be precisely
predicted and controlled by tuning the solvents and bases used in
the reactions (Scheme 1). Moreover, boryl and silyl functionalized
alkenes can be easily accessed via the transformation of 2,3-allenol
products.
PhMe2Si
R1
R1
R2
OH
SiMe2Ph
SiMe2Ph
3
4
5
(Bpin)2
[Cu]
R2
PhMe2Si
R1
Bpin
6
Scheme 1. Copper-Catalyzed Synthesis of Multi-substituted Fuanctional 2,3-
Allenols and Alkenes Using Propargyl Epoxides.
Therefore, we attempted to use copper salts as the catalysts to
test the silylation reaction of propargyl epoxides.[12] Firstly, the
propagyl epoxide 1a and silylboronate 2 were chosen for the model
reaction to optimize the reaction conditions. To our delight, the
desired product 2,3-allenol 3a could be obtained in 45% isolated
yield in the presence of 3 mol % CuCN as the catalyst and 10 mol %
diisopropylethylamine as the additive in isopropanol solution at
28 °C (Table 1, entry 1). Next, different solvents were screened, and
methanol was found to be the optimal solvent to provide the
As a class of versatile building blocks,[8] the 2,3-allenols have highest product yield (entries 2-4). It was found that other bases
been widely applied in the synthesis of complex organic molecules such as triethylamine and sodium methoxide could be used to give
and natural products such as (+)-varitriol[9] and Liatrin[10]. Among the desired product with comparable efficiency (entries 5 and 6). In
the reliable procedures for the preparation of multisubstituted addition, other copper salts such as CuCl, CuBr or CuI were less
allenols, the SN2′-type reactions between alkynyl oxiranes and efficient to catalyze this reaction (entries 7-9). Finally, increasing
the use of silylboronate 2 up to 1.5 equivalents would greatly
improve the product yield to 92% (Partial silylboronate would
decompose and form unreactive hexamethyldisilane under the
catalytic conditions which could be observed by crude 1H NMR
spectrum analysis, entry 10). The control experiments showed that
both the copper catalyst and base are crucial to make the desired
2,3-allenol product 3a (entries 11 and 12).
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mol % DIPEA in 1.2 mL MeOH at 28 °C under nitrogen atmosphere for 8 hours. [b]
Isolated yield.
Table 1. Optimization of Reaction Conditions of Copper-catalyzed Silylation
Reaction of Propargyl Epoxide 1a with PhMe2Si-Bpin.[a]
entry
Catalyst
(mol %)
Base
solvent
temp
(oC)
yield
(%)[b]
Scheme 2. Determination of Relative Configuration of Compound 3p.
With the optimized reaction conditions in hand, a range of
propargyl epoxides substrates were subjected to this copper(I)
cyanide catalysed silylation reaction. Different aryl-substituted
propargyl epoxides proceeded well to afford the corresponding 2,3-
allenols in moderate to high yields. Various functional groups such
as halides, cyano and acetal in the substrates were well tolerated.
Furthermore, when aliphatic substituted propargyl epoxide
compounds were employed, the corresponding products were also
obtained in high yields. It is noteworthy that the tetrasubstituted
allenols with anti-configuration could be afforded in high yields and
with excellent stereoselectivities. The stereochemical assignment of
the 2,3-allenol 3p was determined by NOE measurement of its
dihydrofuran derivative obtained via treatment 3p with AgNO3
(Scheme 2, please see the details in SI).[13] Other tetrasubstituted
allenols were assigned by the analogy of their 1H NMR spectrum.
1
2
CuCN (3)
CuCN (3)
CuCN (3)
CuCN (3)
CuCN (3)
CuCN (3)
CuI (3)
DIPEA
DIPEA
DIPEA
DIPEA
Et3N
isopropanol
ethylene glycol
THF
28
28
28
28
28
28
28
28
28
28
28
28
45
13
14[c]
78
69
74
16
43
25
92
9c
3
4
MeOH
5
MeOH
6
MeONa
DIPEA
DIPEA
DIPEA
DIPEA
--
MeOH
7
MeOH
8
CuBr (3)
CuCl (3)
CuCN (3)
CuCN (3)
--
MeOH
9
MeOH
10[d]
11
12
MeOH
MeOH
DIPEA
MeOH
--e
[a] Unless noted otherwise, the reaction was conducted with 1a (0.2 mmol), 2 (0.21
mmol, 1.05 equiv), copper catalyst (0.006 mmol, 3 mol %) and base (0.02 mmol, 10
mol %) in solvent (1.2 mL) for 8 h at 28 °C under nitrogen atmosphere. [b] Isolated
yield. [c] 1H NMR yield. [d] The silylboronate 2 was used as 1.5 equivalents. [e] No
reaction.
Chart 2. Copper-catalyzed Disilylation of Propargyl Epoxides for the
Synthesis of Tetrasubstituted Alkenes with PhMe2Si−Bpin. [a,c]
SiPhMe2
CuCN (10 mol %)
K2CO3 (10 mol %)
Chart 1. Synthesis of 2,3-Allenols Using Propargyl Epoxide Substrates and
PhMe2Si-Bpin.[a,b]
O
PhMe2Si-Bpin
+
R
R
DMF, N2, 0 °C, 14 h
R3
SiPhMe2
CuCN (3 mol %)
DIPEA (10 mol %)
R2
OH
PhMe2Si
R1
4
1
2
O
R1
+
PhMe2Si-Bpin
MeOH, N2, 28 °C, 8h
R2
SiPhMe2
SiPhMe2
SiPhMe2
Me SiPhMe2
R3
3
2
1
OH
PhMe2Si
SiPhMe2
SiPhMe2
(77%)
OH
PhMe2Si
OH
PhMe2Si
Me
H
H
4a
4d
4b (71%)
4c (67%)
H
SiPhMe2
SiPhMe2
SiPhMe2
nBu
Me
3c (87%)
PhMe2Si
3b
PhMe2Si
(84%)
3a (92%)
PhMe2Si
OH
OH
OH
OH
SiPhMe2
SiPhMe2
SiPhMe2
(77%)
OH
nBu
F
Cl
H
4e
(71%)
4f (70%)
H
Me
SiPhMe2
SiPhMe2
SiPhMe2
Ph
3d (83%)
3e (66%)
PhMe2Si
3f (60%)
SiPhMe2
NC
SiPhMe2
SiPhMe2
OH
OH
OH
PhMe2Si
PhMe2Si
Ph
Ph
4g (65%)b
SiPhMe2
Cl
b
4i
(67%)
SiPhMe2
4h
(75%)
H
H
H
H
Cl
SiPhMe2
Cl
F
3g (76%)
PhMe2Si
3h (68%)
PhMe2Si
3i (66%)
PhMe2Si
SiPhMe2
SiPhMe2
SiPhMe2
(35%)
OH
b
4j (
68%)
4k
(50%)
4l
H
H
[a] Reaction was run under the following reaction conditions: 0.2 mmol epoxide 1, 0.6
mmol 2 (3.0 equiv), 10 mol % CuCN and 10 mol % K2CO3 in 1.2 mL dry DMF at 0 oC
under nitrogen atmosphere for 14 h. [b] The reaction time was 20 h. [c] Isolated yield.
3j (79%)
PhMe2Si
3k (32%)
NC
Ac
3l (51%)
PhMe2Si
OH
OH
PhMe2Si
OH
H
H
Me
H
Cl
During screening the reaction conditions for the synthesis of 2,3-
allenol 3a, minor disilylation product 4a was detected in some cases.
Given the unique performances of the disilylated alkenes in the
synthesis of organic materials and biologically active molecules,[14]
we intended to develop a practical strategy to prepare these
molecules in a highly stereodefined manner. After further careful
optimization of the reaction conditions, it was found that the
tetrasubstituted alkene product 4a with trans-configuration could
be obtained in 77% isolated yield in the presence of 10 mol % CuCN
Ph
3o (86%)
HO
3m (85%)
3n (88%)
HO
HO
PhMe2Si
PhMe2Si
PhMe2Si
nBu
Me
3p (93%)
dr = 99:1
Ph
3q (92%)
dr = 99:1
3r
(96%)
dr = 99:1
[a] Unless noted otherwise, the reaction condition was performed under the following
reaction conditions: 0.2 mmol epoxide 1, 0.3 mmol 2 (1.5 equiv), 3 mol % CuCN and 10
2 | J. Name., 2012, 00, 1-3
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as the catalyst and 10 mol % K2CO3 in DMF solution. Next, various
Control experiments were carried out to disclose the possible
aryl-substituted propargyl epoxides were tested as substrates for mechanistic pathway of the silylation reactions. The results showed
this reaction. All the desired products could be obtained in good that the disilyl-substituted alkene products 4a and 5a could be
yields and with excellent stereoselectivities. However, only 35% generated in high yields and with excellent stereoselectivities from
isolated yield of 4l was isolated when the aliphatic substituted the 2,3-allenol 3a under the optimized reaction conditions
substrate was subjected to this reaction.
respectively (Scheme 4, eq 1-2).
Finally, we briefly studied the copper-catalyzed silylation reaction
of propargyl aziridine. Under the optimized reaction conditions for
the synthesis of 2,3-allenols, the allenylsilane product 3s was
obtained in 98% yield (Scheme 5, eq 3). Furthermore, the boryl-
silyl-substituted alkenes 6a and 6b could be obtained in high yields
and with moderate stereoselectivities by using B2pin2 under the
optimized reaction conditions for the synthesis of olefin product 4
(Scheme 5, eqs 4 and 5).
Inspired by the observed results, we proposed that the
tetrasubstituted alkene 4 should be generated from the 2,3-allenol
via selective silylcupration of the allenic double bond and β-
hydroxyl elimination processes. Therefore, we hypothesized
whether it was possible to get another silyl-substituted alkene
product 5 via tuning the silylcupration to the other allenic double
bond (Scheme 3). We proposed that rapid protonation step could
favor the formation of the desired product. After careful screening
the reaction conditions, the desired product 5a was obtained in 83%
yield as the major stereoisomer by using 1-pentanol as the solvent
(chart 3). Moreover, other aryl groups substituted propargyl
epoxides could afford the corresponding products in moderate to
high yields and with good stereoselectivities. Unfortunately, no
desired product could be accessible when the aliphatic substituted
substrate was tested in this reaction.
Scheme 4. Control Experiments to Explore the Possible Reaction Pathways.
Scheme 3. Design of Regio- and Stereoselective Silylcupration of 2,3-Allenol.
Chart 3. Copper-catalyzed Disilylation of Propargyl Epoxides for the
Synthesis of Trisubstituted Alkenes with PhMe2Si−Bpin. [a,b]
Scheme 5. Copper-Catalyzed Silylation or Boronation of Propargyl Aziridine
and 2,3-Allenols.
[a] Reaction was run under the following reaction conditions: 0.2 mmol epoxide 1, 0.6
mmol 2 (3.0 equiv), 5 mol % CuCN and 10 mol % K2CO3 in 1.2 mL 1-pentanol at 60 oC
under nitrogen atmosphere for 11 h. [b] Isolated yield.
Scheme 6. Proposed Plausible Mechanism for the Copper-Catalyzed
Hydrosilylation of Propargyl Epoxides.
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Alkynes, Patai’s Chemistry of Functional Groups, Wiley: New
York, 2009
Recently, an elegant work on the synthesis of highly
stereodefined alkenes from allenals was developed by Ma’s
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A
plausible mechanistic pathway of CuCN catalyzed
.
hydrosilylation reaction of propargyl epoxides was depicted as in
5
6
Scheme 6.[15] First,
a [Cu]-Si species I was generated from
silylboronate 2 in the presence of CuCN as catalyst and base as
additive, followed by coordinating with the triple bond of propargyl
epoxide 1 to generate the intermediate II. After addition, an
alkoxycopper species III generated in situ would be protonated by
MeOH to give the desired 2,3-allenol product 3. The released
CuOMe as catalyst (IV) would be involved into next catalytic cycle.
7
8
M. Wang, Z.-L. Liu, X. Zhang, P.-P. Tian, Y.-H. Xu, T.-P. Loh, J.
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In conclusion, a copper-catalyzed silylation reaction of propargyl
epoxides was developed. In this work, the multifunctionalized 2,3-
allenols and stereodefined tri- and tetrasubstituted alkenes could
be selectively obtained in good yields under mild reaction
conditions. Moreover, the useful boryl- and silyl-substituted alkenes
could also be achieved via the derivation of 2,3-allenols obtained in
this approach. Therefore, current work provides a simple and
practical method to prepare multifunctionalized 2,3-allenols and
stereodefined alkenes.
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We gratefully acknowledge the funding support of the National
Natural Science Foundation of China (21672198), the State Key
Laboratory of Elemento-organic Chemistry Nankai University
(201620), the Open Project of Key Laboratory of Organosilicon
Chemistry and Material Technology of Ministry of Education,
Hangzhou Normal University (2017110) and Singapore Ministry of
Education Academic Research Fund (RG111/16) for financial
support.
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4 | J. Name., 2012, 00, 1-3
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