Rhodium-Catalyzed Si-H Bond Insertion Reactions Using Functionalized Alkynes as Carbene Precursors

Article abstract of DOI:10.1021/acscatal.9b01187

Enantioselective transition-metal-catalyzed carbene insertion into Si-H bonds is a promising method for preparing chiral organosilicons; however, all the carbene precursors used to date in this reaction have been diazo compounds, which significantly limit

Full text of DOI:10.1021/acscatal.9b01187

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Letter
Rhodium-Catalyzed Si–H Bond Insertion Reactions
Using Functionalized Alkynes as Carbene Precursors
Ming-Yao Huang, Ji-Min Yang, Yu-Tao Zhao, and Shou-Fei Zhu
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b01187 • Publication Date (Web): 03 May 2019
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ACS Catalysis
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Rhodium-Catalyzed Si–H Bond Insertion Reactions Using
Functionalized Alkynes as Carbene Precursors
Ming-Yao Huang,§ Ji-Min Yang,§ Yu-Tao Zhao, Shou-Fei Zhu*
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State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin
300071, China
ABSTRACT: Enantioselective transition-metal-catalyzed carbene insertion into Si–H bonds is a promising method for
preparing chiral organosilicons; however, all the carbene precursors used to date in this reaction have been diazo compounds,
which significantly limits the structural diversity of the resulting chiral organosilicons. Herein, we report a protocol for
rhodium-catalyzed asymmetric Si–H bond insertion reactions that use functionalized alkynes as carbene precursors. With
chiral dirhodium tetracarboxylates as catalysts, the reactions of carbonyl-ene-ynes and silanes smoothly gave chiral
organosilanes in high yields (up to 98%) with excellent enantioselectivity (up to 98% ee). Kinetic studies suggest that
insertion of the in situ generated rhodium carbenes into the Si–H bonds of the silanes is probably the rate-determining step.
This work represents the first enantioselective Si–H bond insertion reaction using alkynes as carbene precursors and opens
the door for preparing chiral organosilicons with unprecedented structural diversity from readily available alkynes.
KEYWORDS: Asymmetric synthesis, chiral organosilicons, rhodium carbenes, Si–H bond insertion, alkynes
Organosilicon compounds have broad applications in the
fields of materials science,1a agricultural chemistry,1b
pharmaceutical chemistry,1c and organic synthesis.1d–1f The
preparation of structurally diverse chiral organosilicon
compounds can be expected to increase the utility of these
compounds, and various asymmetric catalytic approaches
have been developed for this purpose. Typical methods
include desymmetrization of silanes,2 asymmetric
hydrosilylation,3 and asymmetric silyl conjugated addition.4
Enantioselective transition-metal-catalyzed insertion of
carbenes into the Si–H bond of silanes is another
straightforward route to organosilicon compounds with α-
chiral centers.5 Since Doyle and Moody’s seminal work on
rhodium-catalyzed asymmetric Si–H bond insertion
reactions with diazo compounds as carbene precursors in
1996,5b extensive studies have revealed that chiral catalysts
based on rhodium,5b–5e copper,5f,5g iridium,5h,5i ruthenium,5j
iron,5k and even enzymes generated by directed evolution5l
can afford good, high or excellent enantioselectivity in this
reaction. However, despite significant progress, the carbene
precursors used in asymmetric Si–H bond insertion
reactions are strictly limited to stabilized diazo compounds,
and therefore the structural diversity of the resulting chiral
organosilicon compounds is poor. Recently, alkynes have
emerged as promising carbene precursors when activated
by π-acidic transition-metal catalysts, and alkynes have
been successfully used for an increasing number of
carbene-transfer reactions,6 including some asymmetric
versions.7 Compared to diazo compounds,8 alkynes are safe
and readily accessible and can be used to generate carbenes
with better structural diversity because there is no
particular need for stabilization.
unknown to the best of our knowledge. Herein, we report a
highly enantioselective rhodium-catalyzed Si–H bond
insertion reaction that uses alkynes as carbene precursors.
In the presence of chiral dirhodium tetracarboxylate
catalysts, asymmetric Si–H bond insertion reactions of
carbenes generated in situ from carbonyl-ene-ynes
smoothly gave furan-2-ylmethylsilanes in high yields with
excellent enantioselectivities.
We began by exploring the reaction of carbonyl-ene-yne
1a with tributylsilane 2a in the presence of dirhodium
tetracarboxylates 3 (1 mol %) in 1,2-dichloroethene (DCE)
at 25 °C. (Table 1). All of the tested dirhodium
tetracarboxylates promoted the reaction and gave high
yields of desired product 4aa (entries 1–8); however, the
enantioselectivity depended strongly on the nature of the
chiral ligand. Rh2(S-DOSP)4, which has N-sulfonylprolinate
ligands,10 gave a racemic product (entry 1); and Rh2(S-
PTPA)4, Rh2(R-PTAD)4, Rh2(S-PTTL)4, Rh2(S-tertPTTL)4,
Rh2(S-TBPTTL)4, and Rh2(S-NTTL)4, which have imide-type
ligands,11 gave low to moderate enantioselectivities (entries
2–7). Rh2(R-BTPCP)4, which has triarylcyclopropane
carboxylate ligands,12 exhibited the best enantioselectivity
(90% ee), but the reaction was relatively slow (entry 8). In
addition to DCE, CH2Cl2, CHCl3, chlorobenzene, and toluene
were suitable solvents (entries 9–12). In contrast, a reaction
performed in THF, a coordinative solvent, failed to give the
desired product (entry 13). The enantioselectivity could be
improved to 96% ee by decreasing the reaction
temperature to 0 °C (entry 14).
Although there have been several reports of Si–H bond
insertion reactions using alkynes as carbene precursors,9
the enantioselective version of this reaction remains
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Page 2 of 7
Table 1. Rhodium-catalyzed Asymmetric Si–H Bond
complex mixtures containing none of the desired Si–H bond
insertion product (entries 8 and 9). The disubstituted silane
H2SiPh2 could be used as a Si–H donor, but the yield and ee
value were only modest (entry 10). The monosubstituted
silane H3SiPh gave a messy result with only a trace of the
desired product (entry 11). To sum up, the reactivity of the
silanes was strongly related to their steric bulk as well as
their electronic properties: less bulky silanes and silanes
with electron-rich Si atoms generally exhibited better
results.
Insertion Reaction of Alkynes with Silane HSinBu3:
Optimization of Reaction Conditions a
1
2
3
4
5
6
7
8
SinBu3
Ph
O
O
Me
O
1 mol % [Rh]
solvent, 25 o
Me
O

Ph
HSinBu3
(2 equiv)
+
C
Me
Me
1a
2a
4aa
O
O
Rh
Rh
Bn
N
O
O
Rh
Rh
N
O
Rh
9
O
4
O
S O
O
Table 2. Rhodium-catalyzed Asymmetric Si–H Bond
Insertion Reactions of Alkyne 1a and Various Silanes a
4
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O
Rh
4
N
O
O
C12H25
Ph
[Si]
3c
, Rh2(R-PTAD)4
3b
3a
, Rh2(S-PTPA)4
, Rh2(S-DOSP)4
O
O
Me
O
3h
1 mol %
Me
O
tBu
Ph
tBu
N
O
O
Rh
Rh
*
O
O
Rh
Rh
H-[Si]
(2 equiv)
Ph
Ph
+
O
O
Rh
Rh
DCE, 0 o
C
O
O
N
4
4
Me
4
X
X
O
Me
1a
O
4
2
X
Y
Br
, Rh2(R-BTPCP)4
entry H-[Si]
t (h) yield (%)b
ee (%)c
3g
, Rh2(S-NTTL)4
3h
3d,
X = Y = H, Rh2(S-PTTL)4
t
3e
, X = H, Y = Bu, Rh2(S-tertPTTL)4
1
2
HSinBu3 (2a)
HSinPr3 (2b)
20
20
20
24
10
24
24
92
87
96
95
3f
, X = Y = Br, Rh2(S-TBPTTL)4
entry
1
[Rh]
3a
3b
3c
solvent
DCE
t (h) yield (%)b
eec
0
3
HSiEt3 (2c)
HSiiPr3 (2d)
85
92
N.A. d
2
2
92
90
4
trace
94
2
DCE
12
32
13
22
12
59
90
86
77
83
84
--
5
HSiMe2Ph (2e)
HSiPh3 (2f)
88
3
DCE
2
91
4
3d
3e
DCE
4
94
6
7
92
7e
8e
9e
10e
11e
HSiMe2OEt (2g)
65
85 (S) f
N.A.
N.A.
56
5
DCE
4
92
6
3f
DCE
4
83
HSiMe(OEt)2 (2h) 24
N.D. g
N.D.
38
7
3g
3h
3h
3h
3h
3h
3h
3h
DCE
4
71
HSi(OEt)3 (2i)
H2SiPh2 (2j)
H3SiPh (2k)
24
20
20
8
DCE
10
10
10
10
10
10
20
92
9
CH2Cl2
CHCl3
PhCl
90
trace
N.A.
10
11
12
13
14e
92
a Reaction conditions: 3h/1a/2 = 0.002:0.2:0.4 (mmol), in 2 mL
88
b
c
DCE at 0 °C. Isolated yield. The ee values were determined
d
e
f
toluene
THF
89
N.D.d
by HPLC. N.A. = not analyzed. Performed at 25 °C. The
absolute configuration was determined by oxidation of 4ag to
corresponding chiral alcohol and comparison of the specific
rotation of the alcohol with the literature value.7h See
supporting information (SI) for details. g N.D. = not detected.
DCE
92
96
a Reaction conditions: 3/1a/2a = 0.002:0.2:0.4 (mmol), in
b
c
2 mL solvent.
Isolated yield.
The ee values were
determined by HPLC. d N.D. = not detected. e Performed at 0
°C.
The substrate scope of the reaction with respect to the
carbonyl-ene-yne (1) was then investigated (Scheme 1).
Generally, reactions of aryl-terminated carbonyl-ene-ynes
(R3 = aryl) performed well with catalysis by Rh2(R-BTPCP)4
whereas the alkyl- or alkenyl- terminated substrates (R3 =
alkyl or alkenyl) not (see SI for details). The aryl-terminated
carbonyl-ene-ynes could bear a variety of substituents at
different position of the aryl ring (4ba–4ja). Substrates
with para electron-donating groups showed better
enantioselectivity (4ba–4ca) than substrates with para
electron-withdrawing groups or a para phenyl group (4da,
4ea, 4fa). In addition to a substituted phenyl ring, R3 could
also be a fused-ring moiety (4ka, 4la) or a heteroaromatic
ring (4ma). In addition to an acetyl group (4aa–4ma), R2
could be a propionyl group (4na), an ester (4oa), a sulfonyl
group (4pa), or a benzoyl group (4qa). However, reaction
of the benzoyl substrate required the use of Rh2(S-
Various silanes were then evaluated in the Si–H bond
insertion reaction with carbonyl-ene-yne 1a to give
insertion products 4 (Table 2). Less sterically hindered
trialkylsilanes HSinBu3, HSinPr3, and HSiEt3 afforded good
results, although the enantioselectivity slightly decreased
as the length of the alkyl chain decreased (entries 1–3). In
contrast, the bulky trialkylsilane HSiiPr3 was essentially
inactive (entry 4). The reaction with a phenyl silane
HSiMe2Ph gave the desired product in high yield with good
enantioselectivity (entry 5). As was the case for the
trialkylsilane series, the bulkier phenyl silane HSiPh3
showed a lower yield than the less bulky silane HSiMe2Ph,
but good enantioselectivity was retained (entry 6).
Introduction of alkoxyl substituents to the silane
substantially
decreased
its
reactivity:
the
tertPTTL)4 instead of Rh2(R-BTPCP)4 to achieve
a
monoalkoxylsilane HSiMe2OEt gave a moderate yield and
good enantioselectivity (entry 7), whereas the di- and
trialkoxylsilanes HSiMe(OEt)2 and HSi(OEt)3 gave only
satisfactory outcome. Similarly, when R3 was changed from
an aryl group to an alkyl group (4re, 4se, 4te) or a
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ACS Catalysis
cyclohexenyl group (4ue), good results could be obtained
by using Rh2(S-tertPTTL)4 as a catalyst and HSiMe2Ph as the
Si–H bond donor. The Si–H bond insertion reactions of two
substrates with an E- or Z-cinnamnyl group at R3 also
afforded satisfactory results (4ve and 4we) when Rh2(S-
NTTL)4 and Rh2(S-TBPTTL)4, respectively, were used as
catalysts.
To shed light on the reaction mechanism, we carried out
some in situ IR experiments using the Rh2(R-BTPCP)4-
catalyzed reaction of 1a with 2a and deuterated 2a as
models (Scheme 3). In the name of efficiency, the reactions
were performed at 40 °C so that they were complete within
5 h. Competitive experiments carried out with equimolar
amounts of 2a and 2a-d, either 1.0 or 2.0 equivalents each,
in the same pot afforded identical kH/kD values (1.5, Scheme
3a); and parallel experiments with 2a or 2a-d afforded a
similar value (1.4, Scheme 3b). By analogy with Si–H bond
insertion reactions involving diazo compounds,14 the small
but significant kinetic isotope effect observed in these
experiments imply that Si–H bond cleavage is slow. To
verify this implication, we carried out some kinetics
experiments at various initial concentrations of carbonyl-
ene-yne substrate 1a, silane 2a, and catalyst 3h (Scheme
3c). By tracking the time courses of the concentration of 1a
as the initial concentrations of the three components were
varied independently, we could calculate the initial rates of
reaction of the components and determine the reaction
orders with respect to each of the components. These
results revealed that the initial reaction was first order with
respect to the dirhodium catalyst and the silane and zeroth
order with respect to the substrate 1a. These values result
in a rate equation of r = k[3h][2a], which confirms that Si–
H bond insertion process was most likely the rate-
determining step.
1
2
3
4
5
6
Scheme 1. Rhodium-catalyzed Asymmetric Si–H Bond
Insertion Reactions of Carbonyl-ene-ynes 1 with Silanes
2a or 2e a
7
8
9
10
11
12
13
14
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23
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R3
H
[Si]
R3
R1
R2
O
1 mol % 3
O
R1

+
H
[Si]
DCE, 0 oC or -15 oC, 2- 20 h
2a 2e
(2 equiv)
or
R2
4
1
SinBu3
SinBu3
SinBu3
SinBu3
O
O
O
O
Me
O
Me
Me
Me




O
O
O
OMe
Me
Ph
Me
Me
Me
Me
4aab
4bab
4cab
4dab
92% yield, 96% ee
81% yield, 97% ee
89% yield, 97% ee
82% yield, 89% ee
SinBu3
O
SinBu3
SinBu3
SinBu3
O
O
O
Me
Me
Me
O
Me
O
Me
O
OMe




O
CF3
Cl
Me
Me
Me
Me
4eab
4hab
4fab
4gab
85% yield, 92% ee
84% yield, 97% ee
74% yield, 79% ee
88% yield, 98% ee
SinBu3
O
SinBu3
O
SinBu3
O
SinBu3
O
Me
Me
F
Me
Me
O
O




O
O
O
O
F
Me
Me
Me
Me
4lab
4iab
4jab
4kab
87% yield, 94% ee
Scheme 3. Kinetic Studies
84% yield, 92% ee
83% yield, 96% ee
89% yield, 97% ee
SinBu3
SinBu3
O
SinBu3
O
SinBu3
O
O
Et
O
Me
Me
Me
PhO2




S
O
O
S
Et
Me
OMe
4nab
4pab
4oab
4mab
93% yield, 94% ee
71% yield, 76% ee
86% yield, 94% ee
76% yield, 84% ee
SinBu3
SiMe2Ph
SiMe2Ph
SiMe2Ph
O
O
O
O
Ph
O
Me
O
Me
O
Me




Me
O
Ph
Me
Me
Me
4qac
4rec
4sec
4tec
97% yield, 91% ee
96% yield, 93% ee
91% yield, 91% ee
91% yield, 95% ee
SiMe2Ph
SiMe2Ph
PhMe2Si
Ph
O
O
Me
O
O
Me
O

Me
O


Ph
Me
Me
Me
4uec
4ved
82% yield, 85% ee
4wee
95% yield, 95% ee
98% yield, 92% ee
a Reaction conditions: 3/1/2 = 0.002:0.2:0.4 (mmol), in 2 mL of
DCE. Isolated yield was given. The ee values were determined
by HPLC. b Used Rh2(R-BTPCP)4 (3h) as catalyst and performed
at 0 °C. c Used Rh2(S-tertPTTL)4 (3e) as catalyst and performed
at -15 °C. d Used Rh2(S-TBPTTL)4 (3f) as catalyst and performed
at -15 °C. e Used Rh2(S-NTTL)4 (3g) as catalyst and performed
at -15 °C.
The allylic acylation13 of Si–H bond insertion product 4ue
smoothly gave the corresponding ketone 5 with good
retention of the ee value (Scheme 2). This transformation
demonstrates the potential synthetic utility of the protocol
described herein.
Scheme 2. Transformation of the Product 4ue
Me
SiMe2Ph

O
2 equiv AcCl
2 equiv AlCl3
O
O
Me
O
Me
O

DCM, 0 oC to rt, 2 h
Me
4ue
Me
5
, 64% yield, 92% ee
, 95% ee
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Page 4 of 7
a) Competitive kinetic isotopic experiments
result, the silane favors to approach carbene center from
region III and gives the insertion product with S-
configuration through a Si-face attack.
SinBu3
Ph
Ph
O
(D)H
O
1
2
3
4
5
6
7
8
HSinBu3 (x equiv)
DSinBu3 (x equiv)
Me
O
2a
2a-d
Rh2(R-BTPCP)4 (1 mol %)
Me
O
+
DCE, 40 oC, 5 h
95-96% yield
Me
1a
x = 1.0, 2.0
Me
4aa 4aa-d
Scheme 4. Proposed Mechanism and Stereoselective
Induction Model
+
kH/kD = 1.5
SinBu3
Ph
b) Parallel kinetic isotopic experiments
H
O
[Si]
Me
O
O
Me
Ph
O
H-[Si]
Re
Me
Ph
O
O
Me
O
HSinBu3 (2 equiv) 2a
Rh2(R-BTPCP)4 (1 mol %)
Me
4aa
Me
Me
+
[Rh(II)*]
Me
O
I
II
[or DSinBu3 (2 equiv)] 2a-
DCE, 40 o
kH/kD = 1.4
C
d
O
SinBu3
Ph
O
O
Rh
O
Carbene Plane
D
O
IV
Me
Me
1a
Ph
O
III
Me
9
Si
[Si]-H
or
O
RDS
H-[Si]
O
10
11
12
13
14
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16
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45
46
47
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O
Me
Me
Me
Top view of Int II
O
4aa-d
Me
O
Me
O
c) Initial rates of reactions of 1a with 2a
[Rh(II)*]
Int I
Me
Ph
O
SinBu3
Ph
Ph
[Rh(II)*]
Ph
Me
Br
Br
O
O
Int II
O
3h
)
Me
O
Rh2(R-BTPCP)4
(
O
O
HSinBu3
*
Me
O
+
Rh
O
O
O
DCE, 40 oC, 5 h
O
O
Me
Me
Me
Rh
O
2a
Me 1a
4aa
O
Br
O
1st order to silane 2a
1st order to catalyst 3h
[*(II)Rh]
Ph
Br
Side view of Int II
TS
3h 0.0005 to 0.005 M
1a 0.1 M
2a 0.2 M
3h 0.001 M
1a 0.1 M
2a 0.1 to 0.3 M
In summary, we have realized the first highly
enantioselective rhodium-catalyzed Si–H bond insertion
reactions using functionalized alkynes as carbene
precursors. Kinetics studies revealed that a Si–H bond
insertion reaction of an in situ generated rhodium carbene
is most likely the rate-determining step. Our findings reveal
that organosilicons can be prepared with high
enantioselectivity from readily accessible alkynes, and this
reaction will undoubtedly facilitate the synthesis of
structurally diverse chiral organosilicons.
0th order to alkyne 1a
3h 0.001 M
1a 0.05 to 0.15 M
2a 0.2 M
ASSOCIATED CONTENT
Supporting Information
Experimental procedures, spectral data, specific rotation and
details of in situ IR experiments. The Supporting Information is
available free of charge via the Internet at http://pubs.acs.org.
In analogy with the mechanisms of other carbene-
transfer reactions of carbonyl-ene-ynes,6 we propose that
the rhodium-catalyzed Si–H bond insertion reactions
described herein proceed via the mechanism shown in
Scheme 4. The rhodium catalyst first activates the alkyne by
acting as a Lewis π-acid (Int I) to trigger a 5-exo-dig
cyclization that forms carbene intermediate (Int II), which
undergoes a Si–H bond insertion reaction to afford the
desired product. Again, the above-described kinetics
studies indicate that the Si–H bond insertion is probably the
rate-determining step. We put forward a model to explain
the enantioselectivity of the Si–H bond insertion reaction
using Rh2(R-BTPCP)4 as a catalyst. According to the
structural studies of Rh2(R-BTPCP)4 and its carbene
intermediate by Davies et al.,12 we propose a structure of int
II, in which two opposite ligands stay in upward directions
while the other two in equatorial positions to minimize
steric repulsions between the ligands and carbene residue.
The two upward phenyl rings of ligands block region II and
IV in front of rhodium center. Because int II is a donor-
donor diaryl carbene, the more steric congested and
electron-deficient furyl ring (resulting from the methyl and
the electron-withdrawing acetyl substituents on the furyl
ring) adopts a nearly perpendicular orientation to the
carbene plane and blocks region I, whereas the less
sterically congested phenyl ring aligns coplanar to the
carbene plane to stabilize the rhodium carbene.15 As a
AUTHOR INFORMATION
Corresponding Author
* sfzhu@nankai.edu.cn
Author Contributions
§ M.-Y. Huang and J.-M. Yang contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We thank the National Natural Science Foundation of China
(21625204), the “111” project (B06005) of the Ministry of
Education of China, the National Program for Special Support
of Eminent Professionals for financial support.
DEDICATION
This paper is dedicated to the 100th anniversary of Nankai
University.
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Graphic for TOC
1 mol % [Rh(II)]
1
2
3
4
R3
+
[Si]
R3
H
R1
R2
O
O

R1
H
[Si]
0 oC or -15 oC, DCE
R2
5
up to 98% yield
up to 98% ee
6
7
8
9
tBu
O
O
Rh
Ph
Ph
O
O
Rh
Rh
O
N
Rh
4
or
[Rh(II)] =
O
4
10
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Br
Rh2(R-BTPCP)4
tBu
Rh2(S-tertPTTL)4
7
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