Catalytic Selective Dihydrosilylation of Internal Alkynes Enabled by Rare-Earth Ate Complex

Article abstract of DOI:10.1002/anie.201913773

Hydrosilylation of alkynes generally yield vinylsilanes, which are inert to the further hydrosilylation because of the steric effects. Reported here is the first successful dihydrosilylation of aryl- and silyl-substituted internal alkynes enabled by a rare-earth ate complex to yield geminal bis- and tris(silanes), respectively. The lanthanum bis(amido) ate complex supported by an ene-diamido ligand proved to be the ideal catalyst for this unprecedented transformation, while the same series of yttrium and samarium alkyl and samarium bis(amido) ate complexes exhibited poor activity and selectivity, indicating significant effects of the ionic size and ate structure of the rare-earth catalysts.

Full text of DOI:10.1002/anie.201913773

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Accepted Article
Title: Catalytic Selective Dihydrosilylation of Internal Alkynes Enabled
by Rare-Earth Ate Complex
Authors: Wufeng Chen, Haibin Song, Jianfeng Li, and Chunming Cui
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Angewandte Chemie International Edition
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COMMUNICATION
Catalytic Selective Dihydrosilylation of Internal Alkynes Enabled
by Rare-Earth Ate Complex
[a]
[a]
[a]
[a,b]
Wufeng Chen, Haibin Song, Jianfeng Li* and Chunming Cui*
Abstract: Hydrosilylation of alkynes generally yielded vinylsilanes,
which are generally inert to the further hydrosilylation because of the
steric effects. We report here the first successful dihydrosilylation of
aryl- and silyl-substituted internal alkynes enabled by a rare-earth ate
complex to yield geminal bis and tris(silanes), respectively. The
lanthanum bis(amido) ate complex supported by an ene-diamido
ligand proved to be the ideal catalyst for this unprecedented
transformation, while the same series of yttrium and samarium alkyl
and samarium bis(amido) ate complexes exhibited poor activity and
selectivity, indicating the significant effects of the ionic size and ate
structure of the rare-earth catalysts.
acidity of rare-earth ions.[10b] These unique transformations
prompted us to investigate the possibility of dihydrosilylation of
alkynes with rare-earth complexes as catalysts.
Herein, we report on the first successful dihydrosilylation of
internal alkynes with an ene-diamido lanthanum ate complex as
catalyst to produce geminal bis and tris(silanes) (Scheme 1). It
was found that this ate complex with the large size of lanthanum
ion is crucial for the realization of the challenging transformation.
Organosilanes are indispensable intermediates in synthesis of
valuable silicon materials both in industry and academia.[1] Among
them, geminal bis and tris(silanes) featuring (R
Si) C moieties are one of the most important multifunctional
synthons because of their unique structures.
3 2
Si) C and
(
R
3
3
[2,3]
However, the
efficient synthesis of these classes of silanes is still a challenge.[
Despite of several available catalytic protocols, such as insertion
of carbene into disilanes, C–Si coupling of geminal bis(bromides)
and hydrosilylation of vinylsilanes, for synthesis of geminal
bis(silanes), they still suffered from very limited substrate scopes
and low efficiency.[5-7] Catalytic dihydrosilylation of alkynes may
present the most atom-economic and straight-forward strategy for
synthesis of geminal bis(silanes). Although catalytic
4]
Scheme 1. Catalytic dihydrosilylation of internal alkynes.
hydrosilylation of alkynes have been extensively studied for
synthesis of vinylsilanes,[8] dihydrosilylation of alkynes has been
rarely studied because of the difficulty in the hydrosilylation of the
resulting vinylsilanes as well as the control of the two-step
regioselectivity (Scheme 1). In particular, hydrosilylation of
internal alkynes using transition metal and main group metal
catalysts could yield trisubstituted vinylsilanes, which are
generally inert to further hydrosilylation due to the steric effects.[8]
Very recently, Zhu et al. demonstrated catalytic dihydrosilylation
of aliphatic terminal alkynes with primary silanes enabled by 2,9-
In the course of the investigation of rare-earth-catalysed
hydrosilylation reactions, we observed that a samarium alkyl
complex bearing a bulky ene-diamdio ligand partly enabled
dihydrosilylation of 1-propynylbenzene, and the reaction also
yielded a significant amount of side products (Table 1, entry 2). In
order to achieve satisfactory dihydrosilylation, we decided to
investigate the main factors that control the selectivity and activity.
In the first place, the effects of the ionic radii of rare-earth ions
were considered. Thus, the synthesis of lanthanum complexes
was conducted.
diaryl-1,10-phenanthroline-FeCl
2
complex in the presence of
EtMgBr.[9] However, to the best of our knowledge there are no
The lanthanum iodide LLaI(THF)
Ar = 2,6-iPr ) was prepared in 60% yield by the three-
component reaction of the α-diimine, LaI (THF) and two
equivalents of sodium in THF (Scheme 2). The reaction of 1 with
one and two equivalents of KN(SiMe in n-hexane afforded
lanthanum amido complex LLaN(SiMe (THF) (2) and bis(amido)
ate complex KLLa(N(SiMe (3) in 65% and 72% yields,
2
(1, L = ArNC(Me)C(Me)NAr,
2
6 3
C H
catalysts that have been reported to catalyse dihydrosilylation of
internal alkynes.
We have recently shown that rare-earth complexes are
powerful catalysts for regioselective hydrosilylation of alkenes.[10]
In particular, they could enable highly selective hydrosilylation of
trisubstituted alkenes because of the large size and high Lewis
3
4
3 2
)
3 2
)
3 2 2
) )
respectively. In the 13C NMR spectra, the resonances of the
NCCN backbone in 1 (δ 112.3 ppm) and 2 (δ 112.3 ppm) are
slightly up-field shifted compared to that in 3 (δ 115.3 ppm),
[
a]
b]
W. Chen, Dr. H. Song, Dr. J. Li, Prof. Dr. C. Cui
State Key Laboratory of Elemento-Organic Chemistry and College
of Chemistry, Nankai University, Tianjin 300071, China
E-mail: lijf@nankai.edu.cn, cmcui@nankai.edu.cn
Prof. Dr. C. Cui
3+
indicating the π bonding between La ion and the C=C double
[11,12]
bond in 1 and 2.
X-ray diffraction studies disclosed that
complex 2 is monomeric (Figure S1 in Supporting Information)
while the ate complex 3 features a polymeric structure in the solid
[
Collaborative Innovation Center of Chemical Science and
Engineering (Tianjin), Tianjin 300072, China
]− anion is linked by
state (Figure 1), in which the [LLa(N(SiMe ) )
3 2 2
potassium ion via π interactions to the two aryl groups in the
neighbouring two units. The structural analysis of 3 revealed that
Supporting information for this article is given via a link at the end of
the document.
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Angewandte Chemie International Edition
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COMMUNICATION
each La atom is four-coordinate with a distorted tetrahedral
geometry. The bond lengths of La1–N3 and La1–N4 (2.448(3)
and 2.447(3) Å) in 3 are noticeably longer than those in the four-
coordinate lanthanum bis(amido) complexes (La−N ranging from
3) only led to the formation of monohydrosilylation product 6a in a
low yield. To our delight, lanthanum ate complex 3 (entry 4) could
enable highly efficient and selective dihydrosilylation reaction,
leading to the clean formation of 8a in 98% yield in 4 hours. These
results indicated that the ate structure might be crucial for the high
efficiency and selectivity. Thus, the similar samarium ate complex
2
.374 to 2.414 Å) and that in 2 (2.411(8) Å).[13] The C1−C2 bond
length of 1.343(3) Å in 3 is very close to the corresponding bond
length (1.339(2) Å) in the free ene-diamine LH
.[14] In addition, the
2
KLSm(N(SiMe
also synthesized and examined for the model reaction under the
similar conditions. However, KSmN (entry 5) was found to be
3 2 2
2
) ) (KSmN , see Supporting Information) was
long distances (3.274 and 3.275 Å) of the La atom to the carbon
atoms in the NCCN backbone disclosed the absence of π
interactions. In contrast, complex 2 features a σ ,π-coordination
mode as indicated by the short La–C distances (av. 2.790 Å).[11b]
2
2
much less selective and the reaction still led to ca. 25% of side
products.
Table 1. Reaction condition optimization of rare-earth-catalysed
dihydrosilylation of 1-propynylbenzene.[
a]
time
h)
T
(°C)
conv.
(%)[
entry
cat.[b]
solvent
6a/7a/8a/8a’[c]
c]
(
1
2
3
4
5
6
7
8
9
YC
toluene
toluene
toluene
toluene
toluene
toluene
n-hexane
THF
24
24
24
4
80
80
80
80
80
40
40
40
80
75
100/0/0/0
22/1/69/8
100/0/0/0
0/2/98/0
Scheme 2. Synthesis of lanthanum complexes 1−3.
SmC
100
30
2
3
100
100
100
100
70
KSmN
2
4
17/8/75/0
55/1/44/0
69/1/30/0
100/0/0/0
100/0/0/0
3
3
3
3
4
4
4
THF
4
100
[
a] Reaction conditions: n
mmol), catalyst (0.012 mmol,
LYCH SiMe (THF) SmC
KLSm(N(SiMe
C
6
H
13SiH
3
4a (1 mmol), 1-propynylbenzene 5a (0.4
3
mol%), 0.6 mL solvent. [b] YC
LSmCH SiMe (THF) KSmN
=
=
2
3
2
,
=
2
3
2
,
2
Figure 1. Molecular structure of complex 3 with 30% ellipsoid probability.
Hydrogen atoms and iPr groups have been omitted for clarity. Selected bond
lengths (Å) and angles (°): La1−N1 2.423(3), La1−N2 2.417(3), La1−N3
3
1
)
)
2 2
. [c] Conversion of alkyne and ratio of products were
determined by H NMR and GC-MS with the crude mixture.
2
.448(3), La1−N4 2.447(3), N1−C1 1.438(5), N2−C2 1.433(5), C1−C2 1.343(5),
We also investigated the effects of temperature and solvents
on the dihydrosilylation reaction with 3 as catalyst. Lowing the
reaction temperature from 80 to 40 °C (Table 1, entry 6) mainly
led to monohydrosilylation product 6a, indicating the significant
temperature effects on the reaction efficiency. The reaction in n-
hexane (entry 7) mostly resulted in monohydrosilylation product
with only ca. 30% dihydrosilylation product probably due to the
relatively poor solubility of catalyst 3 in n-hexane. In sharp
contrast, the reactions in THF (entries 8 and 9) only yielded the
monohydrosilylation product 6a probably due to the interactions
of the solvent molecules to the lanthanum ion, which suppress the
coordination-insertion process.
N1−La1−N2 70.14(11), N3−La1−N4 115.14(12).
With the lanthanum complexes 2 and 3 in hand, we investigated
their applications for catalytic dihydrosilylation of internal alkynes.
For comparison, the same series of alkyl complexes
LYCH
also examined.[
propynylbenzene 5a with two equivalents of n-hexylsilane 4a was
selected as the model reaction for the optimization of catalysts.
The results are shown in Table 1. The yttrium alkyl YC catalyst
2
SiMe
3
(THF)
2
(YC) and LSmCH
2
3 2
SiMe (THF) (SmC) were
15,10b]
The catalytic dihydrosilylation of 1-
(
Table 1, entry 1) could only afford the monohydrosilylation
Under the optimized conditions (Table 1, entry 4), reactions of
product 6a with an excess of the hydrosilane. Hydrosilylation with
SmC (entry 2) could yield the dihydrosilylation product 8a, but
monohydrosilylation product 6a, hydrogenation product 7a and
dihydrosilylation isomer 8a’ were also generated in ca. 31% yield.
Under the same conditions, the neutral lanthanum amide 2 (entry
n
n
6 3 8 3
ca. two equivalents of hydrosilanes ( C H13SiH and C H17SiH )
with various internal alkynes were examined with 3 mol% of 3 as
catalyst in toluene. As shown in Table 2, all of the internal alkynes
5a–s can undergo highly efficient dihydrosilylation to afford
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Angewandte Chemie International Edition
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COMMUNICATION
geminal bis and tris(silanes) products 8a–s in good to excellent
proceed under the similar condition. The gram scale reactions
were conducted to demonstrate potential practicality of this
catalytic reaction (Scheme S1 in Supporting Information).
yields, and other hydrosilylation products were not detectable by
NMR and GC-MS spectroscopy. Both of the RH Si groups are
2
regioselectively added to the same carbon bonded to aryl and silyl
groups. The regioselectivity of the aryl-substituted alkynes is due
3
to the ƞ coordination mode of the aromatic fragment to the rare-
earth ion,[16] whereas that of silyl-substituted alkynes could be
attributed to the polarized Si–C bond, in which the -carbon atom
with higher electron density tends to bond with the rare-earth
ion.[17] The catalytic protocol could tolerate amino (8c), alkoxy
(
8d–f, 8n and 8s), fluoro (8g), arylsilyl (8o) and alkylsilyl (8p–s)
groups. Dihydrosilylation of alkynes featuring a long alkyl chain
8j, 8k, 8m, 8n, 8q and 8s), cyclohexyl (8l) and cyclopropyl (8r)
(
groups yielded the dihydrosilylation products smoothly in good to
excellent yields. For the methoxyphenyl-substituted alkynes, the
o-OMe substituent (8f) resulted in much more rapid
dihydrosilylation than the m- and p-OMe ones (8e and 8d).[18]
Table 2. Dihydrosilylation of internal alkynes catalysed by 3.[a]
Scheme 3. Synthesis of dinuclear lanthanum hydride ate complex 10.
9
10
Figure 2. Molecular structures of complexes 9 and 10 with 30% ellipsoid
probability. Hydrogen atoms except those on lanthanum atoms and iPr groups
have been omitted for clarity. Selected bond lengths (Å) and angles (°): La1−H
2.44(9), La1−Ha 2.35(9), La2−H 2.28(8), La2−Ha 2.31(9), La2−Hb 1.7(2),
La1−N1 2.490(8), La1−N2 2.399(6), La1−N3 2.408(7), La2−N4 2.356(7),
La2−N5 2.377(7), La2−C1 2.701(12), C8−C9 1.350(14), C36−C37 1.370(12),
H−La1−Ha 61(3), H−La2−Ha 64(3), Ha−La2−Hb 66(8), N2−La1−N3 74.3(2),
N4−La2−N5 75.1(2), N1−La1−N2 115.7(3), C1−La2−N4 133.5(4).
To obtain the possible intermediates in the catalytic cycle, the
stoichiometric reactions of neutral lanthanum amide 2 and ate
n
complex 3 with C
6
H13SiH
3
were investigated. The reaction of 3
with 1.5 equivalents of the silane in toluene at room temperature
gave the dinuclear lanthanum hydride ate complex KLLa(μ-H) [μ-
N(SiMe )Me SiCH ]La(THF)LK (10) as red crystals in high yield
82%, Scheme 3). However, an excess of nC
led to a
2
3
2
2
(
6 3
H13SiH
complicated mixture. In sharp contrast, no reaction was observed
n
between 2 and C
6
H13SiH
3
even at 80 °C . The characteristic low-
a] Reaction conditions: hydrosilane 4 (1 mmol, R = n
alkyne 5 (0.4 mmol), catalyst 3 (0.012 mmol, 3 mol%), 80 °C and 0.6 mL
toluene. The yield is isolated yield of 8.
13, R’ = n
8
C H17),
field shift of La-H resonance in 10 was observed as a singlet at δ
7.72 ppm in 1H NMR spectrum.[19] The diagnostic methylene
protons in N(SiMe )Me SiCH group exhibit one singlet at δ −0.47
[
C
6
H
3
2
2
ppm. In addition, two singlets at δ 0.66 and 0.56 ppm were
attributed to SiMe and SiMe , respectively. The IR spectrum of
0 shows a moderate stretching vibration band for La−H at 1112
Notably, silyl-substituted alkynes also work efficiently and
selectively to give geminal tris(silanes) exclusively in good yields
2
3
1
(
Table 2). To the best of our knowledge, this reaction represents
−
1
cm , which is similar to that in bis(pentamethylcyclopentadienyl)
the first catalytic approach for the efficient and selective synthesis
of geminal tris(silanes). However, dihydrosilylation with the
secondary silanes such as Ph SiH and PhMeSiH could not
2 2 2
−
1 [19a]
lanthanum hydride (1120 cm ).
The structure of 10 was
determined by X-ray single crystal analysis (Figure 2). The two
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Angewandte Chemie International Edition
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COMMUNICATION
3
+
La ions in 10 are bridged by one N(SiMe
3
)Me
2
SiCH
2
and two
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hydrido groups. The two ene-diamido ligands were bonded to the
+
53, 3078–3081; h) Y. Zhang, Q. Guo, X. Sun, J. Lu, Y. Cao, Q. Pu, Z.
Chu, L. Gao, Z. Song, Angew. Chem. Int. Ed. 2018, 57, 942–946; Angew.
Chem. 2018, 130, 954–958.
two K ions via the K-arene interactions. The La
2
H
2
skeleton is
folded with a 39° dihedral angle between the two H-La-H planes.
The La–H bond lengths are comparable to those reported for
lanthanum hydride complexes.[19b] The La2–C1 bond length
[
3]
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1552; b) C. Eaborn, J. Chem. Soc., Dalton Trans. 2001, 3397–3406; c)
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2.701(12) Å) is close to the typical distances reported for
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[
20]
lanthanum alkyl complexes (La–C from 2.510 to 2.632 Å).
It is noted that the single crystals of 10 contain a significant
amount of KL[(Me Si) N]La(μ-H) La(H)(THF)LK 9 probably due to
2
008, 130, 6060–6061.
R. J. P. Corriu, M. Granier, G. Lanneau, J. Organometal. Chem. 1998,
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3
2
2
[
21]
[4]
the low solubility of the ate complexes in organic solvents. It is
reasonable to assume that 9 is the intermediate to 10 via the
activation of the C–H bond. It was found that dissolving 9 in
toluene quickly led to the formation of 10 (Scheme 3), indicating
that 9 is not stable in solution. The structure of 9 with a terminal
La–H bond is shown in Figure 2. To the best of our knowledge, it
is the first example of structurally characterized lanthanum
complex with a terminal La–H bond. The catalytic behaviour of the
hydride 10 (95% isolated yield of 8a after 4 hours at 80 °C) was
comparable to that of 3, indicating that the catalytic cycle adopts
the generally accepted σ-bond metathesis/coordination-insertion
mechanism with the rare-earth hydride intermediates.[10,16]
5
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In summary, we have disclosed that the lanthanum bis(amido)
ate complex
3
enabled highly efficient and selective
dihydrosilylation of aryl and silyl-substituted internal alkynes,
giving geminal bis and tris(silanes), respectively, in high yields.
The high activity could be attributed to the anionic nature of the
catalyst and large lanthanum ion. Compared to the neutral amide
complexes, the ate complex 3 features the much more polarized
La–N bonds, which could facilitate the σ-bond metathesis with
hydrosilanes to form active rare-earth hydride intermediates.
Furthermore, the large lanthanum ion could provide more open
space for the coordination of sterically demanding trisubstituted
alkenes. The present results demonstrated the potentials of rare-
earth ate complexes in the activation of hydrosilanes and
sterically demanding alkenes. Further studies for the broad
catalytic applications of ene-diamido rare-earth ate complexes
are currently in progress.
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We are grateful to the National Natural Science Foundation of
China (Grant No. 21890722 and 21632006) for financial support.
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The authors declare no conflict of interest.
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Keywords: rare-earth metal • hydrosilylation • alkyne • hydride •
ate complex
[
1
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[
[
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Angewandte Chemie International Edition
10.1002/anie.201913773
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n
[
room temperature overnight could result in the formation of single
crystals of 10 and 9, but no suitable single crystals for X-ray diffraction
can been obtained in toluene.
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Angewandte Chemie International Edition
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COMMUNICATION
Wufeng Chen, Haibin Song, Jianfeng Li*
and Chunming Cui*
Page No. – Page No.
Catalytic Selective Dihydrosilylation
of Internal Alkynes Enabled by Rare-
Earth Ate Complex
Magic of big metal and polarized bond: Dihydrosilylation of aryl- and silyl-substituted
internal alkynes is successfully achieved by a lanthanum bis(amido) ate complex to yield
geminal bis and tris(silanes), respectively. The high activity could be attributed to the large
lanthanum ion and anionic nature of the catalyst.
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