Selective Manganese-Catalyzed Oxidation of Hydrosilanes to Silanols under Neutral Reaction Conditions

Article abstract of DOI:10.1002/anie.201900342

The first manganese-catalyzed oxidation of organosilanes to silanols with H₂O₂ under neutral reaction conditions has been accomplished. A variety of organosilanes with alkyl, aryl, alknyl, and heterocyclic substituents were tolerated, as well as sterically hindered organosilanes. The oxidation appears to proceed by a concerted process involving a manganese hydroperoxide species. Featuring mild reaction conditions, fast oxidation, and no waste byproducts, the protocol allows a low-cost, eco-benign synthesis of both silanols and silanediols.

Full text of DOI:10.1002/anie.201900342

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Accepted Article
Title: Manganese-Catalyzed Highly Selective Oxidation of Hydrosilanes
to Silanols under Neutral Conditions
Authors: Kaikai Wang, Jimei Zhou, Yuting Jiang, Miaomiao Zhang,
Chao Wang, Dong Xue, Weijun Tang, Huamin Sun, Jianliang
Xiao, and Chaoqun Li
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10.1002/anie.201900342
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Manganese-Catalyzed Highly Selective Oxidation of Hydrosilanes
to Silanols under Neutral Conditions
Kaikai Wang[a], Jimei Zhou, Yuting Jiang[a], Miaomiao Zhang[a], Chao Wang[a], Dong Xue[a], Weijun
Tang[a], Huamin Sun[a], Jianliang Xiao[a,b], and Chaoqun Li[a]
Abstract: The first manganese-catalyzed oxidation of organosilanes
to silanols with H2O2 under neutral conditions has been
accomplished. A variety of organosilanes with alkyl, aryl, alknyl, and
heterocyclic substituents were tolerated, so were sterically hindered
organosilanes. The oxidation appears to proceed via a concerted
process involving a manganese hydroperoxide species. Featuring
mild conditions, fast oxidation and no waste byproduct, the protocol
allows for a low-cost, eco-benign synthesis of both silanols and
silandiols.
because the silanol product itself may react with the hydrosilane
(Scheme 1b).[9,1a] Whilst water is an ideal oxidant, O2 and H2O2
are also cheap and environmentally friendly in comparison with
[8]
other stoichiometric oxidants.
A few catalysts based on
Ti,[10a,10b] Re,[10c,10d] Te,[10e] and W[10f] have been explored for the
oxidation of hydrosilanes by using H2O2 or O2 as oxidant.
Disiloxanes were also formed with these catalysts, however
(Scheme 1c).[10] More recently, trifluoroacetophenone was
reported to catalyze the oxidation of hydrosilanes with H2O2,
affording a series of silanols with excellent yield and selectivity,
but requiring strictly pH-controlled buffer conditions (Scheme
1c).[11] Clearly, although transition metal-catalyzed hydrolytic
oxidation and oxidation with H2O2 now allow for the oxidation of
hydrosilane to silanols, few of the reported catalytic systems can
avoid the formation of disiloxane or other by-products. Therefore,
it remains valuable to develop a more efficient catalytic system
Silanols have found broad applications as monomers for
silicon-based polymers,[1,2] functional groups of drugs,[1,3]
directing groups for C-H functionalization,[1,4] donors for metal-
catalyzed coupling reactions,[1,5] and organocatalysts[1,6] (see
Figure S1 in Supporting Information). Whilst less bulky silanols
can be synthesized by hydrolysis of chlorosilanes under strictly
controlled conditions, it is difficult to synthesize sterically
hindered silanols, silandiols, and silanols with functional group
sensitive to hydrolytic conditions.[1,7] Silanols can also be
synthesized by oxidation of organosilanes[1a,1b] with strong
oxidants, such as silver salts,[8a] permanganate,[8b] osmium
tetroxide,[8c] dioxiranes,[8d] peracids,[8e] oxaziridines[8f] and ozone.
that features
a cheap, environment friendly catalyst and
operates under neutral conditions for the oxidation of
organosilanes to silanols.
[8g,8h]
Apart from generating stochiometric amounts of waste,
these methods are often accompanied with problems of
selectivity, e.g. producing undesired siloxanes via condensation
of two molecular silanols, or byproducts due to silanol
decomposition.[8] For example, in the oxidation of organosilanes
with permanganate, silanols and silandiols were obtained with
poor selectivity in addition to the formation of wasteful MnO2
(Scheme 1a).[8b] Furthermore, as the reaction condition is basic,
base-catalyzed rearrangement can take place.[8b] Catalytic
oxidation of Si-H bonds with a clean oxidant and high selectivity
is still a challenge.
Noble metal catalysts, e.g. those based on Rh,[9a] Cu,[9b] Re, [9c]
Ru,[9d] Pd, [9e] Ir, [9f] Au,[9g-i] and Ag, [9j,9k] have been demonstrated
to promote efficient oxidation of hydrosilanes to silanols with
hydrogen gas formation. However, such hydrolytic oxidation
cannot completely avoid the formation of disiloxane by-products,
Scheme 1. Synthesis of silanols by oxidation of hydrosilanes.
Whilst manganese-catalyzed oxidation with H2O2 of C=C and
C(sp3)-H bonds has been studied extensively, no examples of
the oxidation of organosilanes with a manganese catalyst have
ever been reported.[12] Owning to the importance of silanols and
our interest in catalytic oxidation,[13] we thought it would be
interesting to develop a more selective catalytic system based
on cheap, eco-benign manganese as catalyst and H2O2 as
oxidant for the oxidation of organosilanes (Scheme 1d). Initially,
we chose dimethyl(phenyl)silane 2a as the model substrate to
identify possible catalyst for the oxidation with H2O2 in an
acetone medium. We quickly found that the simple manganese
salt, Mn(ClO4).6H2O (5 mol%), had no catalytic activity for the
target transformation (entry 1, Table 1). The introduction of
[a]
K. K. Wang, J. M. Zhou, Y. T. Jiang, M. M. Zhang, Prof. Dr. C.
Wang, Prof. Dr. D. Xue, Prof. Dr. W. J. Tang, Prof. Dr. H. M. Sun,
Prof. Dr. J. L. Xiao, Prof. Dr. C. Q. Li
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry
of Education and School of Chemistry and Chemical Engineering,
Shaanxi Normal University, Xi’an, 710119 (China)
E-mail: lichaoqun@snnu.edu.cn
[b]
Prof. Dr. J. L. Xiao
Department of Chemistry，University of Liverpool
Liverpool, L69 7ZD, (UK)
E-mail: j.xiao@liverpool.ac.uk
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201900342
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nitrogen ligands brought about changes. Thus, on combining
bipyridine L1 (10 mol%) with Mn(ClO4).6H2O (5 mol%), silanol 3a
was formed in 6% GC yield (entry 2, Table 1). We then explored
the electronic effect of ligand by using a range of 4,4’-
disubstituted bipyridines (L1-L6) and observed, remarkably, that
the electron-rich 4,4’-diamino bipyridine L5 enabled an almost
full oxidation of 2a to 3a with no formation of the disiloxane by-
product (entries 2-7, Table 1). In sharp contrast, the electron-
deficient L3 is ineffective. The steric effect is equally critical, as
changing the ligand to 6,6’-disubstituted bipyridines brought
about little oxidation of 2a (entries 8-11, Table 1). Further
screening of other ligands as well as the combination of L5 with
other manganese or iron salts demonstrated that L5 combined
with Mn(ClO4)2 exhibits the best catalytic activity in the oxidation
of 2a with H2O2 (Table A, SI). The catalyst loading could be
lowered from 5 mol% to 1 mol% without affecting the yield of 3a
(entry 13, Table 1); but in the absence of Mn(ClO4)2, no reaction
was observed (entry 12, Table 1).
Scheme 2. Formation of
1
and its molecular structure
determined by single-crystal X-ray diffraction. Selected bond
distances: Mn01-N1, 2.179(4) Å; Mn01-N2, 2.182(4) Å; Mn01-
O6, 2.125(6) Å; Mn01-O7, 2.050(5) Å. Selected bond angles:
N1-Mn01-N1a, 117.8(2)˚; N1-Mn01-N2a, 100.47(16)˚; N1-Mn01-
N2, 74.24(16)˚; N2-Mn01-N2a, 170.0(2)˚.
Under the optimized conditions, the catalytic system proved to
be generally effective for the selective oxidation of various
hydrosilanes to silanols in a short time (Table 2). Thus, the
protocol was shown to tolerate sterically varied substituents in
substrates 2a-2c, affording the corresponding silanols 3a-3c in
high yields without byproduct formation. Both electron-donating
and electron-withdrawing phenyl substituents are suitable,
leading to the silanol products with excellent isolated yields
(Table 2, 3d-3j). Replacing the phenyl with 2-naphthyl did not
affect the efficacy of the catalysis; but the steric hindered 1-
naphthyl necessitated a longer time of 1 h to complete (3k vs 3l).
A heterocyclic thiofuran-substituted silanol was also obtained in
good yield in 1 h (3m), so were the benzyl and alkyl substituted
silanols (3n-3q). Notably, the substrate 2r with an alkynyl
functional group was well tolerated under the oxidation
Table 1. Oxidation of dimethyl(phenyl)silane with H2O2 catalyzed
by manganese catalystsa
Table 2. Scope of 1-catalyzed oxidation of hydrosilanesa
Reacting L5 with Mn(ClO4).6H2O led to the complex 1. The
structure of 1 has been determined by X-ray diffraction and
shows a severely distorted octahedral geometry (Scheme 2; see
SI for more details). The isolated 1 displayed a similar activity as
that prepared in situ (entries 13 and 14, Table 1). Further
screening led to the optimized oxidation conditions, i.e. 1 (1
mol%) being the catalyst and H2O2 (2.5 equiv.) as the oxidant in
acetone at room temperature (Table A, SI). Under such neutral
conditions, 2a was oxidized to 3a with high yield and no
formation of any disiloxane byproduct (entry 14, Table 1). It is
noted that compared with the literature reports on manganese-
catalyzed oxidation reactions, acid or base additives suppressed,
instead of promoting, the oxidation in question (Table B, SI).[12]
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conditions, affording the silanol 3r in 93% yield. However, for the
substrate 2s which contains a 4-vinyl substituent, both the
hydride and C=C double bond were oxidized, affording the
silanol 3s under the standard conditions. Furthermore, the
substrate 2t with two Si-H groups was completely oxidized to a
silandiol in excellent yield (3t). The silanol 3s with an epoxide
and 3t with two Si-OH functional groups could be used as
building blocks for material synthesis.
shown in Scheme 3, the corresponding silanols 3b and 6a were
obtained in excellent yield. Notably, this gram-scale oxidation
could be performed at a lower catalyst loading of 0.1 mol%, as
showcased by the conversion of 2b to 3b.
To gain insight into the oxidation mechanism,
a few
experiments were performed. In the absence of H2O2 but with
the reaction opened to the air, the model substrate 2a did not
undergo any oxidation in the presence of 1, with or without water
(Table B, SI). Introducing H218O (5.5 equiv.) to the reaction
under the standard conditions, 3a was obtained in 99% yield; but
no 18O-labeled silanol was observed by HRMS analysis
(Scheme 4, a). These observations indicate that molecular
oxygen or water is not the oxygen source of the silanol product.
A small but significant kinetic isotope effect, comparable to that
observed in the polyoxotungstate-catalyzed oxidation of
hydrosilanes,[10f] could be seen in the oxidation of 2a vs that of
2a-D (Scheme 4, b),[14] suggestive of the involvement of Si-H
bond scission in the turnover limiting step. To detect possible
intermediate silane species, the oxidation of 2b under the
standard conditions was monitored with in situ IR spectroscopy
by following the absorption at vSi-H = 806 cm-1 and vSi-OH = 874
cm-1. The result indicates the oxidation to be complete in 20 min,
with no other silane species being accumulated during the
oxidation (Figure S1, SI).
Table 3. Scope of 1-catalyzed oxidation of dihydrosilanesa
Geminal silandiols have found applications in silicon-based
materials,[1,2] drugs,[1,3] and organocatalysis[1,6] (Figure S1, SI).
However, the synthesis of silandiols via transition metal-
catalyzed oxidation of dihydrosilanes is usually more difficult
than that of silanols, because of the formation of disiloxanes and
incomplete oxidation products.[8-10] Our catalytic system is
effective, allowing for the oxidation of various substituted
dihydrosilanes to silandiols. Thus, under the catalysis of 1 (2
mol%) with H2O2 (5 equiv.) as oxidant in acetone, dihydro-
diphenylsilane 5a was oxidized to the silandiol 6a in 94%
isolated yield in 1 h reacction time (Table 3, 6a). Both electron-
donating and electron-withdrawing aryl substituents are suitable,
furnishing the silandiol products with excellent isolated yields
with no disiloxane formation (Table 3, 6b-6h). Replacing one of
the aryl substituents with an alkyl one did not significantly affect
the product yields (Table 3, 6i-6k). Oxidation of the less bulky
dihydro diethylsilane 5l led to the silandiol 6l, which has been
used as an organocatalyst for 1,4-addition reactions.[6]
Scheme 4. Reactions aimed to probe the oxidation mechanism.
A more revealing experiment is the oxidation of an optically
active hydrosilane (+)-2u (66% ee) with H2O2 under the catalysis
of 1 (Scheme 4, c). The reaction proceeded selectively to afford
the corresponding silanol (+)-3u in 95% isolated yield and 53%
ee. Note the high-degree retention of the configuration of silicon;
this suggests that the oxidation in question may not involve
hetero- or homo-lysis of the Si-H bond before the formation of
the silanol; rather it may proceed via a concerted process.[8,10c,
10d,10f]
Considering the observations above, we propose the
following catalytic cycle for the oxidation catalyzed by
1
(Scheme 5). Initially, 1 reacts with H2O2 to form the active
hydroperoxide A. Although highly active manganese oxo
species could be formed from A in the presence of an acid or
water, the suppressing effect of acid on the oxidation (Table B,
SI) and the lack of 18O incorporation from H218O mentioned
above indicate that a species, such as B, is not involved in the
oxidation.[15] Instead, A might react directly with the hydrosilane
via a transition state C involving concerted transfer of the silicon
and hydride to the electrophilic hydroperoxide moiety of the
manganese species to afford the siloxide D.[15,16] Protonation of
Scheme 3. Gram-scale oxidation of hydrosilanes.
To further demonstrate the synthetic utility of the 1-catalyzed
oxidation of organosilanes, the bulky triphenylsilane 2b and
diphenylsilane 4a were subjected to a gram-scale reaction. As
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D by H2O2 then generates the silanol product and the active
intermediate A, restarting the catalysis.
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Scheme 5. Proposed mechanism for the 1-catalyzed oxidation
of hydrosilanes.
In conclusion, by harnessing the remakrable catalytic
activity of the electrion-rich manganese complex 1, we have
realized the highly efficient oxidation of organosilanes to
silanols with H2O2 under neutral conditions.
A series of
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hydrosilanes and dihydrosilanes were oxidized to silanols and
silandiols, respectively, with excellent isolated yields and no
waste byproduct formation in a short reaction time. Preliminary
mechanistic studies suggest that the oxidation may proceed via
a concert reaction of a Mn(III)-OOH species with the hydrosilane.
Further investigation is in progress.
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yield of 3a-OD is due to H-D exchange with water in the system.
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[16] Following the suggestion of a reviewer, we also carried out the 1-
catalyzed oxidation of 2a using the single oxygen atom donors tBuOOH,
CH3C(O)OOH and PhIO under the optimized conditions (Table 1). The
former two oxidants afforded 99% yield (GC) of 3a; but no oxidation
was observed with PhIO (Table B, SI). These results appear to be
supportive of the concerned mechanism suggested.
Acknowledgements
We gratefully acknowledge the financial support by the
Fundamental Research Funds for the Central University
(GK201603052), start-up funds from Shaanxi Normal University,
Shaanxi Provincial Natural Science Foundation (2017JM2002),
and the Program for Changjiang Scholars and Innovative
Research Team in University (IRT_14R33), and the 111 project
(B14041).
Keywords: silanols • silandiols • hydrosilanes • catalytic
oxidation • manganese complex
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COMMUNICATION
Kaikai Wang, Jimei Zhou,Yuting
Jiang, Miaomiao Zhang, Chao Wang,
Dong Xue, Weijun Tang, Huamin Sun,
Jianliang Xiao, and Chaoqun Li
Page No. – Page No.
Manganese Catalyzed Highly
Selective Oxidation of Hydrosilanes
to Silanols under Neutral Conditions
A manganese complex catalyzes the chemoselective oxidation of hydrosilanes and
dihydrosilanes with H2O2 to afford various silanols and silandiols, with the selectivity
controlled solely by the catalyst 1.
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