Practical and scalable synthesis of bench-stable organofluorosilicate salts

Article abstract of DOI:10.1039/d0cc05400c

Silanes have enjoyed significant success as synthetic tools in the last few decades. In many of the reactions that use silanes, a pentacoordinate silicate is proposed as the reactive intermediate. Despite this, there is no general method to synthesize pentacoordinate fluorosilicates and use them as reagents instead of organo- or alkoxysilanes. Herein, we report the first practical synthesis of organotetrafluorosilicates. The method is tolerant of a number of different functional groups including electrophiles with preferential attack of the fluoride on the silane rather than the electrophile. This transformaton is generally high yielding, even at the mole scale. Furthermore, we demonstrate that organotetrafluorosilicates are both more reactive than the corresponding trialkoxysilanes and more stable under solvolytic conditions. Organotetrafluorosilicates can be used as substrates for a variety of coupling reactions, oxidations, and radical reactions. Overall, organotetrafluorosilicates represent a new platform on which to develop challenging transformations.

Full text of DOI:10.1039/d0cc05400c

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DOI: 10.1039/D0CC05400C
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Practical and scalable synthesis of bench-stable
organofluorosilicate salts
Jarett M. Posz, Stephan R. Harruff, and Ryan Van Hoveln*
Received 00th January 20xx,
Accepted 00th January 20xx
Silanes have enjoyed sigificant success as synthetic tools in the last few decades. In many of the reactions that use silanes,
a pentacoordinate silicate is proposed as the reactive intermediate. Despite this, there is no general method to synthesize
pentacoordinate fluorosilicates and use them as reagents instead of organo- or alkoxysilanes. Herein, we report the first
practical synthesis of organotetrafluorosilicates. The method is tolerant of a number of different functional groups including
electrophiles with preferential attack of the fluoride on the silane rather than the electrophile. This transformaton is
generally high yielding, even at the mole scale. Furthermore, we demonstrate that organotetrafluorosilictes are both more
reactive than the corresponding trialkoxysilanes and more stable under solvolytic conditions. Organotetrafluorosilicates
DOI: 10.1039/x0xx00000x
can be used as substrates for
a variety of coupling reactions, oxidations, and radical reactions. Overall,
organotetrafluorosilicates represent a new platform on which to develop challening transformations.
benchtop since they do not undergo self-condensation like
boronic acids8 and are less prone to hydrolysis than boronic
esters.9 Recently, effort has been made to synthesize and
explore the reactivity of bis(catecholato)silicates for a number
of different transformations, however, these transformations
tend to suffer from poor atom economy.3 Additionally, Kumada
published a series of papers in the late 1970’s and early 1980’s
Introduction
Silanes have been used widely in a broad range of different
reactions.1-4 Activated silanes can be oxidized to form a number
of different carbon-heteroatom bonds, most notably, alcohols
can be produced by the Fleming-Tamao oxidation.1 In the last
three decades, silanes have experienced an influx of new
reactivity since the introduction of the Hiyama coupling.2 They
have received much attention because of their ease of
synthesis, mild reactivity, and high selectivity. However,
because silanes tend to have low reactivity, they almost always
need an activating agent in order for the reaction to proceed.
Silicates have also been widely used as radical precursors for a
number of photoredox transformations.3 Because of this
propensity to form radicals, silanes can also participate in
radical reactions as radical mediators.4
which
synthesized
organopentafluorosilicates
and
demonstrated their reactivity (Figure 1, a).10 Unfortunately,
these coordinatively saturated species tended to suffer from
low reactivity mainly due to the poor solubility. Since their initial
report, the chemistry of pentafluorosilicates has only recently
been explored further as alkyl radical precursors to form C(sp3)-
C(sp3) bonds.11 One of the first reported means of synthesizing
previous work:
SiF5K2
1) HSiCl3, H2PtCl6 (cat.)
In nearly every coupling reaction developed for silanes, a
stoichiometric amount of either a fluoride or a base is necessary
for the reaction to proceed.1,2 This base or fluoride attacks the
silane to form an oft-invoked pentacoordinate silicate, which is
the reactive species. To our surprise, and in spite of the fact
that these intermediates seem to be more reactive, there has
been no general method to synthesize pentacoordinate
fluorosilicates to be used as a starting material.5
(a)
2) KF
HF
R2N
Si(OMe)3
R2HN
SiF4
n
(b)
(c)
n
H
O
N
Si(OEt)3
KHF2
NH
Other ‘ate’ species have been synthesized, particularly
organotrifluoroborates. Treatment of a boronic acid or ester
with KHF2 yields the corresponding trifluoroborate salt cleanly
O
R
SiF4K
S
N
H
and in high yield.6
Furthermore, not only do
organotrifluoroborates have a wider range of reactivity than
boronic acids, particularly in transition metal catalysed cross
coupling reactions,7 they tend to be more stable on the
this work:
Si(OR)3
SiF4NH4
NH4HF2
(d)
Department of Chemistry and Physics, Indiana State University, 600 Chestnut Street,
Terre Haute, Indiana, 47809. Email: ryan.vanhoveln@indstate.edu
Electronic Supplementary Information (ESI) available: experimental procedures and
spectra of novel compounds. See DOI: 10.1039/x0xx00000x
Figure 1: Methods to synthesize organofluorosilicate
compounds.
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fluoride source still produced mixtures which indicated that the
organofluorosilicates involves treating aminosilanes with dry
HF.12 There are
few methods that synthesize
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prDefOeIr: r1e0d.1039/D0CC05400C
over the
a
tetrafluorosilicate
might
be
organotetrafluorosilicates, but none of them represent a
general procedure that can be used in a number of different
contexts. Trialkoxysilanes with appended amines have been
treated with HF to generate a zwitterion (Figure 1, b).13
Organotetrafluorosilicates have also been synthesized by
treating ArylSiF3 with KF and 18-crown-6 for an early study of
the structure of an organotetrafluorosilicate.14 Lastly, a biotin
derivative with an appended trialkoxysilane was treated with
KHF2 to make an organotetrafluorosilicate for potential use in
18F PET imaging Figure 1, c).15 However, we were not able to
reproduce their results using a model substrate (see below,
Table 1, entry 2). In fact, their characterization data seems to
indicate a mixture of fluorosilicates rather than a homogenous
organotetrafluorosilicate. Thus, we set out to develop a general
method that would synthesize this potentially useful class of
compounds.
pentafluosilicate. Indeed, when the stoichiometry was reduced
to 2.0 equivalents of potassium bifluoride, the
tetrafluorosilicate was produced cleanly and in high yield (entry
3). The method was also tolerant of ammonium counter ions,
though some re-optimization was necessary. At more dilute
concentrations, the product did not precipitate. Higher
concentrations with short reaction times did not allow the
silane to fully dissolve, and therefore minimal product was
formed, but using a more concentrated solution with longer
0.25 M KHF2
R
R
Si(OR)3
R
SiF4K
conditions A
conditions B
acetone/H2O
4 M NH4HF2
H2O
1a,b,c,g
2a,b,c,g
While synthesis of organofluorosilicates should be straight-
forward, their synthesis exhibits challenges not present with
organotrifluoroborates. For instance, either the tetra- or
pentafluorosilicate could be formed in the presence of a
nucleophilic fluoride source, so mixtures of products are likely,
whereas there is only one possible product from fluoroborate
Si(OR)3
R
SiF4NH4
1a-n
3a-n
entry substrate conditions
product
yield
SiF4NH4
SiF4K
1
2
1a
1a
B
A
3a
2a
67%
89%
formation.
Additionally, fluorosilicate polymers and/or
O
O
oligomers could form.16 Ideal reaction conditions would form
one product selectively without the presence of the others.
Herein, we report a convenient synthesis of organotetra-
fluorosilicates from readily available starting materials (Figure
1, d). We demonstrate that organotetrafluorosilicates are both
more stable under solvolytic conditions and more reactive in
couplings and oxidations than a trialkoxysilane. Furthermore,
because we want this reaction to enjoy wide use, this
transformation has been performed on the mole scale without
loss of yield.
3
4
1b
1b
B
A
3b
2b
91%
74%
O
O
SiF4NH4
SiF4K
O
5
6
1c
1d
B
B
3c
3d
80%
99%
O
O
SiF4NH4
O
P
SiF4NH4
SiF4K
O
O
P
7
1d
A
2d
77%
Results and discussion
O
O
8
9
1e
1f
B
B
B
A
3e
3f
>99%
98%
91%
96%
NC
H2N
HS
HS
SiF4NH4
Given its success with generating trifluoroborates and the
previous report using a biotin derivative as the substrate, initial
optimization was performed with potassium bifluoride (Table
1). The identity of the solvent proved to be essential as alcohols
and DMSO produced mixtures of products rather than the
desired tetra- or pentaflurosilicate (entries 1-2). Excesses of the
SiF4NH4
SiF4NH4
SiF4K
10
11
1g
1g
3g
2g
SiF4NH4
12
13
1h
1i
B
B
3h
3i
80%
93%
MHF2 (2 equiv)
SiF4NH4
R
Si(OR)3
R
SiF4M
R
SiF5M2
2h, solvent
1
T
P
Br
14
15
1j
B
B
3j
85%
75%
entry substrate fluoride
solvent
conc.
T
P
SiF4NH4
1a
1a
1a
1a
1b
KHF2
KHF2
1:1 H2O:MeOH
1:1 H2O:DMSO
0.25 M
0.25 M
mixture
F3C
1k
3k
SiF4NH4
2
mixture
16
1l
B
3l
85%
3
KHF2
1:1 H2O:acetone 0.25 M 89%
H2O 4 M 91%
0
0
4b
NH4HF2
N
SiF4NH4
17
18
1m
1n
B
B
3m
3n
64%
81%
O
Si(OMe)3
1a
1b
SiF4NH4
SiF4NH4
O
Si(OEt)3
H4NF4Si
a10 equiv of KHF2 was used. bThe reaction was stirred for 16 h.
Table 2: Substrate scope.
Table 1: Optimization of reaction conditions.
2 | J. Name., 2012, 00, 1-3
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reaction times produced the product in excellent yield (Table 1, timeframe. This clearly indicates that tetrafluorosilicates are
View Article Online
DOI: 10.1039/D0CC05400C
entry 4).
However, when the substrate scope was explored (Table 2),
we found that the method which formed potassium salts
(conditions A) was not robust and produced varying results
more stable under solvolytic conditions than trialkoxysilanes.
[0.012]
= trimethoxysilane
[0.010]
= tetrafluorosilicate
depending on the substrate.
A
few potassium
[0.008]
[0.006]
[0.004]
[0.002]
0
tetrafluorosilicates were able to be formed in good yield (Table
2, entries 2, 4, 7, and 11). However, many substrates produced
mixtures of products and none of them were more than slightly
soluble in a small number of solvents. In fact, they could not be
detected by NMR at all in most solvents. Additionally, the
potassium salts tended to hydrolyse appreciably in 1-2 hours,
whereas the ammonium salts were highly resistant to hydrolysis
(see below).
0
100
200
300
400
500
600
minutes
With a reliable procedure in hand that produced ammonium
salts rather than potassium salts, the substrate scope was
explored further (Table 2). Moreover, ammonium salts were at
least moderately soluble in a wide number of polar, aprotic
organic solvents. A number of different functional groups were
tolerated including electrophiles such as epoxides, esters,
nitriles, and phosphonates (entries 3-8). Notably, the fluoride
preferred to attack the silicon rather than the appended
electrophile in all cases. No competing fluoride attack on any
electrophile was detected. Substrates with labile protons, such
as amines and thiols, were also tolerated (entries 9-11).
Synthetically useful products, such as vinyl and phenyl
tetrafluorosilicates, were formed in high yield as well (entries
12-14). Even (bis)silanes were tolerated in the reaction
conditions when 4.0 equiv of NH4HF2 was used (entry 18).
Overall, the method seems to be general and is highly tolerant
of a number of different functional groups.
Figure 2: Hydrolysis of trimethoxysilane vs. tetrafluorosilicate.
Next, the difference in reactivity was studied in popular
reactions that use silane starting materials (Figure 3). For both
the Hiyama Coupling and Fleming-Tamao Oxidation, almost no
reaction occurred with the trialkoxysilanes as starting materials.
Conversely, the yields were substantially increased when the
tetrafluorosilicates were used instead. This is not surprising as
these reactions usually require the formation of a transient
pentacoordinate silicate species for the reaction to proceed.
Notably, the Hiyama coupling with the tetrafluorosilicate is a
rare example of a coupling reaction occurring under acidic (due
to the ammonium counter ion) rather than basic conditions.
However, this shows that the organotetrafluorosilicates are
much more reactive than their trialkoxysilane counterparts in
spite of their increased stability.
With a substrate scope established, the scalability of the
method was explored (eq. 1). On larger scales, more
concentrated NH4HF2 (8 M) performed better than lower
concentrations (see Electronic Supplementary Information for
more details). Since the product is slightly soluble in water, this
increase in yield was likely due to reduced loss of material that
was still dissolved in the water. At smaller scales, loss of
material from filtration is less of a concern since the reactions
experience significant evaporation which aids in precipitating
the product. Overall, the reaction was able to be scaled up to
one mole of starting material with 163g of product isolated.
Even at this significantly larger scale, the yield was not affected
appreciably.
Hiyama coupling
SiF4NH4
PhI, Pd(PPh3)4 (5%)
DMSO, 150 o
60%
C
Si(OMe)3
same conditions
<10%
Fleming-Tamao oxidation
O
H2O2 (10 equiv)
H2O
SiF4NH4
95%
O
O
OH
Si(OMe)3
SiF4NH4
8 M NH4HF2
82%
163g
eq. 1
O
O
H2O
same conditions
Si(OMe)3
0%
To test the stability of the organotetrafluorosilicates under
solvolytic conditions, their decomposition in water was studied
and compared to the trimethoxysilane starting material.
Saturated solutions of 4-BrC6H4Si(OMe)3 and 4-BrC6H4SiF4NH4
were prepared and the concentration of the corresponding
silanol was measured by NMR (Figure 2). The trialkoxysilane
hydrolysed slowly over the course of 10 hours, however, the
tetrafluorosilicate did not hydrolyse at all in the same
O
Figure 3: Comparison of the reactivity of trialkoxysilanes and
tetrafluorosilicates.
Conclusions
In conclusion, organotetrafluorosilicates can be synthesized
selectively over organopentafluorosilicates and in high yield.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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2254-2259; G. Ikarashi, T. Morofuji, N. Kano, Chem. Commun.,
This procedure tolerates a large number of different functional
groups and can be scaled without degradation of yield.
Additionally, organotetrafluorosilicates seem to be both more
stable under solvolytic conditions than their trialkoxysilane
counterparts as well as more reactive. We hope that access to
this uncommon silicon functional group will be a platform to
develop new reactivity and new couplings.
View Article Online
Advance Article.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This research was funded by Indiana State University,
including student scholarship support from the Center for
Student Research and Creativity and the Summer
Undergraduate Research Experiences (SURE) program.
Instrumentation is supported by the National Science
Foundation (CHE-0521075 MRI for the Bruker Avance 400 MHz
NMR and CHE-1531972 MRI for the Thermo Scientific Q Exactive
MS) and the National Institutes of Health (S10 OD012245 for the
Bruker Avance 600 MHz NMR). The authors would also like to
thank Prof. Rick Fitch for his helpful conversations pertaining to
this project, Jake Wilkinson for editing this manuscript, and
Charlie Fry (UW-Madison) for his assistance acquiring spectra.
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ChemComm
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DOI: 10.1039/D0CC05400C
Table of Contents Entry:
Ammonium organotetrafluorosilicates were synthesized in high yield for a wide range of substrates from readily
available starting materials.