Synthesis of Alkyl Silanes via Reaction of Unactivated Alkyl Chlorides and Triflates with Silyl Lithium Reagents

Article abstract of DOI:10.1021/acs.orglett.0c02337

The reaction of unactivated secondary and primary alkyl chlorides as well as primary alkyl triflates with silyl lithium reagents to access tetraorganosilanes is reported. These nucleophilic substitutions proceed in the absence of any transition metal catalyst under mild conditions in moderate to very good yields. The silyl lithium reagents are readily generated from the corresponding commercially available chlorosilanes. Enantioenriched secondary alkyl chlorides react with high stereospecificity under inversion of configuration.

Full text of DOI:10.1021/acs.orglett.0c02337

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Letter
Synthesis of Alkyl Silanes via Reaction of Unactivated Alkyl
Chlorides and Triflates with Silyl Lithium Reagents
̈
Shubhadip Mallick, Ernst-Ulrich Wurthwein, and Armido Studer*
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ABSTRACT: The reaction of unactivated secondary and primary alkyl chlorides as well as
primary alkyl triflates with silyl lithium reagents to access tetraorganosilanes is reported. These
nucleophilic substitutions proceed in the absence of any transition metal catalyst under mild
conditions in moderate to very good yields. The silyl lithium reagents are readily generated from
the corresponding commercially available chlorosilanes. Enantioenriched secondary alkyl
chlorides react with high stereospecificity under inversion of configuration.
Scheme 1. Different Approaches for the Preparation of
Tetraorganosilanes
espite the great achievements in the area of carbon−
D
heteroatom bond formation, the development of novel
methodology in this field is still of high importance to organic
chemists, since most compounds used in materials science as
well as in agrochemical and pharmaceutical industry contain
heteroatoms. In this context, carbon−silicon bond formation
has become highly fascinating,1 and organosilicon compounds
have found wide applications as reagents in organic chemistry.2
Moreover, they often appear as important components in
materials science3 and are also valuable in medicinal
chemistry.4
Several approaches have been developed for the synthesis of
organosilicon compounds (Scheme 1). Hydrosilylation5 as the
most commonly applied method has to be named first
(Scheme 1a). However, considering secondary alkyl silanes
derived from internal alkenes, the regioselectivity problem has
to be addressed.6 In addition, in most cases a transition metal
catalyst is required, which increases the overall costs of the
hydrosilylation process. Another well-established approach to
access organosilicon compounds is the transition metal
catalyzed coupling of a carbon nucleophile with a silicon
electrophile (Scheme 1b).7 Considering a stereoselective
procedure, this strategy has been found to be challenging.8
As a third approach, transition metal catalyzed C(sp3)-silicon
coupling processes of an alkyl electrophile with a silicon
nucleophile have been developed by the groups of Fu9 and
Oestreich10 (Scheme 1c). However, considering unactivated
chiral secondary C-electrophiles, this strategy has its
limitations.11 Along these lines, Oestreich and co-workers
have developed stereospecific reactions using activated electro-
philes.12 To the best of our knowledge, little is known about
the preparation of chiral alkyl silanes via C(sp3)−Si coupling of
unactivated alkyl electrophiles with silicon nucleophiles.13 38
years ago, Kumada disclosed a single example on the
stereospecific reaction of a chiral secondary alkyl chloride
with Ph3SiLi, but surprisingly this highly interesting trans-
formation remained unnoticed.13a When considering the cost
of transition metal catalysts, a transition metal free general
Received: July 14, 2020
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© XXXX American Chemical Society
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A

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a
approach to form various primary and secondary alkyl silanes
using silyl nucleophiles and cheap readily accessible alkyl
electrophiles would be desirable.
Scheme 3. Reaction of Various Alkyl Chlorides with 2a
As part of our research program on the use of silyl lithium
reagents in synthesis,1g,k we decided to explore the transition-
metal-free reaction of various electrophiles with Si−Li
compounds. Herein, we report a general method for the
preparation of various alkyl silanes using readily generated silyl
lithium reagents and unactivated primary and secondary alkyl
electrophiles (R-Cl/R-OTf). It is shown that silyl lithium
compounds react efficiently with various primary and
secondary alkyl chlorides, whereas the reaction with the
triflates is restricted to primary alkyl derivatives. The product
silanes are obtained in moderate to very good yields.
Considering the secondary alkyl chlorides as substrates,
displacement of the chloride occurs via an SN2 type
substitution under inversion of the configuration with high
stereospecificity.
We commenced our studies by examining the reaction of 2-
chloro octane (1a, racemic) as a test substrate with different
SiLi reagents 2a−d (Scheme 2). The best result was obtained
a
Scheme 2. Variation of the Silyl Nucleophile
a
Reaction conditions: 1 (0.3 mmol, 1.0 equiv), Si reagent (0.6 mmol,
a
b
Reaction conditions: 1a (0.3 mmol, 1.0 equiv), Si reagent (0.6
2.0 equiv), THF (1 mL). Reaction conducted on 5 mmol scale.
b
mmol, 2.0 equiv), THF (1 mL). Contains a small amount of
HSiMePh2 impurity.
Preparation of 3fa was also conducted at larger scale (5
mmol, 55%). Substrates containing Lewis basic atoms such as
oxygen and nitrogen as found in 1i and 1j were also tolerated,
and the corresponding silylated products 3ia and 3ja were
isolated in moderate to good yields. Reaction of the sterically
less hindered primary alkyl chlorides 1k−1p with 2a worked
rather well, and the alkyl silanes 3ka−3pa were obtained in
42−75% yield.
Noting that aliphatic alcohols are far more abundant than
the corresponding alkyl chlorides which are often derived from
these alcohols, we decided to also test activated alcohols as
electrophiles in the reaction with 2a. Careful experimentation
revealed that the triflate moiety acts as the best leaving group
for this substitution reaction (for full optimization, see SI).
Unlike the chlorides that work efficiently for both primary and
secondary electrophiles, triflates derived from secondary
alcohols are not stable and the corresponding alkenes formed
by β-elimination were observed during triflation. Other
activated alcohol derivatives did not engage in the silylation
and reaction worked very well on various primary alkyl triflates
(Scheme 4).
As compared to the reaction with the tested primary alkyl
chlorides 1k−1n, the corresponding triflates reacted more
efficiently and the silanes 3ka−3na were isolated in good to
excellent yields (65−94%). The 3-aryl-substituted triflates 4a
and 4b provided in the reaction with 2a the desired
tetraalkylsilanes 5aa and 5ba in 79% and 90% yield,
respectively. 2-Aryl substituted ethyl triflates (4c,d) which
are prone toward triflate elimination to give styrene derivatives
gave the targeted silylated products 5ca (80%) and 5da (74%).
upon running the substitution in THF using 2 equiv of
Me2PhSiLi (2a) for 12 h to provide 2-octanyl silane 3aa in
70% isolated yield. The Si−Li reagent solution, freshly
prepared from the corresponding chlorosilane and elemental
lithium in THF, was added at 0 °C to the alkyl chloride in
THF. The reaction mixture was then allowed to warm to room
temperature and maintained at this temperature for an
additional 12 h. Other silyl lithium reagents, such as t-
BuPh2SiLi (2b), MePh2SiLi (2c), and H2PhSiLi (2d), could
also be used to give the corresponding silanes 3ab−3ad in 40−
65% yield.
While 2a was maintained as the silyl nucleophile, the halide
leaving group was varied next and the chloride anion was
found to be the most efficient nucleofuge in this series. For
alkyl bromides the yield was very low, and no product
formation was observed for alkyl fluorides and iodides (see the
Supporting Information (SI)).
We next investigated the scope and limitations of the
method by testing various primary and secondary alkyl
chlorides (Scheme 3). For these studies, Me2PhSiLi was
mainly used as the silyl nucleophile. As expected, other 2-
chloro alkanes 1b and 1c reacted well with 2a to give the
corresponding products 3ba and 3ca in 60% and 63% yield.
Phenyl-containing (3-chlorobutyl)benzene (1d) gave the
substitution product 3da in 90% yield, and a slightly lower
yield was noted for 3ea (75%). The developed reaction is not
restricted to acyclic chloroalkanes as various cyclic alkyl
chlorides (1f−h) engaged in the substitution to give the
corresponding silylated products 3fa−3ha (61%−74%).
B
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standard conditions led to a significantly reduced selectivity
(51% es). We further showed that LiCl formed during the
reaction does not racemize the starting chiral alkyl chloride
under our reaction conditions (see the Supporting Informa-
tion). The absolute configuration of (R)-3da was unambigu-
ously assigned after Tamao−Fleming oxidation of (R)-3da to
the corresponding known secondary alcohol. In analogy,
chloride (S)-1a reacted with high stereospecificity to produce
silane (R)-3aa (92% es). Thus, the displacement of the
chlorine atom in these secondary alkyl chlorides by the silyl
lithium reagent 2a proceeds with inversion of the configuration
via an SN2-type mechanism, in agreement with the pioneering
Kumada study conducted with Ph3SiLi.13a
Scheme 4. Reaction of 2a with Various Primary Alkyl
Triflates
a
The preference of inversion over retention under the
experimental reaction conditions is nicely supported by
quantum chemical calculations (TPSSTPSS/def2-tzvp +
GD3BJ + PCM(THF)14 indicating clearly kinetic control.
Thus, the transition state for inversion is calculated to 14.5
kcal/mol (ΔG298) with respect to the best complex of the
starting compounds (Me2PhSiLi*2THF + 2-chlorobutane),
whereas the TS for retention has a value of 20.0 kcal/mol (for
details, see the Supporting Information).
Finally, we studied whether the known15 reaction of an aryl
chloride with a SiLi-reagent proceeds faster than the herein
disclosed transformation with secondary alkyl chlorides. To
this end, chloroarene 6 was first subjected to the standard
conditions using Me2PhSiLi (2a) as the nucleophile and the
aryl silane 7 was obtained in 46% yield (Scheme 6). Next, we
Scheme 6. Reaction of Aryl Chloride 6 with 2a
a
Reaction conditions: 4 (0.3 mmol, 1.0 equiv), Si reagent (0.6 mmol,
b
2.0 equiv), THF (1 mL). Reaction conducted with 4.0 equiv of 2a.
Functional groups like phenoxy (4f) and acetal (4g) were
compatible with the applied conditions, and substrates bearing
a terminal C−C multiple bond were also tolerated providing
the corresponding silanes in good yields (see 3na and 5ha).
Notably, the acidic proton of the terminal alkyne did not
interfere with the substitution reaction. The β- and γ-branched
alkyl triflates 4i and 4j also engaged in the silylation reaction
(5ia, 5ja). Tetrahydrofuran, ether, carbazole, and thiophene
functionalities were tolerated (see 5oa−5ra). Notably,
bissilane 5pa was formed by double nucleophilic substitution
from the corresponding bistriflate 4p in 66% yield.
We next investigated the stereospecificity of the nucleophilic
substitution in secondary alkyl chlorides (Scheme 5). To our
delight, the selected enantioenriched alkyl chloride (S)-1d
reacted with 2a at −50 °C to give the desired silane (R)-3da
that was isolated with high enantiospecificity (93% es) in 50%
yield. Of note, reaction at room temperature under our
ran a competition experiment with 2a (1 equiv) using an equal
amount of chloroarene (6) and chlorocyclohexane (1f) (1
equiv each). Exclusive formation of the aryl silane 7 (37%)
revealed the aryl chloride 6 to be much more reactive toward
Me2PhSiLi than the secondary alkyl chloride 1f. Of note, a
similar result was obtained upon running the competition
experiment with 4-fluorobiphenyl1k in place of 6 (see the
Supporting Information).
In summary, we have developed a straightforward method
for the preparation of a variety of tetraorganosilanes.
Nucleophilic displacement of the chloride and trifluorome-
thylsulfonyl moiety in alkyl chlorides and alkyl triflates using
silyl lithium reagents occurred in the absence of any transition
metal catalyst under mild conditions. Reaction of chiral
secondary alkyl chlorides with PhMe2SiLi occurred in an SN2
fashion with high stereospecificity under inversion of
configuration allowing to access highly enantioenriched chiral
alkyl silanes via this approach.
Scheme 5. Stereospecific Nucleophilic Substitution of
a
Enantioenriched Secondary Alkyl Chlorides
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c02337.
a
Experimental details and characterization data for the
starting material and products (PDF)
Reaction conditions: 6 (0.3 mmol, 1.0 equiv), Si reagent (0.6 mmol,
2.0 equiv), THF (1 mL). Reaction conducted at −50 °C.
C
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AUTHOR INFORMATION
■
Corresponding Author
̈
Armido Studer − Institute of Organic Chemistry, Westfalische
Wilhelms University, 48149 Munster, Germany; orcid.org/
0000-0002-1706-513X; Email: studer@uni-muenster.de
̈
Authors
Shubhadip Mallick − Institute of Organic Chemistry,
̈
̈
Westfalische Wilhelms University, 48149 Munster, Germany
Ernst-Ulrich Wu
̈
rthwein − Institute of Organic Chemistry,
́
(b) Lacout-Loustalet, M.; Dupin, J.; Metras, F.; Valade, J. Reactions
̈
̈
Westfalische Wilhelms University, 48149 Munster, Germany
́
́
́
́
non classiques au cours de l’alkylation de derives d’elements de la
́
́
colonne IVB par des reactifs de Grignard: III. Etude du comporte-
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c02337
́
́
ment de derives RnSiΣ4-n. J. Organomet. Chem. 1971, 31, 187−204.
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Palladium-catalyzed cross-coupling of silyl electrophiles with alkylzinc
halides: a Silyl-Negishi reaction. J. Am. Chem. Soc. 2017, 139, 7741−
7744. (e) Vulovic, B.; Cinderella, A. P.; Watson, D. A. Palladium-
Catalyzed Cross-Coupling of Monochlorosilanes and Grignard
Reagents. ACS Catal. 2017, 7, 8113−8117.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
̈
We thank the Westfalische Wilhelms University for continuous
support.
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