Palladium-Catalyzed Cross-Coupling of Monochlorosilanes and Grignard Reagents

Article abstract of DOI:10.1021/acscatal.7b03465

Using a palladium catalyst supported by DrewPhos, the alkylation of monochlorosilanes with primary and secondary alkylmagnesium halides is now possible. Arylation with sterically demanding aromatic magnesium halides is also enabled. This transformation ov

Full text of DOI:10.1021/acscatal.7b03465

Letter
pubs.acs.org/acscatalysis
Cite This: ACS Catal. 2017, 7, 8113-8117
Palladium-Catalyzed Cross-Coupling of Monochlorosilanes and
Grignard Reagents
Bojan Vulovic,‡ Andrew P. Cinderella,‡ and Donald A. Watson*
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States
S
* Supporting Information
ABSTRACT: Using a palladium catalyst supported by DrewPhos, the
alkylation of monochlorosilanes with primary and secondary
alkylmagnesium halides is now possible. Arylation with sterically
demanding aromatic magnesium halides is also enabled. This
transformation overcomes the high bond strength of the Si−Cl
bond (113 kcal/mol) and is a rare example of a transition-metal
catalyzed process involving its activation. Because of the availability of
both chlorosilanes and organomagnesium halide reagents, this method
allows for the preparation of a wide range of alkyl and aryl silanes.
KEYWORDS: palladium, alkylation, arylation, silane, Grignard reagents
lkyl silanes are broadly useful materials with a vast range of
1
2
Aapplications, including usage in materials, pharmaceut-
icals,3 and agrochemicals,4 as well as organic synthesis.5
Although hydrosilylation is useful for the synthesis of n-alkyl
silanes,2d,6 the synthesis of silanes at secondary carbon centers
(α-branched silanes) has been a long-standing challenge.
Particularly, for the preparation of tetra-organosilanes, classical
methods such as the addition of organometallic nucleophiles to
halosilanes normally fail.7 Instead of the desired alkylation,
these reactions result in the formation of hydrosilanes (Si−H).
In the rare cases where they do work (we are aware of only five
such reports in all of the chemical literature),8 harsh conditions
or exotic reagents are required, and yields are typically very
poor. Recently, Fu and Oestreich have independently
developed approaches to α-branched silanes using transition-
metal-catalyzed umpolung cross-couplings of silyl nucleophiles
with alkyl electrophiles, which provide one solution to this
problem.7,9
Earlier this year, as part of our study of transition-metal-
catalyzed cross-couplings of silicon electrophiles,10 we demon-
strated that linear and α-branched silanes could be prepared via
the cross-coupling of silyl iodides and alkyl zinc halides using
palladium catalysis (Figure 1, top).11 This “silyl-Negishi”
strategy represents the natural polarity of the Si−C bond and
takes advantage of the natural electrophilicity of Si centers.
While this reaction is highly complementary to the umpolung
methods mentioned above and provides a useful strategy for
preparing α-branched silanes, it was limited to the use of silyl
iodide electrophiles. Critically, silyl chlorides have failed to
provide more than a trace yield of product.11
Figure 1. Palladium-catalyzed silyl halide alkylation.
iodides typically require multiple steps to access, chlorosilanes
are the product of the Muller−Rochow “Direct” Process,12
̈
which is widely practiced on a commodity scale. Thus, the
ability to directly engage monochlorosilanes in cross-coupling is
important for the ability to modify feedstock chemicals of
critical importance to the silane industry.
Despite this appeal, the high bond strength of the Si−Cl
bond (113 kcal/mol)13−16 has severely hampered the develop-
ment of transition-metal methods involving its activation.
Reports of productive chlorosilane activation have been limited
to the weaker Si−Cl bonds of polychlorosilanes or hydro-
chlorosilanes.17 However, those reactions have not been
exploited in synthetic applications. In addition, three reports
of monochlorosilane activation using iridium(I) complexes
The development of cross-coupling conditions that allow for
the use of silyl chlorides would be a significant advance, because
silyl chlorides are not only much less sensitive to air and
moisture, but they also are much more abundant and
functional-group-tolerant than silyl iodides. Whereas silyl
Received: October 10, 2017
Revised: October 20, 2017
© XXXX American Chemical Society
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Letter
have also been described, but the resultant silyliridium chlorides
are unstable with regard to β-hydride elimination.17c,d,18
Finally, Oshima has reported on several metal-catalyzed
arylations of monochlorosilanes.19 However, these reactions are
believed to proceed via nucleophile activation, and not via
activation of the Si−Cl bond. Moreover, none of those
conditions exhibited any advantage in the case of alkyl
Grignard reagents.
Herein, we report conditions for the direct cross-coupling of
silyl monochlorides with alkyl nucleophiles (Figure 1, bottom).
We have found that these reagents participate in palladium-
catalyzed cross-coupling with primary and secondary Grignard
reagents to provide linear and α-branched alkyl silanes in very
high yield. The scope of this formal silyl-Kumada reaction is
high, and it represents a rare example of the direct utilization of
monochlorosilanes in transition-metal-catalyzed cross-coupling
without the need for external activating agents. Moreover, since
both silyl chlorides and Grignard reagents are inexpensive,
broadly available, and routinely used in commodity scale
synthesis, the potential for application of this reaction is high.
Finally, we also report that the catalytic conditions are directly
applicable to the cross-coupling of highly sterically demanding
aryl magnesium halide reagents, making these conditions also
relevant to the preparation of challenging aryl silanes.
Similar phenomena have been observed in many Kumada cross-
coupling reactions.23 Control experiments in both THF and
Et2O showed no background reactivity (entry 7 in Table 1). In
addition, the coupling was amenable to lower chlorosilane
loading by extending the reaction time.22
Utilizing alkylmagnesium bromides, the scope of Grignard
reagent was explored (Scheme 1). The model substrate 1 was
a b
,
Scheme 1. Scope of the Grignard Reagent
As mentioned, our previous study showed that alkyl zinc
halides failed to give more than trace alkylation of
monochlorosilanes under palladium-catalyzed conditions.11
Thus, we began this investigation by studying the use of
other classes of alkyl nucleophiles. To this end, we investigated
the reactivity of dimethylphenylsilyl chloride with isopropyl-
magnesium chloride, using tetrahydrofuran (THF) as solvent.
Gratifyingly, we found modest reactivity using (Drew-
Phos)2PdI2 as catalyst; however, selectivity was shifted from
sec-alkylsilane (1) in favor of the linear alkylsilane product (2)
(see Table 1, entry 1).20 The use of iPrMgCl·LiCl (the so-called
a
b
Isolated yields. Parenthetical yields run without catalyst; as
c
d
determined by NMR. 1.05 equiv of Me2PhSiCl. exo:endo 72:28.
e
From RMgCl.
isolated in quantitative yield on a 1 mmol scale. On a larger 100
mmol scale, the product could be isolated in almost the same
yield (96% yield, 17.2 g of product), demonstrating that the
process is highly scalable.24 Primary Grignard reagents show
modest background reactivity; however, the catalyzed reaction
resulted in quantitative yields (3). Acyclic and cyclic secondary
Grignard reagents were high, yielding 4−6, as well as 10−13 in
the reaction. Stereoselectivity in the formation of product 6 is
notable. 1H NMR analysis confirmed that the bicyclic
norbornyl Grignard reagent was formed in a 41:59 exo:endo
ratio (as has been reported in the literature).25 However, the
product is formed in a 73:27 exo:endo ratio, suggesting that a
stereoconvergent mechanism may be at play.26 α-Trimethylsi-
lylmagnesium chloride was effective at generating disilyl-
methane 7, which is a highly useful class of carbon
pronucleophiles for Peterson olefination and related reac-
tions.27,27c,28 Sterically hindered neopentylsilanes 8 and 9 were
also successfully synthesized, even when utilizing the less-active
alkylmagnesium chloride reagents (9).29
Aryl halides and aryl ethers (11 and 12, repsectively) were
tolerated in the reaction, and offer further cross-coupling
handles for downstream manipulation.16c−e,30 Benzylic sub-
strate 13 was successfully formed while avoiding the formation
of styrene byproducts, exemplifying the ability of the catalyst to
disfavor β-hydride elimination. While sterically unencumbered
aryl Grignard reagents can be added to chlorosilanes efficiently
without catalysis (14), ortho substitution severely diminishes
the uncatalyzed yield. Palladium catalysis allows full conversion
of bulky aryl groups to form encumbered silanes (15 and 16).
The addition of ortho-tolyl magnesium bromide to prepare 15
Table 1. Reaction Optimization
a
a
entry
[Mg]
MgCl
solvent
THF
1 + 2 (%)
1:2 ratio
1
2
3
4
5
6
45
92
96
24
99
99
0
38:62
31:69
34:66
>99:1
>99:1
>99:1
MgCl·LiCl
MgBr
THF
THF
MgCl
Et2O
MgBr
Et2O
MgI
Et2O
b
7
MgBr
Et2O or THF
a
b
As determined by GC. No Pd.
“Turbo Grignard”)21 and PrMgBr both improved the yield of
the reaction, but the selectivity remained poor (see entries 2
and 3 in Table 1). Critically, changing the solvent to the less-
polar Et2O maintained the yield while providing complete
selectivity in favor of the sec-alkyl product 1 (entry 5 in Table
1). Alternative acyclic ethers such as Bu2O, MTBE, and CPME
were also effective in maintaining selectivity for the sec-alkyl
product 1.22 The halide of the Grignard reagent also affected
reactivity, wherein I ≥ Br ≫ Cl (entries 4−6 in Table 1).
i
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Letter
ab
,
compares well with the prior catalytic conditions reported by
Oshima;19 however, those studies did not report the addition of
larger Grignard reagents, such as mesityl magnesium bromide.
These examples demonstrate the ability of this catalytic system
to accommodate highly sterically hindered coupling partners to
form silanes that are otherwise inaccessible.
Scheme 3. Scope of Larger Silanes
After establishing the generality of the Grignard coupling
partner, we sought to determine the scope of chlorosilane
(Scheme 2).31 Various alkyl substitutions such as trimethyl-
a b
,
Scheme 2. Scope of Chlorosilane
a
b
Isolated yields. Parenthetical yields run without catalyst; as
c
determined by NMR. Run at 100 °C.
effect on the reaction. Increasing the reaction temperature to
100 °C even allowed for modest reactivity of tert-
butyldimethylsilyl chloride, resulting in a 30% yield of 33.
While modest in yield, the only other example of tert-
butyldimethylsilyl halide (TBS-X) activation is through the
use of more-reactive TBS−OTf under nickel catalysis.10c
From a synthetic standpoint, the ability to directly alkylate
silyl chlorides with simple Grignard reagents represents a major
advance in the synthesis of alkyl silanes. From a mechanistic
standpoint, however, considering that both the Grignard
reagent and the palladium precatalysts introduce heavier halides
(bromide and iodide) to the reaction, we cannot rule out the
possibility that the reactions in Schemes 2 and 3 are proceeding
via initial halogen exchange at the silicon center.10a,34 To better
understand the role of the various halides in the reaction, we
investigated reaction conditions that excluded heavier halogens.
Using isopropyl magnesium chloride and the palladium
chloride precatalyst (DrewPhos)2PdCl2, the alkylation of
Me2PhSiCl was investigated (Table 2). Although, under these
a
b
Isolated yields. Parenthetical yields run without catalyst; as
Table 2. All Chloride Conditions
determined by NMR.
(17), dimethylphenethyl- (18), and dimethylneohexyl- (19) all
reacted cleanly. Trifluoromethyl substitution (20) was also
tolerated. Primary alkyl chloride (21 and 22) and bromide (23)
substrates performed well, demonstrating remarkable selectivity
of this catalyst for Si−Cl over C−halide activation and allowing
further reactivity such as substitution and cross-coupling
reactions.16c,32 In contrast to our previously published silyl-
Negishi reaction,11 synthetically useful terminal alkenes33 (24)
also progressed without incident. Aryl substitution such as
pentafluoroaryl (25), biphenyl (26), and phenyl ether (27)
substrates were well-tolerated. Overall, this cross-coupling
demonstrates a wide functional group tolerance that allows
for a wide range of downstream manipulations.
Although larger chlorosilanes gave moderate yields at room
temperature (rt), increasing the temperature to 50 °C in Bu2O
allowed for highly efficient reactions (Scheme 3). Triethylsilyl
chloride gave quantitative yields of 28. Again, this directly
contrasts with the silyl-Negishi reaction, wherein sterically
encumbered reagents as small as triethylsilyl iodide showed
poor reactivity.11 Cyclohexyl- and isopropyldimethylsilyl
chloride also gave excellent yields of doubly α-branched silanes
29 and 30. Increasing aryl substitutions such as diphenylsilyl
chloride (31) and triphenylsilyl chloride (32) showed minimal
a
entry
solvent
temperature
additive
yield (%)
1
2
3
Et2O
Bu2O
Et2O
rt
6
70
52
50 °C
rt
0.25 equiv TMEDA
a
Determined by GC.
“all chloride” conditions, low reactivity was observed at room
temperature (entry 1), simply warming the reaction to 50 °C
provided efficient cross-coupling (entry 2). These results clearly
demonstrate that the heavier halogens are not required for the
cross-coupling to proceed. Alkyl magnesium chloride reagents
are known to be highly aggregated in solution, and are often
inferior Grignard reagents, compared to their heavier halogen
congeners.21 We believe that aggregation may be the reason for
the sluggish reactivity observed in this study. Supporting this,
addition of substoichiometric TMEDA, which is known to
break up RMgCl aggregates, dramatically increased the
observed reactivity under the “all chloride” conditions (entry
3).35 Taken together, these results support the hypothesis that
this catalytic system is capable of direct Si−Cl bond activation.
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Based on the Carbon/Silicon Switch Strategy. In Atypical Elements in
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Studies to further elucidate the mechanism of this trans-
formation are currently underway.
In conclusion, we report a general, palladium-catalyzed
alkylation of chlorosilanes with primary and secondary
alkylmagnesium halides. This transformation tolerates a
multitude of reactive functional handles, such as ethers,
halogens, and alkenes, as well as sterically demanding
nucleophilic and electrophilic coupling partners, which opens
the products to a wide range of downstream manipulations.
Overall, utilizing widely available Grignard reagents and
chlorosilanes, this methodology allows access to a vast range
of linear and α-branched alkyl silanes, as well as sterically
demanding aromatic silanes, in a simple and straightforward
manner.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.7b03465.
■
S
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Experimental procedures and spectral data (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: dawatson@udel.edu.
■
ORCID
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Donald A. Watson: 0000-0003-4864-297X
Author Contributions
‡These authors contributed equally to this work.
Notes
The authors declare the following competing financial
interest(s): The University of Delaware has applied for a
provisional patent related to this methodology.
ACKNOWLEDGMENTS
■
The University of Delaware, the National Science Foundation
(No. CAREER CHE-1254360), the Delaware Economic
Development Office (Grant No. 16A00384), Gelest, Inc.
(Topper Grant Program), and the Research Corp. Cottrell
Scholars Program are gratefully acknowledged for support. Data
was acquired at the University of Delaware on instruments
obtained with the assistance of NSF and NIH funding (NSF
Nos. CHE0421224, CHE0840401, CHE1229234; NIH
S10RR026962, P20GM104316, and P30GM110758).
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8117
DOI: 10.1021/acscatal.7b03465
ACS Catal. 2017, 7, 8113−8117