Intermolecular Dehydrogenative C?H/Si?H Cross-Coupling for the Synthesis of Arylbenzyl Bis(silanes)

Article abstract of DOI:10.1002/ejoc.202100474

An iridium-catalyzed intermolecular dehydrogenative C?H/Si?H cross-coupling reaction for the synthesis of arylbenzyl bis(silanes) is developed. This hydrosilyl group steered intermolecular C?H silylation process features high chemo- and regioselectivity,

Full text of DOI:10.1002/ejoc.202100474

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: Intermolecular Dehydrogenative C−H/Si−H Cross-Coupling for
the Synthesis of Arylbenzyl Bis(silanes)
Authors: Lijun You, Wei Yuan, and Chuan He
This manuscript has been accepted after peer review and appears as an
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.202100474
Link to VoR: https://doi.org/10.1002/ejoc.202100474
01/2020

10.1002/ejoc.202100474
European Journal of Organic Chemistry
COMMUNICATION
Intermolecular Dehydrogenative C−H/Si−H Cross-Coupling for the
Synthesis of Arylbenzyl Bis(silanes)
Lijun You,† Wei Yuan,† and Chuan He*
[*]
L. You, Dr. W. Yuan, Prof. Dr. C. He
Shenzhen Grubbs Institute and Department of Chemistry
Guangdong Provincial Key Laboratory of Catalysis
Southern University of Science and Technology
Shenzhen 518055, Guangdong, China
E-mail: hec@sustech.edu.cn
[†]
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of the document.
Abstract: An iridium-catalyzed intermolecular dehydrogenative
C−H/Si−H cross-coupling reaction for the synthesis of arylbenzyl
bis(silanes) is developed. This hydrosilyl group steered
intermolecular C−H silylation process features high chemo- and
regioselectivity, giving access to a wide range of multi-functionalized
organosilanes in good yields from readily available starting materials
with atom economy, efficiency, and environmental benignity.
Organosilanes are a class of valuable and versatile compounds
with unique chemical, physical, and biological properties, which
grant them widespread applications in organic chemistry,
agrochemistry, medicinal chemistry, and materials science.[1]
Accordingly, substantial efforts have been dedicated to the
development of practical and effective approaches for the
synthesis of organosilanes from simple silicon-based starting
materials. In the past decades, the extraordinary advances
achieved
by
transition-metal-catalyzed
C−H
bond
functionalization have revolutionized the rules for assembling
molecules, enabling the rapid construction of functional
molecules in a more efficient and straightforward manner.[2]
Among them, the silylation of C−H bonds presents a prominent
example offering a superior step and atom economic approach
to organosilicon compounds.[3] Although with many success,
direct intermolecular silylation of aryl C−H bonds using
hydrosilanes as the silylation reagents usually required harsh
conditions and a large excess of arene substrates.[4] Since 2000,
the Murai group reported a series of pioneering works of
directing groups assisted ruthenium-catalyzed silylation of aryl
C−H bonds with hydrosilanes.[5] The use of directing groups
facilitate the proximal C−H bond activation, enabling the facile
regioselective C(sp2)−H silylation. Later, a variety of directing
groups such as nitrogen-containing heterocycles, imines, and
amides have been introduced in various transition-metal-
catalyzed intermolecular aromatic C−H silylation with
monohydrosilanes serving as the silicon sources (Scheme 1a).[6]
Although these directed C−H silylation reactions are now
commonly used, the directing groups must be installed and
removed with extra steps if they are not part of the products,
which inevitably leads to the formation of nonproduct waste with
a significant environmental footprint, and compromises the
overall step- and atom-economical nature of C−H
functionalization.
Scheme 1. Metal-catalyzed silylation of aryl C−H bonds.
On the other hand, transition-metal-catalyzed intramolecular aryl
C−H silylation has also been extensively studied in recent
years.[7] This type of aryl C−H silylation is actually an
intramolecular dehydrogenative Si−H/C−H coupling reaction,
presumably proceeding via the formation of a cyclometalated
species (Scheme 1b). The tethered hydrosilyl group is proposed
to initiate the process reacting with metal catalyst, and deliver
the metal atom to the proximal C−H bond site allowing the C−H
activation, as well as participate the C−Si cyclization reaction.[3c]
It is worth mentioning that, a number of enantioselective
intramolecular aryl C−H silylation reactions have also been
1
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10.1002/ejoc.202100474
European Journal of Organic Chemistry
COMMUNICATION
achieved by using rhodium catalysts ligated with chiral
diphosphine ligands or iridium catalysts ligated with chiral
pyridinyloxazoline ligands.[7g,7m] With the continued interest in
organosilicon chemistry and C−H functionalization,[8] we
wondered whether the hydrosilyl group could serve just as a
directing group allowing the selective C−H activation;[9] then
enable an intermolecular dehydrogenative C−H/Si−H cross-
coupling with another hydrosilane partner, generating the
bis(silane) compound. Given the versatile convertible property of
silyl group, the hydrosilyl group steered C−H silylation process
would provide an attractive approach for the assembly of multi-
functionalized organosilanes from the viewpoint of economy,
efficiency, and environmental benignity. To realize this
hypothesis, the precise control of chemo- and regio-selectivity is
essential, which could be very challenging. Herein we report the
development of an Ir-catalyzed hydrosilyl group steered
intermolecular dehydrogenative C−H/Si−H cross-coupling for the
synthesis of arylbenzyl bis(silanes) (Scheme 1c).
At
the
outset
of
our
studies,
we
choosed
benzhydryldimethylsilane 1a bearing appropriate tethered
hydrosilyl group as the substrate, and dimethyl(phenyl)silane 2a
as the silylation agent to attempt the intermolecular
dehydrogenative Si−H/C−H coupling reaction (Table 1). In the
presence of [Ir(cod)OMe]2 catalyst, we first examined the
pyridinyl oxazoline ligand (L1), which usually performed well in
the intramoleclar aryl C−H silylation.[7m] Unfortunately, after
many efforts, only trace desired product could be observed
(entry 1). Further screening of several bidentated nitrogen
ligands disclosed that, diamine (L2, L3) and amine-oxazoline
(L5, L6) ligands afforded the target cross-coupling arylbenzyl
bis(silane) product 3a in 52−81% yields (entries 2−6). After
indentifying amine-oxazoline L6 as the best ligand with Ir
catalyst, additional reaction parameters, including solvent and
temperature, were screened. To our delight, the yield of product
3a could be improved to 99% when the reaction was conducted
in the solvent of DCE (1,2-dichloroethane) at 50 °C (entry 7).
However, toluene and 1,4-dioxane reduced the yield significantly
(entries 8−9). When the reaction was carried out at room
temperature, the yield of 3a decreased to 32% yield (entry 10). It
is noteworthy that, at this stage we could obitain 27% ee of 3a
when L6 was used as the ligand (entry 7), which underpins
preliminary studies towards enantioselective version of this
interesting intermolecular dehydrogenative Si−H/C−H coupling
reaction.
Table 1. Condition optimization.[a]
With optimized conditions in hand, we next assessed the scope
of this dehydrogenative C−Si coupling reaction (Table 2). In
general, a wide range of aryldimethylsilane silylation agents 2
bearing different electronically and sterically varied substituents
on the aromatic ring all reacted smoothly with 1a, affording the
corresponding arylbenzyl bis(silane) compounds 3a−3h in
27−95% yields. Electron-withdrawing group such as fluoro (3b,
3d), and electron-donating groups such as methoxy (3c, 3f),
tert-butyl (3e) and morpholinyl (3g) were well tolerated in the
reaction. Thiophene (3h) also participated to generate the
corresponding product, albeit in
a low yield. Moreover,
triarylsilanes, methyldiphenylsilane and triethylsilane were found
to be competent silylation reagents, giving the desired C−H
silylation products 3i−3m in 57−84% yields. The introduction of
chloro and trifluoromethyl substituents on the aromatic ring give
the bis(silane) products 3j, 3k without any problem. For the
scope of hydrosilyl group tethered substrate 1, various benzyl
monohydrosilanes could undergo selective ortho C−H silylation
with dimethyl(phenyl)silane (2a), leading to the corresponding
arylbenzyl bis(silane) products 3n−3q in good to outstanding
yields (68−99%). It is noteworthy that arylbenzyl bis(silanes) are
particularly attractive compounds given their versatile convertible
property of the two silyl groups. Traditionally, the access of
arylbenzyl bis(silanes) mainly relied on the use of Grignard
reagents, nBuLi or other strong bases, which displayed poor
selectivity and low compatibility with many functional groups.[10]
Under the current conditions, the ee values of most compounds
3 were low (see Supporting Information for details).
Entry
Ligand
L1
Solvent
THF
Yield [%]
trace
52
1
2
L2
THF
3
L3
THF
65
4
L4
THF
trace
76
5
L5
THF
6
L6
THF
81
7[b]
8
L6
DCE
99 (95)
trace
14
L6
toluene
1,4-dioxane
DCE
9
L6
10[c]
L6
32
[a] Conditions: 1a (0.20 mmol), 2a (0.40 mmol), [Ir(cod)(OMe)]2 (0.0080 mmol),
ligand (0.020 mmol), norbornene (0.24 mmol), 4Å molecular sieves (20.0 mg)
in 1.0 mL of solvent under argon atmosphere at 50 °C for 24 h. The yield was
determined by 1H NMR using 1,1,2,2-tetrachloroethane as internal standard;
yield in parentheses was isolated yield. [b] 27% ee was obtained. [c] Room
temperature.
To demonstrate the utility of the arylbenzyl bis(silanes), a
sequential substitution reaction showcasing the discrepancy of
aryl C−Si bond and benzyl C−Si bond were performed (Scheme
2). The prepared silylation product arylbenzyl bis(silane) 3a was
first subjected to a fluoride-mediated carboxylation at ambient
pressure of CO2, followed by the methylation with
2
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10.1002/ejoc.202100474
European Journal of Organic Chemistry
COMMUNICATION
iodomethane.[11] It was interesting to find that the benzylsilyl
group fully converted while the arylsilyl group was intact,
affording the methyl ester 4a in 50% yield along with
protodesilylation product 4b in 33% yield (see Supporting
Information Page S19). Moreover, the aromatic C−Si moiety
could be further transfered into aryl iodide in 35% yield in the
presence of iodine monochloride.
Table 2. Scope of arylbenzyl bis(silanes).[a]
[a] Reaction conditions: 1 (0.20 mmol), 2 (0.40 mmol), [Ir(cod)OMe]2 (4.0 mol%), L6 (10 mol%), norbornene (0.24 mmol), 4Å molecular sieves (20.0 mg) in 1.0 mL
of 1,2-dichloroethane under argon atmosphere at 50 °C for 24 h. Isolated yields. The ee values of representative compounds 3a, 3e, 3f, 3i, 3k, 3l, 3m, 3n, 3o,
and 3p were determined by chiral HPLC (see Supporting Information for details). [b] 70 °C. [c] 36 h. [d] 48 h. [e] L3 (10 mol%) was used, in 1.0 mL of toluene. 2-
Np = 2-naphthyl.
in good yields with excellent chemo- and regio-selectivity.
Further
derivatization
of
the
arylbenzyl
bis(silanes)
demonstrated the rich chemistry of these multi-functionalized
organosilanes, which could be useful as versatile building blocks
in synthetic chemistry.
Scheme 2. Derivatization of the arylbenzyl bis(silanes). [a] 3a (0.20 mmol),
CsF (1.0 mmol), CO2 (1 atm), DMF (2.0 mL), 100 °C , 2 h, then MeI (0.40
mmol), Cs2CO3 (0.40 mmol), rt, 30 min. [b] 4a (0.10 mmol), ICl (0.60 mmol),
CH2Cl2 (1.0 mL), 50 °C , 20 h.
Acknowledgements
We are grateful for financial support from the National Natural
Science Foundation of China (21901104), the start-up fund from
Southern University of Science and Technology, Shenzhen
In summary, we have developed an efficient intermolecular
dehydrogenative C−H/Si−H cross-coupling to access bis(silane)
compounds. Under simple and mild conditions, a variety of new
functionalized arylbenzyl bis(silane) compounds were obtained
Science
and
Technology
Innovation
Committee
3
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10.1002/ejoc.202100474
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Keywords: organosilanes • arylbenzyl bis(silanes) • C−H
functionalization • dehydrogenative cross-coupling •
intermolecular C−H silylation
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4
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Entry for the Table of Contents
COMMUNICATION
An efficient intermolecular dehydrogenative C−H/Si−H cross-coupling to access bis(silane) compounds is described. Under simple
and mild conditions, a variety of new functionalized arylbenzyl bis(silane) compounds were obtained in good yields with excellent
chemo- and regio-selectivity from readily available starting materials. Further derivatization of the arylbenzyl bis(silanes)
demonstrated the rich chemistry of these multi-functionalized organosilanes, which could be useful as versatile building blocks in
synthetic chemistry.
5
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