Silylation of C–H bonds in aromatic heterocycles by an Earth-abundant metal catalyst

@article{Toutov2015SilylationOC,
  title={Silylation of C–H bonds in aromatic heterocycles by an Earth-abundant metal catalyst},
  author={Anton A. Toutov and Wen-Bo Liu and Kerry N Betz and Alexey Fedorov and Brian M Stoltz and Robert H. Grubbs},
  journal={Nature},
  year={2015},
  volume={518},
  pages={80-84}
}
Heteroaromatic compounds containing carbon–silicon (C–Si) bonds are of great interest in the fields of organic electronics and photonics, drug discovery, nuclear medicine and complex molecule synthesis, because these compounds have very useful physicochemical properties. Many of the methods now used to construct heteroaromatic C–Si bonds involve stoichiometric reactions between heteroaryl organometallic species and silicon electrophiles or direct, transition-metal-catalysed intermolecular… Expand
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References

SHOWING 1-10 OF 41 REFERENCES
Rhodium-Catalyzed Intermolecular C–H Silylation of Arenes with High Steric Regiocontrol
TLDR
A catalytic intermolecular C–H silylation of unactivated arenes that manifests very high regioselectivity through steric effects of substituents meta to a potential site of reactivity is reported. Expand
Efficient iridium-catalyzed C-H functionalization/silylation of heteroarenes.
TLDR
An efficient, regioselective protocol for the bipyridine-ligated, iridium-catalyzed C-H functionalization/silyation of a wide variety of heteroarenes under comparatively mild conditions is reported. Expand
Gold-Catalyzed Direct Arylation
TLDR
It is reported that, in the presence of 1 to 2 mole percent of a gold catalyst and a mild oxidant, a wide range of arenes undergo site-selective arylation by arylsilanes to generate biaryls (Ar1-Ar2), with little or no homocoupling, which expedite biaryl preparation. Expand
Direct transition metal-catalyzed functionalization of heteroaromatic compounds.
TLDR
This critical review summarizes the progress made in this field until November 2006 and describes the development of C-H activation methods for direct functionalization of heterocyclic molecules. Expand
Fused heteroaromatic dihydrosiloles: synthesis and double-fold modification.
TLDR
An efficient method for the synthesis of fused heteroaromatic dihydrosiloles via Ni-catalystzed hydrosilylation/intramolecular Ir-catalyzed dehydrogenative coupling of the Si-H bond with the heterOaromatic C-H Bond has been developed and exhibits high functional group tolerance and good regioselectivity. Expand
Cooperative catalytic activation of Si-H bonds by a polar Ru-S bond: regioselective low-temperature C-H silylation of indoles under neutral conditions by a Friedel-Crafts mechanism.
Merging cooperative Si-H bond activation and electrophilic aromatic substitution paves the way for C-3-selective indole C-H functionalization under electronic and not conventional steric control. TheExpand
Ru3(CO)12-catalyzed silylation of benzylic C-H bonds in arylpyridines and arylpyrazoles with hydrosilanes via C-H bond cleavage.
TLDR
Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes and Ru3(CO)12 complex showed high catalytic activity. Expand
Lewis-base silane activation: from reductive cleavage of aryl ethers to selective ortho-silylation
We report a transition-metal-free protocol for the efficient reductive cleavage of diaryl and aryl alkyl ethers. The combination of triethylsilane with common bases forms an unusually powerfulExpand
Direct C-H arylation of electron-deficient heterocycles with arylboronic acids.
TLDR
A direct arylation of a variety of electron-deficient heterocycles with arylboronic acids with inexpensive reagents has been developed, allowing for rapid access to a wide range of arylated heterocycle groups that would be more difficult to access with traditional methods. Expand
Palladium-catalyzed cross-coupling reactions of silanolates: a paradigm shift in silicon-based cross-coupling reactions.
TLDR
A mild and practical palladium-catalyzed cross-coupling of alkenyl-, aryl-, and heteroaryl silanolates has been developed and the mechanistic underpinnings, methodological extensions, and the successful applications of this technology to the synthesis of complex molecules are described. Expand
...
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