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

Toutov, Anton A.; Liu, Wenbo; Betz, Kerry N.; Fedorov, Alexey; Stoltz, Brian M.; Grubbs, Robert H.

doi:10.1038/nature14126

Cited by 355 publications

(218 citation statements)

References 31 publications

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“…Although significant progress has been made in developing catalysts for aryl C−H silylation, the silylation of alkyl C−H bonds has been far less explored3738. In particular, examples of undirected intermolecular alkyl C−H silylation are few394041, and there is no report of such transformation with trialkoxysilanes. Direct installation of a trialkoxysilyl group via alkyl C−H bond activation generates alkyltrialkoxysilanes, which are not only useful precursors to commercial polymers but also widely used as silylating agents for surface functionalization and as nontoxic transmetalation agents in cross-coupling reactions.…”

Section: Resultsmentioning

confidence: 99%

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

et al. 2016

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Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

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Section: Resultsmentioning

confidence: 99%

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

et al. 2016

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“…Characterization data and copies of the 1 H and 13 a Reaction conditions: 2a (1 mmol), 3 (10 mmol, 10 equiv), 4 (2 mmol, 2 equiv); between each run the catalyst was washed 3 times with dichloromethane, dried with a nitrogen flow, and directly reused. b Determined by gas chromatography.…”

Section: * S Supporting Informationmentioning

confidence: 99%

A Catalytic Peterson-like Synthesis of Alkenyl Nitriles

et al. 2016

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A heterogeneous fluoride catalyst was found to enable the straightforward formation of alkenyl nitriles from the reaction of aldehydes and simple or substituted acetonitriles, in the presence of commercially available silazanes and in solvent-free conditions. The protocol afforded the products in good to excellent yields with selectivity values dependent on the nature of the substrates. It represents an alternative to classic approaches using stoichiometric strong bases, and the catalyst can be easily recovered and reused for consecutive cycles.

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“…1-3). Komplex 2b, welcher zuvor für die dehydrierende Kupplung von Enaminen [8] verwendet worden war, war 2a aus der Hydrosilylierung von Pyridinen [7] überlegen;Katalysator 2c [18] mit einem elektronenarmen Phosphinliganden war ebenfalls weniger effektiv.A ndere Tr iorganosilane als da wären EtMe 2 SiH, MePh 2 SiH und Et 3 SiH nahmen an dieser mehrstufigen Sequenz nicht teil (Tabelle 1, Nr.4-6).…”

Section: Angewandte Chemieunclassified

Katalytische elektrophile C‐H‐Silylierung von Pyridinen ermöglicht durch vorübergehende Aufhebung der Aromatizität

Wübbolt

Oestreich

2015

Angewandte Chemie

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

Cited by 355 publications

References 31 publications

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

A Catalytic Peterson-like Synthesis of Alkenyl Nitriles

Katalytische elektrophile C‐H‐Silylierung von Pyridinen ermöglicht durch vorübergehende Aufhebung der Aromatizität

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