Iron-Catalyzed Carbometalation of Propargylic and Homopropargylic Alcohols
Donghui Zhang,Joseph M. Ready +1 more
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It is demonstrated that Fe(III) salts are effective precatalysts for the carbometalation of alkynes through an unusual addition/cyclization reaction to generate cyclic dienes.Abstract:
Nucleophilic addition to alkynes represents an attractive approach to the synthesis of olefins. Obstacles to this strategy include the low reactivity of alkynes toward many organometallic reagents and difficulties associated with controlling the regioselectivity of addition. Here we demonstrate that Fe(III) salts are effective precatalysts for the carbometalation of alkynes. Primary and secondary propargylic and homopropargylic alcohols react with alkyl and aryl Grignard reagents to provide Z-allylic and -homoallylic alcohols as single stereo and regioisomers. Alkylation and arylation occur distal to the alcohol. Common oxygen protecting groups and tertiary nitrogens are tolerated. The intermediate vinyl magnesium or iron species can be trapped with a variety of electrophiles including aldehydes, allyl bromide, and N-bromosuccinimide. Diyne substrates undergo an unusual addition/cyclization reaction to generate cyclic dienes. A brief discussion of mechanism is included.read more
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Iron-Catalyzed C-H Bond Activation.
TL;DR: This review includes reactions that take place via reactive organoiron intermediates, and it covers the reactions of simple substrates and substrates possessing a directing group that anchors the catalyst to the substrate, providing an overview of iron-mediated and iron-catalyzed C-H activation reported in the literature by October 2016.
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Stereocontrolled synthesis of tetrasubstituted olefins.
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Iron-catalyzed C-C bond formation by direct functionalization of C-H bonds adjacent to heteroatoms.
Zhiping Li,Rong Yu,Haijun Li +2 more
TL;DR: Transition-metal-catalyzed C H functionalization for the atomand step-economical synthesis of functional molecules has attracted tremendous efforts in both academia and industry, with high efficiency, low cost, and minimal environmental impact.
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A Cheap Metal for a “Noble” Task: Preparative and Mechanistic Aspects of Cycloisomerization and Cycloaddition Reactions Catalyzed by Low-Valent Iron Complexes
Alois Fürstner,Kaisuke Majima,Ruben Martin,Helga Krause,Egmont Kattnig,Richard Goddard,Christian W. Lehmann +6 more
TL;DR: The structures of ferrates 1 and 4 in the solid-state reveal the capacity of the reduced iron center to share electron density with the ligand sphere, which is thought to be responsible for the ease with which different enyne or diyne substrates undergo oxidative cyclization as the triggering event of the observed skeletal reorganizations.
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Metal-catalyzed cross-coupling reactions
TL;DR: In this paper, the authors present an approach to the formation of C-X (X = N, O, S) bonds in metal-catalyzed cross-coupling reactions.
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Synthetic applications of organochlorozirconocene complexes
Peter Wipf,Heike Jahn +1 more
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Controlled carbometalation as a new tool for carbon-carbon bond formation and its application to cyclization
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