On the Mechanism of Au-Catalyzed Enynamide-yne Dehydro-Diels-Alder Reactions: An Experimental and Computational Study.

Gold-catalyzed dehydro-Diels-Alder reactions of ynamide derivatives allow efficient access to a variety of N-containing aromatic heterocycles. A dual gold catalysis mechanism was postulated for transformations involving the formation of C-C bonds by reaction between a terminal alkyne and an enynamide fragment. In this article, complete experimental and computational investigations into the mechanism of such a transformation are reported.

Diastereoselective Intramolecular Hydride Transfer Triggered by Electrophilic Halogenation of Aryl Alkenes.

Diastereoselective hydride transfer could be triggered by electrophilic halogenation (bromination or fluorination) of homoallylic alcohol O-Bn ethers. The resulting diastereomerically enriched haloalkyl alcohols underwent subsequent intramolecular nucleophilic substitution to afford the corresponding tetrahydrofurans.

Gold-Catalyzed Formal Dehydro-Diels-Alder Reactions of Ene-Ynamide Derivatives Bearing Terminal Alkyne Chains: Scope and Mechanistic Studies.

A new protocol for the synthesis of a variety of N-containing aromatic heterocycles by a formal gold-catalyzed dehydro-Diels-Alder reaction of ynamide derivatives has been developed. Deuterium-labeling experiments and kinetic studies support the involvement of a dual gold catalysis mechanism in which a gold acetylide moiety adds onto an aurated keteneiminium.