Gold(I)-Catalyzed Hydroaminaloxylation and Petasis–Ferrier Rearrangement Cascade of Aminaloalkynes

An efficient method has been developed to generate a diverse array of indolizidines and quinolizidines from readily available aminaloalkynes via a gold­(I)-catalyzed hydro­aminal­oxylation and Petasis–Ferrier rearrangement cascade. The method enabled a formal synthesis of (±)-antofine

Aminoindolines versus Quinolines: Mechanistic Insights into the Reaction between 2-Aminobenzaldehydes and Terminal Alkynes in the Presence of Metals and Secondary Amines

DFT computational studies in the cyclization of aminoalkyne (see structure), which is generated in situ by 2-aminobenzaldehydes and terminal alkynes in the presence of metals and secondary amines, has been investigated. The study revealed that the mode of cyclization (<i>exo</i> vs <i>endo</i>) depends on the protecting group on nitrogen, the oxidation state of copper, and substitution on alkyne

Cross-Coupling Reactions of Aryldiazonium Salts with Allylsilanes under Merged Gold/Visible-Light Photoredox Catalysis

A method for the cross-coupling reactions of aryldiazonium salts with trialkylallylsilanes via merged gold/photoredox catalysis is described. The reaction is proposed to proceed through a photoredox-promoted generation of an electrophilic arylgold­(III) intermediate that undergoes transmetalation with allyltrimethylsilane to form allylarenes

Gold vs Rhodium Catalysis: Tuning Reactivity through Catalyst Control in the C–H Alkynylation of Isoquinolones

A site-selective C-4/C-8 alkynylation of isoquinolones catalyzed by gold and rhodium complexes is reported. A broad range of synthetically useful functional groups (−F, −Cl, −Br, −CF₃, −OMe, alkyl, etc.) were tolerated, providing an efficient and robust protocol for the synthesis either C-4- or C-8-alkynylated isoquinolones