Unlocking the Chain-Walking Process in Gold Catalysis

Abstract

The successful realization of gold-catalyzed chain-walking reactions, facilitated by ligand-enabled Au(I)/Au(III) redox catalysis, has been reported for the first time. This breakthrough has led to the development of gold-catalyzed annulation reaction of alkenes with iodoarenes by leveraging the interplay of chain-walking and π-activation reactivity mode. The reaction mechanism has been elucidated through comprehensive experimental and computational studies.

Rhodium(III)-Catalyzed Remote Hydroamidation of Internal Alkenes Via Chain Walking

“…The intermolecular hydroamination of alkenes is a straightforward and useful method to add complexity to readily available feedstock molecules while forging a desirable C–N bond. As such, this transformation has recently seen great development, with many reports of transition-metal-catalyzed hydroamination − and hydroamidation − procedures having both Markovnikov and anti-Markovnikov selectivities and using a variety of nitrogen sources (Scheme A). − Photoredox methods − have also been developed, as well as other radical-based procedures. , Less explored is the remote hydroamination of alkenes, by which a position distal to the original double bond is functionalized, usually via an alkene chain walking mechanism. − These remote functionalizations are attractive for multiple reasons. Prime among these is the ability to functionalize specific unactivated sp 3 carbons.…”