A functional group tolerant cobalt-catalyzed method for the intermolecular hydrofunctionalization of alkenes with oxygen- and nitrogen-based nucleophiles is reported. This protocol features a strategic use of hypervalent iodine­(III) reagents that enables a mechanistic shift from conventional cobalt–hydride catalysis. Key evidence was found supporting a unique bimetallic-mediated rate-limiting step involving two distinct cobalt­(III) species, from which a new carbon–heteroatom bond is formed.

Abstractα-Tertiary amides are of great importance for medicinal chemistry. However, they are often challenging to access through conventional methods due to reactivity and chemoselectivity issues. Here, we report a single-step approach towards such amides via cobalt-catalyzed intermolecular oxidative hydroamidation of unactivated alkenes, using nitriles of either solvent- or reagent-quantities. This protocol is selective for terminal alkenes over groups that rapidly react under known carbocation amidation conditions such as tertiary alcohols, electron-rich alkenes, ketals, weak C−H bonds, and carboxylic acids. Straightforward access to a diverse array of hindered amides is demonstrated, including a rapid synthesis of an aminoadamantane-derived pharmaceutical intermediate.

Visible-light-induced triple-domino cyclization between aryl alkynoates and diethyl bromomalonate was developed for the synthesis of indeno-coumarins.