A new copper-catalyzed enantioselective aza-Freidel-Crafts reaction between phenols and N-sulfonyl aldimines that provides chiral secondary benzylamines in good to excellent yields and excellent enantioselectivities (up to 99% ee) is disclosed. In particular, excellent scope with alkylimines was observed for the first time. The synthetic utility of the products was demonstrated in the first enantioselective synthesis of a dual orexin receptor antagonist, a compound that contains an amine-bearing stereocenter adjacent to a bis- ortho-functionalized arene.

The oxidative coupling of alkyltrifluoroborates with heteroatom-tethered vinylarenes leads to a broad range of saturated oxygen and nitrogen heterocycles.

Alkene aminooxygenation reactions provide vicinal amino alcohol derivatives, moieties that frequently appear in catalysts, drugs, and other valuable molecules. This Chapter reviews transition‐metal‐catalyzed aminooxygenations of alkenes and aims to serve as a guide in the selection of appropriate reagents and procedures for specific substrate classes and desired transformations. Inter‐ and intramolecular aminooxygenation reactions catalyzed by osmium, palladium, platinum, gold, copper, iron, iridium, rhodium, ruthenium, and manganese are presented, as is a discussion of the factors involved in reactivity and selectivity. A brief section on non‐metal catalyzed alkene aminohydroxylation is also included. A complete set of alkene aminooxygenation reactions through mid‐2020 is provided in the Tabular Survey.