This review seeks to provide coverage on recent advances in catalytic enantioselective halofunctionalization of alkenes. The aim is to give an overview of various reports, highlighting the new reaction types and strategies developed during the past two years. The scope and challenges of intra- and intermolecular reaction variants are discussed as well.

A highly facile, efficient, and enantioselective bromolactamization of olefinic amides was effected by a carbamate catalyst and ethanol additive. The amide substrates underwent N-cyclization predominantly to give a diverse range of enantioenriched bromolactam products containing up to two stereogenic centers.

The stereoselective bromofunctionalization of alkenes, particularly the enantioselective format, has been a subject of intense research in recent years. The ground-breaking works are documented in recent reviews. On the other hand, this account will provide an insight into our group's approach in tackling the challenges in enantioselective bromocyclization of alkenes as well as the development of diastereoselective N-bromosuccinimide-initiated multicomponent reactions.

An efficient, catalyst-free, and metal-free bromoamidation of unactivated olefins has been developed. 4-(Trifluoromethyl)benzenesulfonamide and N-bromosuccinimide were used as the nitrogen and halogen sources, respectively. The methodology is applicable to both cyclic and aliphatic olefins.

A complete switch of regioselectivity in the aminobromination of olefins is realized from delicate changes in the reaction temperature from 25 °C to 40 °C and the atmosphere from air to argon, under catalyst‐free conditions. The resulting α‐bromoamides can be transformed easily to high‐value compounds (e.g., Clobenzorex). Mechanistic studies revealed that the reaction went through a radical pathway governed by in‐situ generated bromo(tosyl)amine (TsNHBr).magnified image