The utilization of a halogen bond in a number of chemical fields is well-known. Surprisingly, the incorporation of this useful noncovalent interaction in chemical reaction engineering is rare. We disclose here an uncommon use of halogen bonding to induce intermolecular Csp 3–H amination while enabling a hydrogen atom transfer relay strategy to access privileged pyrrolidine structures directly from alkanes. Mechanistic studies support the presence of multiple halogen bond interactions at distinct reaction stages.

A novel iodide-catalyzed intermolecular aminooxygenation strategy is described here. Amide is used as the O- and N- source to probe for regiocontrol strategies. Notably, simple additives can be selectively introduced to achieve regiodivergent oxyamination processes for electronically activated alkenes while being regio-complementary for unactivated alkenes. Our preliminary data demonstrates that this regiocontrol strategy based on nucleophile can also be applied in asymmetric processes using chiral hypervalent iodine catalysis.

A new class of intermolecular olefin aminooxygenation reaction is described. This reaction utilizes the classic halonium intermediate as a regio‐ and stereochemical template to accomplish the selective oxyamination of both activated and unactivated alkenes. Notably, urea chemical feedstock can be directly introduced as the N and O source and a simple iodide salt can be utilized as the catalyst. This formal [3+2] cycloaddition process provides a highly modular entry to a range of useful heterocyclic products with excellent selectivity and functional‐group tolerance.

An intermolecular sulfenoamination reaction utilizing a stable sulfur precursor with a broad range of alkene structures is described. More importantly, these reactions proceed in a highly regio- and stereoselective manner to afford interesting heterocyclic motifs ready for biological studies. In addition, a highly regiodivergent approach to access the opposite regioisomers for styrene derivatives was also developed.

Intermolecular alkene difunctionalizations for the direct synthesis of saturated heterocycles.