Development of a Universal Enantioselective Halofunctionalization Strategy

Electrophilic halofunctionalization of alkenes is a fundamental transformation of organic chemistry.

Asymmetric halofunctionalizations would deliver nonracemic chiral halogenated molecules, which are highly versatile synthetic building blocks in the construction of structural motifs common to natural products, pharmaceuticals, and functional materials.

While such compounds are increasingly demanded by academics and industries, their utilization is hindered by the lack of robust general methods for asymmetric halofunctionali­zation of alkenes.Our goal is to develop the first general protocol for intermolecular asymmetric halogenation of alkenes.

This will be achieved using a modular catalytic system based on halogen bonding, a field the applicant is internationally leading expert in.

A reactive halenium ion will be held in a halogen bond complex positioned in a chiral environment, to which the alkene will coordinate.

The modular nature of the system will ensure unprecedented control of steric and electronic factors influencing the transformation and applicability with all four types of halogens.

Specifically, we willsynthesize chiral ligands capable of efficient stabilization of halenium ions,gain understanding of the structure of the stabilized chiral halonium-olefin complexes,further develop the halogenation agent to a catalytic asymmetric halofunctionalization system, andapply the developed technique to synthesize chiral building blocks of universal importance.