Since 2010, our lab has disclosed several successful methodologies for the asymmetric halofunctionalization of olefins, including chlorolactonization of alkene amides and alkene carbamates, chlorocyclization of alkene amides, chlorocyclization of alkene carbamates, chloroetherification of alkene amides, chloroamidation of alkene amides and dichlorination of alkene amides. Despite advancements, mechanistic understanding of these reactions remains largely underdeveloped. the aforementioned halogenation chemistry can be achieved with DCDMH as the chlorenium source. In this study, we explored the effect of the halenium source on reaction rate, to gain a better mechanistic understanding of the interaction between the chlorenium source with other components of the reaction. Match-mismatch behaviors were interrogated as well, using chiral chlorohydantoins. Furthermore, kinetic analysis with different aryl substituted chlorohydantoin showed linear relationship ΔΔG‡ [=RT ln(kAr/kPh)] and HalA, which suggests chlorine transfer in an early transition state. Nonetheless, intermolecular halofunctionalization reactions, seem to behave differently, as evident of radically altered kinetic parameters.

Mechanistic studies of asymmetric chloroetherification reactions

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