(DHQD)2PHAL and its analogs have been reported to catalyze numerous asymmetric halo-functionalization reactions. Yet, there is a critical dearth in detailed mechanistic studies of these reactions in the literature. In fact, recent reports on the mechanism of uncatalyzed olefin halo-functionalization has already begun challenging “conventional” mechanistic interpretations. For instance, recent reports have suggested that the nucleophile could be playing a role in pre-activating the alkenes before the electrophile could attack. This contradicts textbook schematics where the nucleophile is portrayed as just a trapping agent for the intermediate generated after the electrophilic attack of halirenium on the alkene. This inevitably demanded a deeper investigation into the mechanism of catalyzed, asymmetric versions of halo-functionalization reaction. We undertook a comprehensive kinetic analysis of these (DHQD)2PHAL catalyzed asymmetric halo-functionalization reaction, that is backed by computational modeling. Kinetic analysis would provide insight into the molecularity of the rate determining step which ultimately would inform us about the catalytic cycle. Ultimately, our mechanistic studies have unearthed a surprisingly diverse set of mechanisms among various asymmetric halo-functionalization that switches with change in factors like, alkene functional group handle, solvent, as well as nucleophile.

Mechanistic insight into (DHQD)2PHAL catalyzed asymmetric chloro-functionalization of olefins

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.