Cinchona alkaloid dimer catalysts, like (DHQD)<sub>2</sub>PHAL, are well known catalysts for a multitude of asymmetric chloro-functionalization of alkenes. But the mechanism of these reactions are relatively unexplored. Even though each reaction is fundamentally a result of electrophilic addition of chlorenium and a nucleophilic addition of some nucleophile to an alkene, stereochemical outcomes of each of these events have been shown to be independently controlled by the catalyst. Furthermore, it has also been shown that stereo-chemical outcomes by the same catalyst can be completely switched based on the alkene substrate, solvent or nucleophile used, while retaining high selectivity. These results indicate that the underlying mechanism of these reactions are controlled by diverse number of factors and could be very different on each case. A better understanding of the mechanistic landscape of these reactions, and factors that control them would likely pave the way for more efficient asymmetric chloro-functionalization reactions. This presentation aims to illustrate some of our most recent findings from a comprehensive investigation of these reactions using various kinetic, spectroscopic, computational and crystallographic techniques.

Mechanism of cinchona-alkaloid catalyzed asymmetric chloro-functionalization of alkenes

2019 Fall National Meeting

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