Enantioselective olefin halofunctionalization has proven to be an enabling strategy in the synthesis of biologically-active natural products with halogen-bearing stereocenters. As previously reported, our lab has discovered that enantioselective bromochlorination and dichlorination of allylic alcohols can be promoted by a chiral Ti(IV) complex. A wide range of substrates are well-tolerated under both conditions, and we have undertaken combined mechanistic and computational studies to elucidate how the enantio- and regioselectivity are controlled in these reactions. Notably, kinetic isotope effect studies demonstrate striking differences in bromo- and chlorofunctionalization processes. Moreover, we leverage our mechanistic study to illuminate differences in substrate scope between bromochlorination and dichlorination reactions, particularly regarding <i>trans</i>-disubstituted olefins.

Mechanistic insights into titanium-catalyzed dihalogenation: Distinctions in bromonium and chloronium pathways

ACS Fall 2021

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