Light-enabled, AlCl3-catalyzed regioselective intramolecular nucleophilic addition of non-nucleophilic alkyls to alkynes.

Abstract

Light-enabled, AlCl3-catalyzed regioselective intramolecular nucleophilic cyclization of alkynes using non-nucleophilic alkyls as the nucleophile is reported. Upon photoexcitation, o-alkylphenyl alkynyl ketones can be transferred into (E)-photoenols. Thus, a nucleophilic methylene is formed from the non-nucleophilic alkyl. An AlCl3 catalyst can stabilize the (E)-photoenol intermediate and facilitate further intramolecular nucleophilic cyclization. DFT calculations indicated that the AlCl3-catalyzed cyclization is the regioselectivity determining step.