Previous research in the Tunge group has established efficient, one-step methods to synthesize α-aryl-γ-ketoacids and methyl ester derivatives via photocatalytic decarboxylative acylation. This project explores how yields were affected upon scaling up the reaction size and investigates potential reactions in which these compounds might be utilized. In one application, both the γ-ketoacid and methyl ester were used to synthesize a vinyl lactone when allowed to react with a vinyl Grignard reagent. Of the two potential synthetic routes, it was determined that the methyl ester leads to a higher conversion of starting material to the lactone compared to the ketoacid. It was also determined that increasing the equivalents of Grignard reagent used does not necessarily improve the conversion to the desired product. After purification, the resulting lactone was then subjected to dual-catalytic conditions established by previous research in intermolecular decarboxylative allylation. By utilizing both an oxidizing photocatalyst (PC) and a palladium(0) catalyst, it was predicted that the lactone could undergo intramolecular cyclization via decarboxylative allylation. Based upon initial reaction results, it appeared that the elimination mechanism may have outcompeted the substitution pathway, resulting in a functionalized diene instead of the proposed cyclic products. This reaction may present a novel route to synthesizing functionalized dienes.

Photoredox catalysis with decarboxylative coupling

ACS Spring 2022

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