Mechanistic Studies and Development of Novel Palladium Catalyzed Methods Towards Functionalized Building Blocks

The following dissertation will highlight the discovery and development of two new palladium-catalyzed reactions for both academic and industrial applications. The common theme of these projects is catalysis that are intertwined with detailed mechanistic interrogations to ultimately identify the best process to deliver the corresponding products in high yield and purity. This dissertation will demonstrate the synthesis of substituted allenes, a class of unique and underutilized substrates that represent the only common functional group in organic chemistry that can possess axial chirality. Toward this goal, the first Pd-catalyzed intermolecular alkynyl Heck reaction between alkynes and aryl chlorides was developed and optimized to provide substituted allenes in good yields. Preliminary data on the asymmetric alkynyl-Heck reaction between alkynes and aryl chlorides will also be disclosed. This dissertation will also disclose an academic/industrial collaboration between the Frantz group at UTSA and the Chemical Process Group (CPD) at Bristol Myers Squibb (BMS). A unique Pd-catalyzed chemoselective alkylation of a class of ambident nucleophiles, 2-quinolinones, was developed as part of an active scale-up campaign at BMS and as a general method for the synthetic organic chemistry community.