Stereoselective Synthesis of Diazaheterocycles by Decarboxylative Asymmetric Allylic Alkylation

Author: Sun, Alexander Wang

Year: 2019

Degree: Dissertation (Ph.D.)

Advisor: Stoltz, Brian M.

Committee Members: Dervan, Peter B.; Grubbs, Robert H.; Davis, Mark E.; Stoltz, Brian M.

Option: Chemistry

DOI: 10.7907/E2YS-GJ06

Abstract

The Stoltz group has developed transition-metal catalyzed methods to synthesize quaternary and tetrasubstituted stereocenters over the past fourteen years. Using iridium, palladium, copper, and nickel, the group has synthesized a myriad cyclic and acylic quaternary motifs of incredible synthetic and medicinal utility. This thesis presents several projects that further expand the scope of Pd-catalyzed decarboxylative allylic alkylation and examine its applications to the synthesis of medicinally important small molecules. The synthesis of chiral gem-disubstituted five-, six-, and seven-membered diazaheterocycles is presented. Their utility as building blocks for complex medicinal compounds is highlighted. Then, we explore the utility of gem-disubstituted heterocycles in the context of medicinal chemistry.

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