Bronsted Acid Catalysis in Enantioselective Acyl Substitution

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The Chemical Catalysis Program supports Professor Vladimir B. Birman of Washington University for a project that will explore the application of Brønsted acids to catalytic, asymmetric acyl substitution reactions, such as enantioselective O- and S-acylation and enantioselective alcoholysis of chiral acyl donors. The two basic modes of activation that will be applied to several classes of acyl donors are acid-assisted acyl transfer catalysis and direct Brønsted acid catalysis using axially chiral phosphoric acids.The acyl transfer catalysis will utilize primarily achiral carboxylic acids in combination with amidine-based enantioselective acylation catalysts previously developed in the Birman laboratory. These studies will lead to the development of new methods for the nonenzymatic kinetic resolution (KR), dynamic kinetic resolution (DKR), desymmetrization and deracemization of several classes of substrates. The availability of a simple transition state model will be helpful for introducing students to the basics of asymmetric catalysis. Professor Vladimir B. Birman will work in a topical area called asymmetric organocatalysis that is having considerable potential impact in both industry and academia. The research will lead to a better understanding of non-covalent interactions in the chemical community. The broader scientific impact, for process development outside of academia, could be quite significant. Graduate and undergraduate students will be provided more diverse training in synthetic organic chemistry. The recently developed protocol for the DKR of 4-aryl-azlactones is operationally simple, utilizes easily obtainable starting materials and catalysts, and presents an opportunity to discuss many fundamental concepts of organic chemistry. This makes it an ideal candidate for incorporation into the undergraduate laboratory curriculum at Washington University. These steps will further improve the quality of the graduate and undergraduate programs in chemistry at Washington University and help build its strength as one of the leading research institutions in the Midwest.