APPLICATIONS OF ORGANIC PHOTOREDOX CATALYSIS IN THE DEVELOPMENT OF ALKENE FUNCTIONALIZATION METHODS TOWARD THE SYNTHESIS OF α–BENZYLOXYAMINO- AND HALO-LACTONES

Cavanaugh, Cortney

APPLICATIONS OF ORGANIC PHOTOREDOX CATALYSIS IN THE DEVELOPMENT OF ALKENE FUNCTIONALIZATION METHODS TOWARD THE SYNTHESIS OF α–BENZYLOXYAMINO- AND HALO-LACTONES Public Deposited

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March 21, 2019

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Cavanaugh, Cortney
- Affiliation: College of Arts and Sciences, Department of Chemistry

Abstract

I. Introduction To Organic Photoredox Catalysis An overview of the photophysical and electrochemical components of organic photoredox catalysis and its applications in alkene functionalization reactions is addressed. II. Synthesis of α-Benzyloxyamino-γ-Butyrolactones Via a Polar Radical Crossover Cycloaddition Reaction The development of a direct catalytic synthesis of substituted α-benzyloxyamino-γ-butyrolactones, beginning from simple oxime acids and alkenes, is discussed. The substituted O-benzyloxime acid starting materials undergo cyclization with oxidizable alkenes, via Polar Radical Crossover Cycloaddition (PRCC) reactions. The catalytic reaction is carried out using an acridinium photooxidant and substoichiometric amounts of a redox-active cocatalyst. The utility of this methodology is demonstrated through the cyclization of 3 oxime acids and 19 oxidizable olefins to generate 21 highly substituted α-amino lactone products. III. Reversing The Regioselectivity Of Halofunctionalization Reactions Through Cooperative Photoredox And Copper Catalysis A novel method for reversing the regioselectivity of classic alkene halofunctionalization reactions is presented. This transformation relies on the implementation of a dual-catalytic system, incorporating the use of an acridinium photoredox catalyst in conjunction with a copper cocatalyst. The utility of the method is demonstrated through the application of chloro- and bromo-functionalization conditions in both an intra- and intermolecular fashion. Over 15 synthetically and biologically relevant halo-lactones are accessed in a highly regioselective fashion.

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