Peptides are attractive scaffolds for development of asymmetric catalysts in synthetic organic chemistry because they are modular in both the sidechain identity and stereochemistry of their constituent amino acids. Peptide catalysts have thus been applied to a very broad range of asymmetric transformations, including acylations, epoxidations, and electrophilic aromatic bromination. In the present work, we have applied a combinatorial 'one-bead-one-catalyst' approach used to discover asymmetric epoxidation catalysts to the asymmetric Baeyer-Villiger oxidation of cyclic ketones. Employing this method with polystyrene-immobilized peptides, we have screened over one thousand unique peptide sequences that contain aspartic acid. We have discovered multiple sequences that display promising selectivity for the kinetic resolution and desymmetrization of aryl cyclohexanones. Current efforts are targeted toward improving observed stereoselectivities via the preparation of second generation peptide libraries and the incorporation of directing groups into our substrates.

Combinatorial discovery of aspartate-containing peptide catalysts for the asymmetric Baeyer-Villiger oxidation

248th National Meeting (2014)

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