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Organic Chemistry Seminar

Wednesday, April 24, 2019
4:00pm to 5:00pm
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Noyes 153 (J. Holmes Sturdivant Lecture Hall)
New Strategies for the Catalytic Enantioselective Synthesis of Chiral Amines and Other Challenging Scaffolds
Steve Malcolmson, Assistant Professor of Chemistry, Department of Chemistry, Duke University,

The development of new methods for the stereoselective synthesis of chiral amines is a compelling objective in organic synthesis as these structures are found in a large number of biologically active compounds. Yet many amine motifs remain difficult to prepare in an efficient manner, especially through complexity-building carbon–carbon bond-forming reactions and/or in atom economical ways. In this lecture, I will describe our work in two areas of enantioselective catalysis to prepare chiral amines: 1) carbon–carbon bond formations via electrophilic additions to 2-azadienes, which act as enamine umpolung reagents, and 2) nucleophilic additions of aliphatic amines and anilines to acyclic 1,3-dienes (hydroamination).

Cu-catalyzed reductive couplings of azadienes—virtually unexplored reagents—with ketones and imines has enabled the synthesis of challenging, sterically congested vicinal amino alcohols and diamines, while Pd-catalyzed fluoroarylation of difluoroazadienes has permitted access to alpha-trifluoromethyl benzylic amines. In the latter area, the development of a family of electron deficient Pd–PHOX catalysts for hydrofunctionalization has enabled regio- and enantioselective addition of Lewis basic amines to dienes that furnish allylic amines. Extension to diene hydroalkylation with beta-dicarbonyl-like pronucleophiles delivers myriad unsaturated carbonyl products in atom economical carbon–carbon bond-forming transformations.

For more information, please contact Annette Luymes by phone at x6016 or by email at [email protected].