Part I : fluorinated amine stereotriads via allene amination and part II : visible-light-assisted intramolecular amidation of allenes

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Liu, Lu author

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This thesis is divided into two parts. The first part is centered on "Fluorinated Amine Stereotriads via Allene Amination," which is a continuation of our group's efforts on oxidative functionaliza...

This thesis is divided into two parts. The first part is centered on "Fluorinated Amine Stereotriads via Allene Amination," which is a continuation of our group's efforts on oxidative functionalization of allene motifs. This method allows the diastereoselective synthesis of C-F/C-N/C-O stereotriad motifs via a one-pot Rh(II)-catalyzed oxidative allene amination strategy that was developed by our group. The key C-F bond was built by reacting an enesulfamate precursor with the electrophilic fluorination reagent Selectfluor. The F/ N/ O stereotriad afforded thereby is a common scaffold in bioactive and pharmaceutically relevant compounds. In addition, the stereotriad could be transformed to unnatural fluorinated [small alpha]-, [capital beta]-, [small gamma]- amino acids, which are important building blocks in the design of hyperstable protein folds and potential antitumor or antimicrobial agents. The second part focuses on our group's initial efforts towards development of intramolecular amidyl radical addition to allene motifs. Radical addition to allenes has long been a powerful tool to synthesize both carbo- and heterocyclic building blocks since late 1950s. However, early studies of radical addition to allenes usually have shortcomings including harsh reaction conditions, use of toxic organo-tin reagents as initiators, and complicated functionalization of the radical precursors. In addition, employment of allenes as radical acceptors is inevitably accompanied with issues of regioselectivity, stereoselectivity, and chemoselectivity. Therefore, development of mild and tunable ways of generating amidyl radicals that can potentially undergo regio-, chemo-, and stereoselective addition to allenes would be desirable.

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