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Shorter And Improved Access To The Key Tetracyclic Core Of Sarpagine-Macroline-Ajmaline Indole Alkaloids: The Total Synthesis Of Alkaloids Macrocarpines A-G, Talcarpine, N(4)-Methyl-N(4),21-Secotalpinine, Deoxyperaksine, Dihydroperaksine, Talpinine, O-Acetyltalpinine, And N(4)-Methyltalpinine, Md Toufiqur Rahman

Theses and Dissertations

Extension of the asymmetric Pictet-Spengler (P-S) reaction to bulkier Nb-alkylated tryptophan derivatives resulted in a shorter and improved stereospecific access to the key bicyclo[3.3.1]nonane framework of bioactive C-19 methyl substituted sarpagine/macro-line/ajmaline indole alkaloids with excellent diastereoselectivity via internal asymmetric induction. The asymmetric Pictet-Spengler/Dieckmann protocol with bulky Nb-alkyl substituted systems enabled a more direct and two-step shorter route to this key architecture. Complete stereocontrol of the C-19 methyl function in either the α- or β-configuration was achieved which would enable one to gain rapid access to the crucial intermediates for the total synthesis of any member of this group of seventy …

Studies In Molecular Recognition: Non-Proteogenic Amino Acids For Antibiotic Studies And Chemosensors For Recognition And Reporting Of Metal-Ions, Sarah Anne Oehm

Theses and Dissertations

The field of molecular recognition focuses on the selective and reversible binding of small guest molecules to larger host molecules. This dissertation describes synthesis of small molecules as binding guests for enzymatic substrates as well as molecules as host chemosensors to detect and identify metal ions. Two approaches to new antibiotic drugs have been explored, and an array of sensors for the quantitation of aqueous metals is being commercialized.

As strains of deadly bacteria emerge with evolved resistance to known antibiotics, new drugs are needed with novel mechanisms of action. Natural product antibiotics containing enduracididine, a non-canonical amino acid derived …