TY  - UNPB
ID  - pittir9025
UR  - http://d-scholarship-dev.library.pitt.edu/9025/
A1  - Hoye, Adam Thomas
TI  - Synthesis of Natural and Non-Natural Polycylic Alkaloids
Y1  - 2010/09/30/
N2  - Part one of this dissertation describes the synthesis of novel polycyclic natural product-like compounds from dicyclopropylmethylamine starting materials. Using methodology previously developed in our group, products from the initial one-pot multicomponent reaction via the rearrangement of a bicyclo[1.1.0]butane intermediate were successfully transformed into polycyclic systems. These small, medium and large heterocycles mimic complex alkaloids found in nature, and were further elaborated to incorporate additional functionalities.Part two describes our investigation into the parvistemonine class of Stemona alkaloids. We developed a unified strategy to target several related Stemona natural products. A [3,3]-sigmatropic rearrangement was used to relay key stereochemical information across the characteristic pyrrolo[1,2-a]azepine core of these molecules and install contiguous stereocenters in a controlled fashion. This approach produced advanced intermediates towards the syntheses of parvistemonine and sessilifoliamides B and D, and culminated in the first enantioselective total syntheses of sessilifoliamide C and 8-epi-stemoamide.
AV  - public
KW  -  biosynthetic relationship; cyclodehydration/reduction; Eschenmoser-Claisen; hydroindoline; indole; Ireland-Claisen; Johnson-Claisen; organozirconium; orthoester; stenine; transmetallation; tuberostemonine; tuberostemonone; ring-closing metathesis; total synthesis
ER  -