eprintid: 9025
rev_number: 5
userid: 6
dir: disk0/00/00/90/25
datestamp: 2011-11-10 19:58:40
lastmod: 2016-11-15 13:48:46
status_changed: 2011-11-10 19:58:40
type: thesis_degree
metadata_visibility: show
contact_email: ath7@pitt.edu
item_issues_count: 0
eprint_status: archive
creators_name: Hoye, Adam Thomas
creators_email: ath7@pitt.edu
creators_id: ATH7
title: Synthesis of Natural and Non-Natural Polycylic Alkaloids
ispublished: unpub
divisions: sch_as_chemistry
full_text_status: public
keywords:  biosynthetic relationship; cyclodehydration/reduction; Eschenmoser-Claisen; hydroindoline; indole; Ireland-Claisen; Johnson-Claisen; organozirconium; orthoester; stenine; transmetallation; tuberostemonine; tuberostemonone; ring-closing metathesis; total synthesis
abstract: 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.
date: 2010-09-30
date_type: completed
institution: University of Pittsburgh
refereed: TRUE
etdcommittee_type: committee_chair
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_name: Wipf, Peter
etdcommittee_name: Day, Billy
etdcommittee_name: Curran, Dennis
etdcommittee_name: Floreancig, Paul
etdcommittee_email: pwipf@pitt.edu
etdcommittee_email: bday@pitt.edu
etdcommittee_email: curran@pitt.edu
etdcommittee_email: florean@pitt.edu
etdcommittee_id: PWIPF
etdcommittee_id: BDAY
etdcommittee_id: CURRAN
etdcommittee_id: FLOREAN
etd_defense_date: 2010-08-16
etd_approval_date: 2010-09-30
etd_submission_date: 2010-08-09
etd_access_restriction: 5_year
etd_patent_pending: FALSE
assigned_doi: doi:10.5195/pitt.etd.2011.9025
thesis_type: dissertation
degree: PhD
committee: Peter Wipf (pwipf@pitt.edu) - Committee Chair
committee: Billy Day (bday@pitt.edu) - Committee Member
committee: Dennis Curran (curran@pitt.edu) - Committee Member
committee: Paul Floreancig (florean@pitt.edu) - Committee Member
etdurn: etd-08092010-110833
other_id: http://etd.library.pitt.edu/ETD/available/etd-08092010-110833/
other_id: etd-08092010-110833
citation:   Hoye, Adam Thomas  (2010) Synthesis of Natural and Non-Natural Polycylic Alkaloids.  Doctoral Dissertation, University of Pittsburgh.    (Unpublished)  
document_url: http://d-scholarship-dev.library.pitt.edu/9025/1/hoyeat_ETD2010.pdf