Loading...
SYNTHESIS AND REACTIVITY OF MEDIUM SIZED CYCLIC ETHERS: EFFORTS TOWARDS THE BIOINSPIRED TOTAL SYNTHESIS OF HELIANNUOL C AND TOTAL SYNTHESIS OF HELIANNUOL A AND K
Sherwood, Matthew
Sherwood, Matthew
Citations
Altmetric:
Genre
Thesis/Dissertation
Date
2025-08
Advisor
Committee member
Group
Department
Chemistry
Permanent link to this record
Collections
Research Projects
Organizational Units
Journal Issue
DOI
https://doi.org/10.34944/dgze-1a41
Abstract
Heliannuols are a family of naturally occurring sesquiterpenes found in the common sunflower (helianthus annuus). To date, heliannuols A-N have been isolated, with many possessing strong allelopathic properties, resulting in significant interest from the agrichemical industry as environmentally benign herbicides. All heliannuols feature synthetically challenging medium sized ring systems that have consequently hindered extensive investigations into their properties and biogenesis. Heliannuol C features a 7-membered benzoxecane scaffold with two distinct stereocenters. The proposed biosynthesis of heliannuol C proceeds via an acid mediated ring contraction of a yet to be isolated, oxidized species of the 8-membered heliannuol A. To probe this biosynthetic pathway, a novel high yielding, low step-count synthesis of heliannuol A will be employed. A common intermediate is subsequently transformed to the oxidized allylic alcohol species, a proposed key intermediate towards heliannuol C. Efforts towards the bioinspired total synthesis of heliannuol C are discussed in Chapter 3. Optimization of the synthesis of heliannuol A as well as the total synthesis of heliannuol K are discussed in Chapter two. Additionally improvements to a telescoped one-pot ring expansion, functionalization sequence was also accomplished. The work described herein involves the successful total synthesis of two natural products (Chapter 2), several unnatural analogs (Chapter 3), and improved methods for accessing functionalized, medium size cyclic ethers (Chapter 5).
Description
Citation
Citation to related work
Has part
ADA compliance
For Americans with Disabilities Act (ADA) accommodation, including help with reading this content, please contact scholarshare@temple.edu