Total synthesis of marine terpenoids
type: CreativeWork
description: Complex architectures of marine terpenoids and vast assortments of their scaffolds have served as a proving ground for synthetic chemists, inspiring them to develop, assess, and test new methodologies and disconnections. Moreover, besides advancing the field of organic synthesis, marine natural products have also had an immense influence on medicinal chemistry providing new chemical leads for further development to combat life-threatening diseases. Accordingly, several promising families of marine terpenoids were identified to explore their chemistry and biology. The first chapter of this dissertation describes a full account of our synthetic endeavors towards isomalabaricane triterpenoids, natural products discovered 40 years ago in marine sponges of genera Stelleta, Jaspis, Rhabdastrella, and Geodia. Studies showed that these molecules possess valuable biological properties, such as high cytotoxicity, selectivity over non-transformed cells and, hypothetically, a novel mechanism of action. Consequentially, this family of natural products has attracted significant attention from the synthetic community to solve the problem of sustainable supply, and thereby enable further investigation. All attempts however, have failed. Perhaps this is no surprise as the unique structure of isomalabaricanes encompasses highly strained trans-syn- trans perhydrobenz[e]indene core that poses a great challenge. We have been able to develop a series of unconventional transformations to assemble the core architecture in an expedient and enantioselective fashion. To facilitate the development of strategy and completion of the total synthesis, a number of tools at our disposal were utilized, such as computational techniques and a high-throughput screening platform. Enormous strain associated with the core motif manifested itself in various unforeseen reactivities, which could be avoided only upon judicious orchestration of our synthetic manipulations. Finally, our preliminary results revea…
abstract: Complex architectures of marine terpenoids and vast assortments of their scaffolds have served as a proving ground for synthetic chemists, inspiring them to develop, assess, and test new methodologies and disconnections. Moreover, besides advancing the field of organic synthesis, marine natural products have also had an immense influence on medicinal chemistry providing new chemical leads for further development to combat life-threatening diseases. Accordingly, several promising families of marine terpenoids were identified to explore their chemistry and biology. The first chapter of this dissertation describes a full account of our synthetic endeavors towards isomalabaricane triterpenoids, natural products discovered 40 years ago in marine sponges of genera Stelleta, Jaspis, Rhabdastrella, and Geodia. Studies showed that these molecules possess valuable biological properties, such as high cytotoxicity, selectivity over non-transformed cells and, hypothetically, a novel mechanism of action. Consequentially, this family of natural products has attracted significant attention from the synthetic community to solve the problem of sustainable supply, and thereby enable further investigation. All attempts however, have failed. Perhaps this is no surprise as the unique structure of isomalabaricanes encompasses highly strained trans-syn- trans perhydrobenz[e]indene core that poses a great challenge. We have been able to develop a series of unconventional transformations to assemble the core architecture in an expedient and enantioselective fashion. To facilitate the development of strategy and completion of the total synthesis, a number of tools at our disposal were utilized, such as computational techniques and a high-throughput screening platform. Enormous strain associated with the core motif manifested itself in various unforeseen reactivities, which could be avoided only upon judicious orchestration of our synthetic manipulations. Finally, our preliminary results revea…
author: Boyko, Yaroslav
language: en
keywords: total synthesis, terpenes, isomalabaricanes, norcembranoids, polyene cyclization, annulation strategy
date published: 2021-09-17T04:03:56Z
date modified: 2026-07-22T22:24:52Z
provider: University of Illinois - Urbana-Champaign
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Illinois at Urbana-Champaign

PropertyValue
property ID: Handle
value: http://hdl.handle.net/2142/110771