Graduate Thesis Or Dissertation
 

Synthetic studies toward the total synthesis of azaspiracid-1

Público Deposited

Contenido Descargable

Descargar PDF
https://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/7h149t10p

Descriptions

Attribute NameValues
Creator
Abstract
  • Azaspiracid-1, a novel marine toxin that contains 9 rings and 20 stereogenic centers, has drawn considerable attention from synthetic groups worldwide due to its structural complexity, which includes a unique trioxabisspiroketal fused to a tetrahydrofuran ring (ABCD rings), a piperidine-tetrahydrofuran spiroaminal system fused to a 2,9-dioxabicyclo[3.3.1]nonane system (FGHI rings), a connecting six-membered cyclic hemiketal bridge (E ring) and a γ,δ-unsaturated terminal carboxylic acid side chain. Our efforts toward the total synthesis of azaspiracid-1 led to the completion of both C1-C26 northern and C27-C40 southern halves of azaspiracid-1. Herein, our improved and scalable synthetic studies toward the total synthesis of azaspiracid-1 is described. In particular, an improved and scalable synthesis of sulfone 3.6 with a key one-pot ketalization and methylation of ketone 3.22 to methylated hemiketal 3.24 is illustrated. A total 19 mmol of sulfone 3.6 has been prepared by this approach. An improved and scalable synthesis of aldehyde 3.7 utilizing allyl bromide 3.31 to couple with Evans auxiliary 3.33 has been developed. A total of 10 mmol of aldehyde 3.7 has been prepared by this approach. An improved synthesis toward the ABC ring fragment 3.52 with a high yield Julia coupling step is shown. Large scale improved syntheses of the linkage fragment 3.2, the aldehyde fragment 4.9 and the azide fragment 4.10 of the southern portion of (–)-azaspiracid-1 have been described. With an abundant material prepared by this scalable improved approach, we are confident that completing the total synthesis of (–)-azaspiracid-1 will occur in the near future.
License
Resource Type
Fecha Disponible
Fecha de Emisión
Degree Level
Degree Name
Degree Field
Degree Grantor
Commencement Year
Advisor
Committee Member
Academic Affiliation
Non-Academic Affiliation
Subject
Declaración de derechos
Publisher
Peer Reviewed
Language
Replaces

Relaciones

Parents:

This work has no parents.

En Collection:

Elementos

Miniatura Título Fecha de subida Visibilidad Acciones
file details supplemental NMR.pdf.pdf 08/19/2017 Público
file details SuDong2012.pdf 08/19/2017 Público