Developing Chiral Synthons for Polyketide-Based Natural Product Synthesis via Stereospecific Oxonia-Cope Rearrangement Público

Abstract

Homoallylic alcohols 1 and 2 underwent stereospecific Lewis acid-catalyzed transfer of the bispropionate unit with different aldehydes. By applying this powerful methodology, the synthesis of (-)-invictolide was accomplished in a very concise manner beginning with 2 and ( R)-2-methylpentanal. We are currently working on the total synthesis of polyketide-derived mycotoxins from simple precursors, including fumonisin B1. The key features of our synthesis are the use of oxonia-Cope rearrangements to introduce C5 and C14 stereocenters and construct C1-C9 and C10-C20 carbon skeletons.

Table of Contents

Chapter 1. Developing Chiral Synthons for Polyketide-Based Natural Product Synthesis via Stereospecific Oxonia-Cope Rearrangements

1.1 Introduction and background

1.2 Results and discussion

1.2.1 Initial Study of Allylic Rearrangement

1.2.2 Design of Bispropionate Synthons

1.2.3 Total Synthesis of (-)-invictolide

1.2.4 New Crotyl Reagents

1.3 Conclusions

1.4 Experimental information

1.5 Citations

Chapter 2. Towards the Total Synthesis of Mycotoxin Fumonisin B1

2.1 Introduction and Background

2.2 Retrosynthetic Analysis

2.3 Total Synthesis of Fumonisin B1

2.3.1 Synthesis of Alkyne 26: C1-C9 Subunit of Fumonisin B1

2.3.2 Synthesis of Amide 27: C10-C20 Subunit of Fumonisin B1

2.3.3 Synthesis of Fully Protected Fumonisin B1

2.3.4 Towards the Synthesis of Aminopentol Hexaacetate Derivative

2.4 Conclusions

2.5 Experimental information

2.6 Citations

About this Dissertation

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School	Laney Graduate School
Department	Chemistry
Degree	PhD
Submission	Dissertation
Language	English
Research Field	Chemistry, Organic
Palabra Clave	oxonia-Cope rearrangement polyketide synthesis
Committee Chair / Thesis Advisor	McDonald, Frank, Emory University
Committee Members	Liebeskind, Lanny S, Emory University Gallivan, Justin, Emory University

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