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

Chen, Yi-hung (2007)
Dissertation (127 pages)
Committee Chair / Thesis Adviser: McDonald, Frank
Committee Members: Liebeskind, Lanny S ; Gallivan, Justin
Research Fields: Chemistry, Organic
Keywords: polyketide synthesis; oxonia-Cope rearrangement
Program: Laney Graduate School, Chemistry
Permanent url: http://pid.emory.edu/ark:/25593/13q53

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

Files

application/pdf Dissertation 127 pages (556.9 KB) [Thesis__YiHung_.pdf]
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