Dissertation Information for Alexei V. Novikov NAME: - Alexei V. Novikov
DEGREE:
- Ph.D.
DISCIPLINE:
- Chemistry
SCHOOL:
- Emory University (USA) (2001)
ADVISORS: - David Goldsmith
COMMITTEE MEMBERS: - Albert Padwa - Lanny S. Liebeskind
MPACT Status: Fully Complete
Title: Part I: Preparation of chiral epoxides and cationic cyclization using chiral sulfenium reagents. Part II: Synthesis of clerodanes: A Diels-Alder approach
Abstract: "The dissertation consists of two parts.
In part I of the dissertation a sequence for preparation of chiral epoxides is studied. The proposed sequence is shown in Figure 1 . An alkene is first reacted with a sulfenyl chloride that carries a chiral auxiliary, and the intermediate is trapped with an acetate. The resulting acetoxysulfide is converted to a sulfonium salt, and then treated with sodium hydroxide to remove the acetate and close the epoxide.*
Two chiral sulfenium reagents were prepared and studied, 1 and 2 ( Figure 2 ).*
Another application of the sulfenyl reagents carrying a chiral auxiliary is also studied--a cationic cyclization initiated by a sulfenyl cation ( Figure 3 ).*
In part II of the dissertation an approach to synthesis of clerodanes is described that resulted in a total synthesis of clerodanes 3 , 4 and 5 .*
The key step of the synthetic approach that is used to construct the trans -fused bicyclic system is Diels-Alder cycloaddition, followed by base equilibration. The short summary of the rest of the final synthetic sequence is shown in Figure 4 .*
*Please refer to dissertation for diagrams."
|