Degree Type

Dissertation

Date of Award

1991

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Richard C. Larock

Abstract

The first part of this thesis discusses an unprecedented acylation of allylic mercurials by acyl chlorides promoted by aluminum chloride. A variety of allylic mercurials and acyl chlorides, including aliphatic, aromatic, and [alpha],[beta]-unsaturated acyl chlorides, can be employed successfully in this reaction. This reaction provides a convenient route to allylic ketones. A modified literature procedure to prepare allylic mercuric iodides from the corresponding allylic halides and metallic mercury is also presented in this part;The second part of this thesis discusses the palladium-catalyzed coupling of aryl iodides, nonconjugated dienes, and nucleophiles, which generates more than one carbon-carbon bond or carbon-heteroatom bond at a time via palladium migration chemistry. Considerable functionality can be accommodated in this reaction and the palladium can migrate along a carbon chain as far as ten carbon atoms;The second part of this thesis is divided into three sections. The first section deals with the palladium-catalyzed coupling of aryl iodides and nonconjugated dienes using carbon nucleophiles. The reaction results in a high degree of regioselectivity and stereoselectivity. Applications of nitrogen and oxygen nucleophiles in this unique coupling reaction are reported in the second section. A variety of amines and the azide anion have been used as representative nitrogen nucleophiles and only one regio- and stereoisomer is isolated in good yields. When oxygen nucleophiles, such as acetate anion and phenoxide anion, are used in the coupling process, a mixture of regio- and stereoisomers is obtained. The focus of the third section is the application of the three-component coupling methodology to the synthesis of analogues of some naturally occurring pyridine alkaloids. The palladium-catalyzed coupling-migration approach is the key step and the total synthesis is accomplished in only two steps.

DOI

https://doi.org/10.31274/rtd-180813-12135

Publisher

Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/

Copyright Owner

Yong-de Lu

Language

en

Proquest ID

AAI9212163

File Format

application/pdf

File Size

192 pages

Share

COinS