Date of Award
Doctor of Philosophy
Richard C. Larock
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.
Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/
Lu, Yong-de, "Preparation of allylic ketones via acylation of allylic mercurials ; and, Palladium(0)-catalyzed coupling of aryl iodides, nonconjugated dienes, and nucleophiles " (1991). Retrospective Theses and Dissertations. 9660.