Date of Award

Fall 2010

Project Type


Program or Major


Degree Name

Doctor of Philosophy

First Advisor

Charles K Zercher


A novel ceric ammonium nitrate-mediated oxidative cleavage of hemiacetals generated through the use of the zinc carbenoid-mediated tandem chain extension-aldol reaction was developed. This chemistry has been applied towards the formation of a class of natural products, phaseolinic acids, in two steps from a commercially available beta-keto ester, methyl 4-methoxyacetoacetate.

The tandem chain extension-imine capture reaction has also been developed to provide access to beta-proline derivatives. Two activated imines were studied and provided access to different diastereomers, making the chemistry versatile. beta-Keto esters, beta-keto amides, and beta-keto imides were subjected to the tandem chain extension-imine capture reaction conditions and proved to be reasonably successful in most cases. beta-Keto esters were efficient in the synthesis of free --NH beta-proline derivatives in three steps and beta-keto imides were efficient in the synthesis of Boc-protected beta-proline derivatives in just two steps.

The zinc carbenoid-mediated chain extension imine capture reaction has developed into a flexible route in obtaining different diastereomers of protected and unprotected beta-proline derivatives in minimal steps from commercially available starting materials.