Date of Award
Spring 2015
Project Type
Dissertation
Program or Major
Chemistry
Degree Name
Doctor of Philosophy
First Advisor
Charles K Zercher
Second Advisor
Gary R Weisman
Third Advisor
Glen P Miller
Abstract
A formal synthesis of the natural products CJ-12,954 and CJ-13,014 was successfully accomplished using the zinc-mediated tandem chain extension-aldol reaction methodology. This chemistry was performed on a chiral β-keto imide synthesized using a DCC coupling reaction. The diastereoselectivity of the aldol reaction was controlled by an Evans chiral auxiliary. Comparison between the reported and experimental spectral data for the spiroketals confirmed the structural assignment.
The diastereoselectivity of the homologation-cyclization-rearrangement-lactonization reaction of β-keto imide derived from phenyl carbamate-protected proline was studied. Tetra-n-butylammonium fluoride-mediated rearrangement of trimethylsilyl cyclopropanol demonstrated the role of chiral auxiliary and the amino acid stereocenter in controlling the diastereoselectivity of the bicyclic lactone formation.
Recommended Citation
Bhogadhi, Yashoda Naga Deepthi, "Formal Synthesis of CJ-12,954 and CJ-13,014 using Zinc-Mediated Tandem Chain Extension-Aldol Reaction and Synthesis and Investigation of Diastereoselectivity of Hydroxy-Cyclopropyl Peptide Isosteres" (2015). Doctoral Dissertations. 2204.
https://scholars.unh.edu/dissertation/2204