Progress Toward the Asymmetric Synthesis of (-)-Gephyrotoxin

gephyrotoxin;natural product synthesis;asymmetric synthesis

Miller, Teresa Marie ; Dr. Suzanne T. Purrington, Committee Member,Dr. Carl L. Bumgardner, Committee Member,Dr. Jonathan S. Lindsey, Committee Member,Dr. Daniel L. Comins, Committee Chair,Miller, Teresa Marie ; Dr. Suzanne T. Purrington ; Committee Member ; Dr. Carl L. Bumgardner ; Committee Member ; Dr. Jonathan S. Lindsey ; Committee Member ; Dr. Daniel L. Comins ; Committee Chair

University:North Carolina State University

关键词: gephyrotoxin;    natural product synthesis;    asymmetric synthesis;   

Others  :  https://repository.lib.ncsu.edu/bitstream/handle/1840.16/3356/etd.pdf?sequence=1&isAllowed=y

美国|英语

来源: null

【 摘 要 】

This research has focused on the asymmetric synthesis of the natural product (-)-gephyrotoxin.This product was isolated and characterized by Daly and coworkers in 1977.Kishi and co-workers published the first synthesis of (-)-gephyrotoxin in 1980, and the first synthesis of (+)-gephyrotoxin in 1981.No synthesis of (-)-gephyrotoxin has been published to date. In exploring the possibilities for the synthesis of (-)-gephyrotoxin, many synthetic transformations were investigated including, Horner-Wadsworth-Emmons, Diels-Alder, orthoester Claisen, and Mukaiyama-Michael addition.Diels-Alder and Horner-Wadsworth-Emmons Chemistry was explored for formation of the 6,6 trans ring system necessary for (-)-gephyrotoxin.Previously synthesis of only cis ring systems had been developed.Orthoester Claisen rearrangement and Mukaiyama-Michael addition were investigated to set the C6 and 5a stereocenters. Our progress toward the synthesis of (-)-gephyrotoxin yielded other developments as well.The formation of both the cis and trans 4-hydroxy -3,4-dihydro-2H-pyridines was accomplished for the first time, and the formation of 5-iodo, and 5-vinyl-2,3-dihydro-4-pyridones was improved.