Reagent-directed allylic quadraselection and synthesis of the C1-C27 segment of Aplyronine A
Abstract
A general Methods have been developed for regio- and stereoselective 1,4-syn or 1,4-anti methylation of seven-membered epoxyvinylsulfones. 1,4-Syn addition is achieved via the combination of Me2Zn and catalytic Li2CuCl4, a hitherto unexplored reagent combination. The complementary 1,4- anti addition relies on Cu(I) catalyzed methyl Grignard addition or (CH3)3Al assisted CH3Cu addition. The methods described were assayed on four diastereomeric stereodiads and on their parent epoxide. Application of the above methodologies towards the synthesis of Aplyronine A is investigated. Oxidative cleavage of cyclic vinyl sulfones has been used to prepare key fragments of Aplyronine A. Key precursors are united by Horner-Wadsworth-Emmons and Julia-Kociensky olefination for the elaboration of the C1-C27 segment. The crucial intramolecular macrolactonization of the resulting C1-C27 seco acids was effectively accomplished by Yamaguchi procedure.
Degree
Ph.D.
Advisors
Fuchs, Purdue University.
Subject Area
Organic chemistry
Off-Campus Purdue Users:
To access this dissertation, please log in to our
proxy server.