Enantioselective total Synthesis of the agelastatin and trigonoliimine alkaloids
Name
809537907-MIT.pdf
Description
Full printable version
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19.38 MB
Format
Adobe PDF
Checksum (MD5)
af15c1341e71be8c3eba089d3ef42bb2
Author(s)
Han, Sunkyu, 1982-
Advisor(s)
Mohammad Movassaghi.
Date Issued
2012
Publisher
Massachusetts Institute of Technology
Abstract
I. Total Synthesis of the (-)-Agelastatin Alkaloids The pyrrole-imidazole family of marine alkaloids, derived from linear clathrodin-like precursors, constitutes a diverse array of structurally complex natural products. The bioactive agelastatins are members of this family that possess a tetracyclic molecular framework incorporating C4-C8 and C7-N12 bond connectivities. We provide a hypothesis for the formation of the unique agelastatin architecture that maximally exploits the intrinsic chemistry of plausible biosynthetic precursors. We report the concise enantioselective total syntheses of all known agelastatin alkaloids including the first total syntheses of agelastatins C, D, E, and F. Our gram-scale chemical synthesis of agelastatin A was inspired by our hypothesis for the biogenesis of the cyclopentane C-ring and required the development of new transformations including an imidazolone-forming annulation reaction and a carbohydroxylative trapping of imidazolones. II. Total Synthesis of the (-)-Trigonoliimine Alkaloids The concise and enantioselective total syntheses of (-)-trigonoliimines A, B, and C are described. Our unified strategy to all three natural products is based on asymmetric oxidation and reorganization of a single bistryptamine, a sequence of transformations with possible biogenetic relevance. We revise the absolute stereochemistry of (-)-trigonoliimines A, B, and C.
Description
Thesis (Ph. D. in Organic Chemistry)--Massachusetts Institute of Technology, Dept. of Chemistry, 2012.
Vita. Cataloged from PDF version of thesis.
Includes bibliographical references.
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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