Total synthesis of (-)-enigmazole A / Yanran Ai.

Format:

Book

Manuscript

Thesis/Dissertation

Author/Creator:

Ai, Yanran, author.

Contributor:

Smith, Amos B., III, degree supervisor.

Kozlowski, Marisa C., 1967- degree committee member.

Molander, Gary A., degree committee member.

Winkler, Jeffrey D., degree committee member.

University of Pennsylvania. Department of Chemistry, degree granting institution.

Language:

English

Subjects (All):

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

Local Subjects:

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

Physical Description:

xiv, 265 leaves : illustrations ; 29 cm

Production:

[Philadelphia, Pennsylvania] : University of Pennsylvania, 2015.

Summary:

The dissertation contained herein presents a total synthesis of (-)-enigmazole A utilizing a late-stage large-fragment Petasis-Ferrier union/rearrangement protocol. Chapter One details the isolation, structural elucidation and subsequent biological studies of (-)-enigmazole A. The previous synthetic studies of (-)-enigmazole A are also introduced. The chapter then outlines the Smith three-step Petasis-Ferrier union/rearrangement protocol, as well as a number of the successfultotal syntheses achieved over the years by the Smith group utilizing this protocol. Herein, a late-stage large-fragment Petasis-Ferrier union/rearrangement will be utilized as the synthetic cornerstone for the Smith total synthesis of (-)-enigmazole A. Chapter Two describes the retrosynthetic strategy toward (-)-enigmazole A and subsequent total synthesis. The late-stage large-fragment Petasis-Ferrier union/rearrangement, which generates the entire carbon skeletonof (-)-enigmazole A, is described after the construction of the requisite eastern and western hemispheres. The chapter then describes the subsequent macrolactonization studies and the end game of the total synthesis. In addition to the Smith three-step Petasis-Ferrier union/rearrangement protocol, highlights of the total synthesis includes a Negishi cross-coupling, a dithiane-epoxide union, a Type I ARC multicomponent coupling, a Yamaguchi macrolactonization and chemoselective oxidation/reduction strategies the details of which are also described in Chapter Two.

Notes:

Ph. D. University of Pennsylvania 2015.

Department: Chemistry.

Supervisor: Amos B. Smith, III.

Includes bibliographical references.

OCLC:

950058397