Studies directed toward the total synthesis of (-)-enigmazole B.

Format:

Book

Thesis/Dissertation

Author/Creator:

Orbin, Alia M.

Contributor:

Chenoweth, David M., committee member.

Molander, Gary A., committee member.

Joullie, Madeleine, committee member.

Smith, Amos B., III, advisor.

University of Pennsylvania. Chemistry.

Language:

English

Subjects (All):

Chemistry, Organic.

0490.

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

Local Subjects:

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

0490.

Physical Description:

261 pages

Contained In:

Dissertation Abstracts International 73-09B(E).

System Details:

Mode of access: World Wide Web.

text file

Summary:

Studies toward the total synthesis of (–)-enigmazole B are presented in the dissertation contained herein. Chapter One details both the isolation and subsequent biological studies of (–)-enigmazole B by Professor Gustafson. The chapter then describes Smith's multicomponent lynchpin reaction, further categorized as Type I and Type II Anion Relay Chemistry (ARC). Type I ARC will be called upon for the key strategic transformation toward the total synthesis of (–)-enigmazole B.

The first generation retrosynthetic strategy toward (−)-enigmazole B, which utilizes the Type I ARC tactic to generate the entire carbon skeleton in one reaction, is described in Chapter Two. The synthesis of the requisite C(1–8) and C(10–17) epoxides is described in Chapter Two. Unsuccessful attempts to form the C(1–17) carbon fragment via Type I ARC is presented at the conclusion of Chapter Two.

A second-generation synthetic strategy is described in Chapter Three, where the C(17) oxazole moiety is absent during the multicomponent lynchpin coupling. The formation of the C(1–16) carbon fragment via the Type I ARC tactic is presented in Chapter Three. Use of a C(17) dithiane permitted formation of the C(16–17) bond, resulting in the completion of the carbon skeleton of (–)-enimgazole B. Acid-promoted cyclization to the 2,6-disubstituted dihydropyrone is presented. Chapter Three concludes with a proposed end-game strategy.

Notes:

Thesis (Ph.D. in Chemistry) -- University of Pennsylvania, 2012.

Source: Dissertation Abstracts International, Volume: 73-09(E), Section: B.

Adviser: Amos B. Smith, III.

Local Notes:

School code: 0175.

ISBN:

9781267358486

Access Restriction:

Restricted for use by site license.