Progress towards the enantioselective total synthesis of trichodermamide B

Levinn, Carolyn M

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https://hdl.handle.net/2142/97625 Copy

Description

Title

Progress towards the enantioselective total synthesis of trichodermamide B

Author(s)

Levinn, Carolyn M

Issue Date

2017-04-25

Director of Research (if dissertation) or Advisor (if thesis)

Sarlah, David

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

M.S.

Degree Level

Thesis

Date of Ingest

2017-08-10T19:52:22Z

Keyword(s)

• Trichodermamide B
• Total synthesis
• Microbial arene oxidation
• Arenophile
• Arene oxide

Abstract

Trichodermamide B is an unusual modified dipeptide natural product, with very promising anticancer activities. While the biosynthesis of this molecule is unknown, it is proposed herein that it is formed in vivo through direct oxidation of phenylalanine to the arene oxide or arene dioxide intermediate, which is then opened via nucleophilic attack of an oxime. To probe the feasibility of this biosynthetic hypothesis, a series of bioinspired approaches to trichodermamide B have been investigated, proceeding through arene oxide equivalents. Progress towards the concise and practical total synthesis of this molecule are described herein. Notable transformations explored include the mild installation of an oxime with hydrogen atom transfer, and microbial arene oxidation to generate decagram amounts of enantiopure, value-added starting materials. This strategy has enabled rapid access to large quantities of advanced intermediates, and once complete, should afford the natural product as a single enantiomer in far fewer steps than previously reported.

Graduation Semester

2017-05

Type of Resource

text

Permalink

http://hdl.handle.net/2142/97625

Copyright and License Information

Copyright 2017 Carolyn Levinn

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