Synthetic Studies Toward the Total Synthesis of Enterocin

Citation

Tao, Yujia (2023) Synthetic Studies Toward the Total Synthesis of Enterocin. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/jdhq-sb66. https://resolver.caltech.edu/CaltechTHESIS:05182023-054024067

Abstract

As part of a broader program aimed at the synthesis of complex and highly oxygenated natural products, we initiated a chemical synthesis of the natural polyketide enterocin. This dissertation will disclose our efforts to bridge that gap through the development of synthetic strategies for the total synthesis of the enterocin. The studies herein will address three unique strategies to access the tactical difficulties in the rich oxygenation patterns and caged core structure of enterocin. The program was first inspired by a SeO2 multioxidation reaction, and the methodology has been successfully applied to install bridgehead oxygenation patterns in enterocin. A strategy featuring a radical-polar crossover reaction as an annulation step to quickly construct the [3.2.1] bicyclic core of enterocin is detailed. Initial studies have successfully achieved the radical-polar crossover annulation reaction to forge [3.2.1]bicycles with bridgehead hydroxyl groups, and will guide the future development toward the total synthesis of enterocin. An intermolecular aldol approach will be discussed to address the challenge on pyrone installation and core structure synthesis. In summary, the development of an efficient and general approach will allow the development of novel reactions and a comprehensive evaluation of the potential of caged polyketides to serve as medicinally interesting molecules.

Item Type:

Thesis (Dissertation (Ph.D.))

Subject Keywords:

Total Synthesis, Organic Chemistry

Degree Grantor:

California Institute of Technology

Division:

Chemistry and Chemical Engineering

Major Option:

Chemistry

Thesis Availability:

Not set

Research Advisor(s):

Reisman, Sarah E.

Thesis Committee:

Stoltz, Brian M. (chair)
Arnold, Frances Hamilton
Fu, Gregory C.
Reisman, Sarah E.

Defense Date:

5 May 2023

Non-Caltech Author Email:

yjtao8 (AT) gmail.com

Funders:

Funding Agency	Grant Number
NSF	1800536
NIH	R35GM118191
BASF (United States)	UNSPECIFIED
NSF	CHE-2155163

Record Number:

CaltechTHESIS:05182023-054024067

Persistent URL:

https://resolver.caltech.edu/CaltechTHESIS:05182023-054024067

DOI:

10.7907/jdhq-sb66

Related URLs:

URL	URL Type	Description
https://doi.org/10.1038/s41586-019-1580-x	DOI	Article adapted for ch.1
https://doi.org/10.1021/acs.orglett.2c01343	DOI	Article adapted for ch.2
https://doi.org/10.1021/acs.accounts.0c00858	DOI	Review article published

ORCID:

Author	ORCID
Tao, Yujia	0000-0003-4615-6409

Default Usage Policy:

No commercial reproduction, distribution, display or performance rights in this work are provided.

ID Code:

15189

Collection:

CaltechTHESIS

Deposited By:

Yujia Tao

Deposited On:

26 May 2023 22:34

Last Modified:

08 Nov 2023 00:42

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