자료유형  

 학위논문

Control Number  

0017160361

International Standard Book Number  

9798382789347

Dewey Decimal Classification Number  

547

Main Entry-Personal Name  

Smith, Brendyn Paul.

Publication, Distribution, etc. (Imprint  

[S.l.] : The Scripps Research Institute., 2024

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2024

Physical Description  

252 p.

General Note  

Source: Dissertations Abstracts International, Volume: 85-12, Section: B.

General Note  

Advisor: Baran, Phil S.

Dissertation Note  

Thesis (Ph.D.)--The Scripps Research Institute, 2024.

Summary, Etc.  

요약Natural products that arise from hybrid metabolic pathways offer a unique and exciting opportunity for total synthesis and often result in compelling synthetic campaigns. The dragocin family of natural products represent a peculiar class of these types of secondary metabolites and feature multiple rare or even completely unprecedented structural motifs. Described in this dissertation is a brief background of these intriguing structures along with the strategies that were explored en route to these natural products in five separate chapters. Notably, the approaches described herein represent the first reported synthetic forays into these marine-derived compounds and may inform any future work on these structures or related molecules.Chapter 1 will introduce the dragocins, the synthesis of the only related natural product, AB3217-A, along with preliminary studies towards the preparation of the densely functionalized pyrrolidine found in the dragocins. In chapter 2, [3+2] cycloaddition strategies will be presented, which will feature both azomethine ylide and nitrone synthons along with a discussion of key roadblocks. Chapter 3 will focus on an approach which leveraged an enantioselective pyrrole dearomatization, giving way to the first advanced intermediate which enabled exploration of 9-membered ring formation via an unsuccessful intramolecular glycosylation strategy. In chapter 4, a dearomative furan-based strategy will be presented, which was also unfortunately met with failure. Finally, the first successful approach towards the key 9-membered skeleton and a failed late-stage C-H oxidation strategy will be found in chapter 5. Additionally found in this chapter will be the final successful approach towards these metabolites, which hinged upon a key decarboxylative chlorination of an intermediate which was constructed from an unprecedented intramolecular electrochemical cyclization/etherification event. A brief discussion of these natural products acting as potential covalently reactive compounds will conclude this dissertation.

Subject Added Entry-Topical Term  

Organic chemistry.

Subject Added Entry-Topical Term  

Chemistry.

Subject Added Entry-Topical Term  

Biochemistry.

Index Term-Uncontrolled  

Natural products

Index Term-Uncontrolled  

Dragocin family

Index Term-Uncontrolled  

Hybrid metabolic pathways

Index Term-Uncontrolled  

Dragocins

Added Entry-Corporate Name  

The Scripps Research Institute Chemistry

Host Item Entry  

Dissertations Abstracts International. 85-12B.

Electronic Location and Access  

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Control Number  

joongbu:657487