Studies towards bioinspired synthesis of homodimericin A and total synthesis of dimeric epoxyquinoids and its biologically related monomeric natural products = 생합성 가설을 기반으로 한 호모다이머리신 A의 합성 연구와 이합체 에폭시퀴논 천연물의 전합성

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1. Homodimericin A was proposed to be derived from the two-hydroquinone precursors through a series of intriguing transformations. The monomeric precursor could then undergo homodimerization through a Baldwin forbidden double Michael cyclization. which undergo an intramolecular Diels-Alder reaction to give the pentacyclic framework. Finally, the pentacyclic framework could rearranged to homodimericin A through an intramolecular vinylogous aldol reaction. Herein, we describe the toward bioinspired synthesis of homodimericin A. Keywords: homodimericin A, dimerization, intramolecular Diels–Alder reaction, cascade reaction 2. We describe the total synthesis of epoxyquinoid natural products (+)-pestalofone A and (+)-iso-A82775C. The synthesis of (+)-16-oxo-iso-A82775C, the putative biosynthetic precursor of pestalofone C yet to be isolated, is also presented. The allene moiety present in (+)-iso-A82775C and (+)-16-oxo-iso-A82775C was constructed from the ketodiene-yne group via a biosynthetically relevant sequence involving a conjugate reduction and a base-catalyzed tautomerization. Attempted Diels–Alder reaction-based dimerizations of (+)-16-oxo-iso-A82775C and (+)-iso-A82775C towards pestalofones B and C are also described. Keywords: iso-A82775C, pestalofone A, ketodiene-yne isomerization 3. The first total synthesis of (+)-dimericbiscognienyne A is described. Key to the successful access to (+)-dimericbiscognienyne A was a biosynthetically inspired Diels−Alder reaction between two differential epoxyquinoid monomers and the subsequent intramolecular hemiacetal formation. The selective formation of the natural product among other possible diastereomers during the late-stage [4+2] cycloaddition reaction was investigated by DFT calculations and experimental control studies. Keywords: dimericbiscognineyne A, intermolecular Diels–Alder reaction, biomimetic synthesis
Advisors
Han, Sunkyuresearcher한순규researcher
Description
한국과학기술원 :화학과,
Publisher
한국과학기술원
Issue Date
2020
Identifier
325007
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2020.8,[iv, 184 p. :]

Keywords

natural product▼atotal synthesis▼abioinspired synthesis▼ahomodimericin A▼adimeric epoxiquinone; 천연물▼a전합성▼a호모다이머리신 A▼a이합체 에폭시퀴논▼a생체모방합성

URI
http://hdl.handle.net/10203/284385
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=924430&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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