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Total Synthesis of Strasseriolide Congeners and Progress Towards the Synthesis of Euphopia A and Formation of Chromophores From Cis-Pinonaldehyde Aged in Highly Acidic Conditions
Total Synthesis of Strasseriolide Congeners and Progress Towards the Synthesis of Euphopia A and Formation of Chromophores From Cis-Pinonaldehyde Aged in Highly Acidic Conditions
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20250211152709
- ISBN
- 9798384497042
- DDC
- 547
- 서명/저자
- Total Synthesis of Strasseriolide Congeners and Progress Towards the Synthesis of Euphopia A and Formation of Chromophores From Cis-Pinonaldehyde Aged in Highly Acidic Conditions
- 발행사항
- [Sl] : University of California, Irvine, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 384 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-04, Section: B.
- 주기사항
- Advisor: Rychnovsky, Scott D.
- 학위논문주기
- Thesis (Ph.D.)--University of California, Irvine, 2024.
- 초록/해제
- 요약The first chapter details the completion of the first total syntheses of strasseriolides A and B, two antimalarial natural products. Initially we envisioned a convergent synthesis hinging on ring-closing alkyne metathesis as the macrocyclization event. Ultimately, this approach was unsuccessful. The key features of our revised synthetic strategy include a Nozaki-Hiyama-Kishi cross-coupling reaction to install the trisubstituted (E)-alkene and set the secondary alcohol stereocenter. This strategy enabled us to complete the first reported total syntheses of the two macrolides in 17 and 16 steps longest linear sequence from commercially available chiral starting materials. A follow-up publication by the isolation team revealed that strasseriolide B is acutely toxic in vivo, and that the congener, strasseriolide D, demonstrates promising pharmacokinetic properties. Chapter 1 describes our current work towards synthesizing this related family member with proposed derivatization and SAR analysis to follow.Chapter 2 details our efforts towards the synthesis of euphopia A, a jatrophane diterpenoid. Our synthetic strategy hinged on a Diels-Alder cycloaddition to access the cis-hydrindane AB ring system, while a diastereoselective conjugate addition and Giese cyclizarion would permit access to the C and D rings and furnish the tetracyclic skeleton. Many approaches were evaluated for the formation of the hydrindane, which proved quite challenging. Ultimately, success was found using a formal "Diels-Alder" cycloaddition, although the subsequent conjugate addition resulted in unproductive reactivity. Unfortunately, progress was hindered by the complexity of the molecule. An alternate route has been conceived to mitigate the conformational and electronic effects and is in the midst of being explored.Chapter 3 describes a multidisciplinary project in collaboration with the Nizkorodov group at the University of California, Irvine. Sulfuric acid present in the atmosphere can initiate acid-catalyzed reactions, resulting in increased absorption at visible wavelengths and significant chemical alterations in secondary atmospheric aerosols (SOAs). However, the specific chromophores responsible for these changes remained unidentified. This chapter describes our work to identify these chromophores and elucidate the browning mechanism in highly acidified α-pinene SOA. We investigate the behavior of key α-pinene oxidation products-cis-pinonic acid and cis-pinonaldehyde-under highly acidic conditions. The resulting products were analyzed using ultra-performance liquid chromatography coupled with photodiode array and high-resolution mass spectrometry, UV-vis spectrophotometry, and nuclear magnetic resonance spectroscopy. Cis-pinonic acid was found to generate homoterpenyl methyl ketone, which exhibits no visible radiation absorption. In contrast, cis-pinonaldehyde underwent an acid-catalyzed aldol condensation to form weakly absorbing 1-(4-(propan-2-ylidene)cyclopent-1-en-1-yl)ethan-1-one and 1-(4-isopropylcyclopenta-1,3-dien-1-yl)ethan-1-one.
- 일반주제명
- Organic chemistry
- 일반주제명
- Chemistry
- 일반주제명
- Analytical chemistry
- 키워드
- Nizkorodov group
- 기타저자
- University of California, Irvine Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-04B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■00520250211152709
■006m o d
■007cr#unu||||||||
■020 ▼a9798384497042
■035 ▼a(MiAaPQ)AAI31488548
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a547
■1001 ▼aPazienza, Jessica Elizabeth.
■24510▼aTotal Synthesis of Strasseriolide Congeners and Progress Towards the Synthesis of Euphopia A and Formation of Chromophores From Cis-Pinonaldehyde Aged in Highly Acidic Conditions
■260 ▼a[Sl]▼bUniversity of California, Irvine▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a384 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-04, Section: B.
■500 ▼aAdvisor: Rychnovsky, Scott D.
■5021 ▼aThesis (Ph.D.)--University of California, Irvine, 2024.
■520 ▼aThe first chapter details the completion of the first total syntheses of strasseriolides A and B, two antimalarial natural products. Initially we envisioned a convergent synthesis hinging on ring-closing alkyne metathesis as the macrocyclization event. Ultimately, this approach was unsuccessful. The key features of our revised synthetic strategy include a Nozaki-Hiyama-Kishi cross-coupling reaction to install the trisubstituted (E)-alkene and set the secondary alcohol stereocenter. This strategy enabled us to complete the first reported total syntheses of the two macrolides in 17 and 16 steps longest linear sequence from commercially available chiral starting materials. A follow-up publication by the isolation team revealed that strasseriolide B is acutely toxic in vivo, and that the congener, strasseriolide D, demonstrates promising pharmacokinetic properties. Chapter 1 describes our current work towards synthesizing this related family member with proposed derivatization and SAR analysis to follow.Chapter 2 details our efforts towards the synthesis of euphopia A, a jatrophane diterpenoid. Our synthetic strategy hinged on a Diels-Alder cycloaddition to access the cis-hydrindane AB ring system, while a diastereoselective conjugate addition and Giese cyclizarion would permit access to the C and D rings and furnish the tetracyclic skeleton. Many approaches were evaluated for the formation of the hydrindane, which proved quite challenging. Ultimately, success was found using a formal "Diels-Alder" cycloaddition, although the subsequent conjugate addition resulted in unproductive reactivity. Unfortunately, progress was hindered by the complexity of the molecule. An alternate route has been conceived to mitigate the conformational and electronic effects and is in the midst of being explored.Chapter 3 describes a multidisciplinary project in collaboration with the Nizkorodov group at the University of California, Irvine. Sulfuric acid present in the atmosphere can initiate acid-catalyzed reactions, resulting in increased absorption at visible wavelengths and significant chemical alterations in secondary atmospheric aerosols (SOAs). However, the specific chromophores responsible for these changes remained unidentified. This chapter describes our work to identify these chromophores and elucidate the browning mechanism in highly acidified α-pinene SOA. We investigate the behavior of key α-pinene oxidation products-cis-pinonic acid and cis-pinonaldehyde-under highly acidic conditions. The resulting products were analyzed using ultra-performance liquid chromatography coupled with photodiode array and high-resolution mass spectrometry, UV-vis spectrophotometry, and nuclear magnetic resonance spectroscopy. Cis-pinonic acid was found to generate homoterpenyl methyl ketone, which exhibits no visible radiation absorption. In contrast, cis-pinonaldehyde underwent an acid-catalyzed aldol condensation to form weakly absorbing 1-(4-(propan-2-ylidene)cyclopent-1-en-1-yl)ethan-1-one and 1-(4-isopropylcyclopenta-1,3-dien-1-yl)ethan-1-one.
■590 ▼aSchool code: 0030.
■650 4▼aOrganic chemistry
■650 4▼aChemistry
■650 4▼aAnalytical chemistry
■653 ▼aMacrocyclization event
■653 ▼aAntimalarial natural products
■653 ▼aNizkorodov group
■653 ▼aMagnetic resonance spectroscopy
■653 ▼aLiquid chromatography
■690 ▼a0490
■690 ▼a0486
■690 ▼a0485
■71020▼aUniversity of California, Irvine▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-04B.
■790 ▼a0030
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17163446▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
