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Photoredox-Mediated Radical Coupling Reactions of Acyl Azoliums
Photoredox-Mediated Radical Coupling Reactions of Acyl Azoliums
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20250211150923
- ISBN
- 9798381976502
- DDC
- 547
- 서명/저자
- Photoredox-Mediated Radical Coupling Reactions of Acyl Azoliums
- 발행사항
- [Sl] : Northwestern University, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 235 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 85-10, Section: B.
- 주기사항
- Advisor: Scheidt, Karl A.
- 학위논문주기
- Thesis (Ph.D.)--Northwestern University, 2024.
- 초록/해제
- 요약The quest for novel catalytic techniques in small molecule synthesis remains a central focus in organic chemistry, requiring advancements in synthetic methodologies. This work employs photoredox catalysis in the radical coupling of sulfides and potassium trifluoroborates with persistent azolium-derived ketyl radicals. These radicals effectively couple with transient α-thio radicals and benzyl radicals, leading to the formation of a tertiary alcohol intermediate, confirmed by X-ray diffraction. This pivotal finding informed multiple publications, which determined that the tertiary alcohol is a commonly isolable intermediate undergoing conversion to ketone products upon treatment with a base, thus informing reaction mechanisms and broadening the scope of azolium-mediated radical coupling reactions. The experimental approach to reaction development employed high-throughput experimentation (HTE) for broad screening of reaction conditions; however, translating these HTE results to scalable reactions and isolated products presented a challenge. To resolve this discrepancy, an extensive analysis of the reactions was performed, which involved characterizing both the tertiary alcohol intermediate and several non-productive byproducts. This detailed account of the mass balance enabled a structurally informed mechanistic proposal, which facilitated a hypothesis-driven optimization of two projects. The ability to capitalize on this knowledge exemplifies the synergy of experimental investigation with mechanistic insight, leading to innovative and efficient synthetic methodologies.
- 일반주제명
- Organic chemistry
- 일반주제명
- Chemistry
- 일반주제명
- Analytical chemistry
- 키워드
- Acyl azoliums
- 키워드
- Sulfides
- 기타저자
- Northwestern University Chemistry
- 기본자료저록
- Dissertations Abstracts International. 85-10B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■00520250211150923
■006m o d
■007cr#unu||||||||
■020 ▼a9798381976502
■035 ▼a(MiAaPQ)AAI30987685
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a547
■1001 ▼aRourke, Michael Joseph.
■24510▼aPhotoredox-Mediated Radical Coupling Reactions of Acyl Azoliums
■260 ▼a[Sl]▼bNorthwestern University▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a235 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 85-10, Section: B.
■500 ▼aAdvisor: Scheidt, Karl A.
■5021 ▼aThesis (Ph.D.)--Northwestern University, 2024.
■520 ▼aThe quest for novel catalytic techniques in small molecule synthesis remains a central focus in organic chemistry, requiring advancements in synthetic methodologies. This work employs photoredox catalysis in the radical coupling of sulfides and potassium trifluoroborates with persistent azolium-derived ketyl radicals. These radicals effectively couple with transient α-thio radicals and benzyl radicals, leading to the formation of a tertiary alcohol intermediate, confirmed by X-ray diffraction. This pivotal finding informed multiple publications, which determined that the tertiary alcohol is a commonly isolable intermediate undergoing conversion to ketone products upon treatment with a base, thus informing reaction mechanisms and broadening the scope of azolium-mediated radical coupling reactions. The experimental approach to reaction development employed high-throughput experimentation (HTE) for broad screening of reaction conditions; however, translating these HTE results to scalable reactions and isolated products presented a challenge. To resolve this discrepancy, an extensive analysis of the reactions was performed, which involved characterizing both the tertiary alcohol intermediate and several non-productive byproducts. This detailed account of the mass balance enabled a structurally informed mechanistic proposal, which facilitated a hypothesis-driven optimization of two projects. The ability to capitalize on this knowledge exemplifies the synergy of experimental investigation with mechanistic insight, leading to innovative and efficient synthetic methodologies.
■590 ▼aSchool code: 0163.
■650 4▼aOrganic chemistry
■650 4▼aChemistry
■650 4▼aAnalytical chemistry
■653 ▼aAcyl azoliums
■653 ▼aPhotoredox catalysis
■653 ▼aRadical coupling reactions
■653 ▼aSulfides
■690 ▼a0490
■690 ▼a0486
■690 ▼a0485
■71020▼aNorthwestern University▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g85-10B.
■790 ▼a0163
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17160161▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
