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Exploration of Novel C-H Functionalization Methodologies via Organic Photoredox Catalysis
Exploration of Novel C-H Functionalization Methodologies via Organic Photoredox Catalysis
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202104727
- ISBN
- 9798291561287
- DDC
- 547
- 서명/저자
- Exploration of Novel C-H Functionalization Methodologies via Organic Photoredox Catalysis
- 발행사항
- [Sl] : The University of North Carolina at Chapel Hill, 2025
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2025
- 형태사항
- 133 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 87-02, Section: B.
- 주기사항
- Advisor: Niewicz, David A.
- 학위논문주기
- Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2025.
- 초록/해제
- 요약The selective and facile functionalization of C-H bonds - the most abundant bonds in all chemical space - remains a key driving factor for innovation in modern chemistry. Chapter 1 provides an overview of C-H functionalization research and its importance; discussion of C-H functionalization necessitates an analysis of subjects such as organometallic chemistry, radical generation and functionalization, and the synthetic benefits and challenges presented therein. Intersecting with discussion of C-H functionalization and radical chemistry, photoredox catalysis has played a major role in modern C-H functionalization methodologies, and as such is discussed in detail. Distinct and impactful C-H functionalization works from the Nicewicz lab are explored, providing a basis for the exploratory photoredox catalysis chemistry discussed in subsequent chapters.Chapter 2 explores attempts at generating and functionalizing azaallyl radical species via organic photoredox catalysis. Using the extreme oxidizing power of acridinium photoredox catalysts for novel modes of C-H functionalization circumvents the typically harsh conditions needed for azaallyl radical formation. While methods for α-amino functionalization are abundant, azaallyl radicals are uniquely long-lived, allowing for radical cascade and cyclization reactivity. While some success was afforded C-H functionalization with typical radical traps, control of the reactivity remains tenuous and the desired cascade-like cyclization remains elusive. Chapter 3 details a completed C-H functionalization methodology for the programmable synthesis of decorated piperazine cores via organic photoredox catalysis. The synthetic and medicinal importance piperazines is highlighted, as are the typical shortcomings of both traditional and state-of-the-art approaches for their synthesis. Optimization and scope of the cyclization reaction are explored in depth, and a complementary hydroamination strategy for the synthesis of complex diamine backbones from ene-carbamates via organic photoredox catalysis is demonstrated. Chapter 4 serves as a conceptual successor to the piperazine methodology, establishing the foundation of a synthetic approach for an organic photoredox-catalyzed morpholine synthesis via a C-H functionalization strategy. Initial optimization of the desired reactivity is detailed in full, exploring somewhat divergent results based on seemingly innocuous changes to the reaction system. While the yield in either iteration of the model system remains low, significant options for future optimization remain in terms of catalyst choice and substrate design.
- 일반주제명
- Organic chemistry
- 일반주제명
- Physical chemistry
- 일반주제명
- Chemical engineering
- 키워드
- Catalysis
- 키워드
- Hydroamination
- 기타저자
- The University of North Carolina at Chapel Hill Chemistry
- 기본자료저록
- Dissertations Abstracts International. 87-02B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■00520260202104727
■006m o d
■007cr#unu||||||||
■020 ▼a9798291561287
■035 ▼a(MiAaPQ)AAI32122390
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a547
■1001 ▼aBoley, Alexander Joseph.
■24510▼aExploration of Novel C-H Functionalization Methodologies via Organic Photoredox Catalysis
■260 ▼a[Sl]▼bThe University of North Carolina at Chapel Hill▼c2025
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2025
■300 ▼a133 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 87-02, Section: B.
■500 ▼aAdvisor: Niewicz, David A.
■5021 ▼aThesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2025.
■520 ▼aThe selective and facile functionalization of C-H bonds - the most abundant bonds in all chemical space - remains a key driving factor for innovation in modern chemistry. Chapter 1 provides an overview of C-H functionalization research and its importance; discussion of C-H functionalization necessitates an analysis of subjects such as organometallic chemistry, radical generation and functionalization, and the synthetic benefits and challenges presented therein. Intersecting with discussion of C-H functionalization and radical chemistry, photoredox catalysis has played a major role in modern C-H functionalization methodologies, and as such is discussed in detail. Distinct and impactful C-H functionalization works from the Nicewicz lab are explored, providing a basis for the exploratory photoredox catalysis chemistry discussed in subsequent chapters.Chapter 2 explores attempts at generating and functionalizing azaallyl radical species via organic photoredox catalysis. Using the extreme oxidizing power of acridinium photoredox catalysts for novel modes of C-H functionalization circumvents the typically harsh conditions needed for azaallyl radical formation. While methods for α-amino functionalization are abundant, azaallyl radicals are uniquely long-lived, allowing for radical cascade and cyclization reactivity. While some success was afforded C-H functionalization with typical radical traps, control of the reactivity remains tenuous and the desired cascade-like cyclization remains elusive. Chapter 3 details a completed C-H functionalization methodology for the programmable synthesis of decorated piperazine cores via organic photoredox catalysis. The synthetic and medicinal importance piperazines is highlighted, as are the typical shortcomings of both traditional and state-of-the-art approaches for their synthesis. Optimization and scope of the cyclization reaction are explored in depth, and a complementary hydroamination strategy for the synthesis of complex diamine backbones from ene-carbamates via organic photoredox catalysis is demonstrated. Chapter 4 serves as a conceptual successor to the piperazine methodology, establishing the foundation of a synthetic approach for an organic photoredox-catalyzed morpholine synthesis via a C-H functionalization strategy. Initial optimization of the desired reactivity is detailed in full, exploring somewhat divergent results based on seemingly innocuous changes to the reaction system. While the yield in either iteration of the model system remains low, significant options for future optimization remain in terms of catalyst choice and substrate design.
■590 ▼aSchool code: 0153.
■650 4▼aOrganic chemistry
■650 4▼aPhysical chemistry
■650 4▼aChemical engineering
■653 ▼aC-H functionalization
■653 ▼aCatalysis
■653 ▼aPhotoredox catalysis
■653 ▼aHydroamination
■653 ▼aPiperazine methodology
■690 ▼a0490
■690 ▼a0542
■690 ▼a0494
■71020▼aThe University of North Carolina at Chapel Hill▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g87-02B.
■790 ▼a0153
■791 ▼aPh.D.
■792 ▼a2025
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17358617▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
