서브메뉴
검색
Development of Aliphatic C-H Functionalization Reactions Utilizing Organic Photoredox Catalysis
Development of Aliphatic C-H Functionalization Reactions Utilizing Organic Photoredox Catalysis
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20250211152646
- ISBN
- 9798346873631
- DDC
- 547
- 서명/저자
- Development of Aliphatic C-H Functionalization Reactions Utilizing Organic Photoredox Catalysis
- 발행사항
- [Sl] : The University of North Carolina at Chapel Hill, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 183 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-06, Section: B.
- 주기사항
- Advisor: Nicewicz, David A.
- 학위논문주기
- Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2024.
- 초록/해제
- 요약C-H functionalization has been an invaluable tool for the synthesis of complex molecules within the pharmaceutical industry. Late-stage diversification of molecules via accessing C-H bonds has been sought after and the ability to achieve selective C-H bond functionalization is crucial. Distinguishing between other reactive functional handles, as well as the most abundant bond in nature, is an extraordinary challenge in modern chemical synthesis in which new methodologies are continuously being developed. Photoredox catalysis has been an important facet of reactivity over the past few decades and has seen a wide variety of use within the realm of C-H functionalization. Due to the unique properties of organic photocatalysts, these reagents have promoted access to and control of high energy intermediates that transition metal photoredox catalysts or conventional polar chemistry are unable to access. Additionally, late row transition metal complexes are costly and difficult to synthesize, leading to more sought-after sustainable methods of single electron catalysis.Development of a novel methodology for activating the homoallylic C-H bonds of olefins is described in Chapter 2. This utilizes an established strategy of accessing readily oxidizable intermediates in-situ via tandem photoredox catalysis and cobalt(II) dehydrogenation catalysis. Ultimately, the selectivity of C-H functionalization between the 1,2- vs 1,4-addition adducts remains a challenge with this approach. Further experiments are needed to induce desired reactivity in order to functionalize a C-H bond that is classically difficult to access considering the lability of the allylic C-H bond.A strategy for selective aliphatic C-H functionalization of alcohols is presented in Chapter 3. This concept draws on literature precedent surrounding the photophysical properties of transient aryl sulfoxide cation radical intermediates and their fate over the course of typical reaction conditions. Serendipitously, it was discovered that alkoxy radical generation could be induced through utilization of these high energy species. Described herein is the generation of alkoxy radicals and their subsequent reaction pathways.Chapter 4 delineates the foundation for β-C-H functionalization of alcohols in a manner reminiscent of the previously established alkoxy radical generation methodology. Synthesis of radical mediators in the form of Y=X bonding patterns and their subsequent reactivity are described.
- 일반주제명
- Organic chemistry
- 일반주제명
- Chemistry
- 일반주제명
- Pharmaceutical sciences
- 키워드
- Alkoxy radicals
- 기타저자
- The University of North Carolina at Chapel Hill Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-06B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
008250123s2024 us c eng d■001000017163272
■00520250211152646
■006m o d
■007cr#unu||||||||
■020 ▼a9798346873631
■035 ▼a(MiAaPQ)AAI31486050
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a547
■1001 ▼aFinis, Dominic Schaefer.
■24510▼aDevelopment of Aliphatic C-H Functionalization Reactions Utilizing Organic Photoredox Catalysis
■260 ▼a[Sl]▼bThe University of North Carolina at Chapel Hill▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a183 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-06, Section: B.
■500 ▼aAdvisor: Nicewicz, David A.
■5021 ▼aThesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2024.
■520 ▼aC-H functionalization has been an invaluable tool for the synthesis of complex molecules within the pharmaceutical industry. Late-stage diversification of molecules via accessing C-H bonds has been sought after and the ability to achieve selective C-H bond functionalization is crucial. Distinguishing between other reactive functional handles, as well as the most abundant bond in nature, is an extraordinary challenge in modern chemical synthesis in which new methodologies are continuously being developed. Photoredox catalysis has been an important facet of reactivity over the past few decades and has seen a wide variety of use within the realm of C-H functionalization. Due to the unique properties of organic photocatalysts, these reagents have promoted access to and control of high energy intermediates that transition metal photoredox catalysts or conventional polar chemistry are unable to access. Additionally, late row transition metal complexes are costly and difficult to synthesize, leading to more sought-after sustainable methods of single electron catalysis.Development of a novel methodology for activating the homoallylic C-H bonds of olefins is described in Chapter 2. This utilizes an established strategy of accessing readily oxidizable intermediates in-situ via tandem photoredox catalysis and cobalt(II) dehydrogenation catalysis. Ultimately, the selectivity of C-H functionalization between the 1,2- vs 1,4-addition adducts remains a challenge with this approach. Further experiments are needed to induce desired reactivity in order to functionalize a C-H bond that is classically difficult to access considering the lability of the allylic C-H bond.A strategy for selective aliphatic C-H functionalization of alcohols is presented in Chapter 3. This concept draws on literature precedent surrounding the photophysical properties of transient aryl sulfoxide cation radical intermediates and their fate over the course of typical reaction conditions. Serendipitously, it was discovered that alkoxy radical generation could be induced through utilization of these high energy species. Described herein is the generation of alkoxy radicals and their subsequent reaction pathways.Chapter 4 delineates the foundation for β-C-H functionalization of alcohols in a manner reminiscent of the previously established alkoxy radical generation methodology. Synthesis of radical mediators in the form of Y=X bonding patterns and their subsequent reactivity are described.
■590 ▼aSchool code: 0153.
■650 4▼aOrganic chemistry
■650 4▼aChemistry
■650 4▼aPharmaceutical sciences
■653 ▼aPhotoredox catalysis
■653 ▼aDehydrogenation catalysis
■653 ▼aPharmaceutical industry
■653 ▼aAlkoxy radicals
■690 ▼a0490
■690 ▼a0572
■690 ▼a0485
■71020▼aThe University of North Carolina at Chapel Hill▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-06B.
■790 ▼a0153
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17163272▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
