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Functionalization of Nitrogenous Sulfur(VI) Compounds Enabled by Proton-Coupled Electron Transfer
Functionalization of Nitrogenous Sulfur(VI) Compounds Enabled by Proton-Coupled Electron Transfer
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202103509
- ISBN
- 9798280748460
- DDC
- 547
- 저자명
- Lin, Angela.
- 서명/저자
- Functionalization of Nitrogenous Sulfur(VI) Compounds Enabled by Proton-Coupled Electron Transfer
- 발행사항
- [Sl] : Princeton University, 2025
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2025
- 형태사항
- 137 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-12, Section: B.
- 주기사항
- Advisor: Knowles, Robert R.
- 학위논문주기
- Thesis (Ph.D.)--Princeton University, 2025.
- 초록/해제
- 요약Proton-coupled electron transfer (PCET) is a redox process in which a proton and an electron are transferred to two site-separated acceptors in either a concerted or stepwise fashion. This mechanism is present in a variety of important biological redox processes including photosynthesis, respiration, and nitrogen fixation, as well as inorganic contexts for the development of energy conversion technologies. More recently, concerted PCET has emerged as a powerful tool for small molecule activation, enabling the homolytic cleavage of native C-H, O-H, and N-H bonds to generate radical intermediates that can be leveraged for new synthetic transformations. Its unique thermodynamic and kinetic features offer opportunities to control chemoselectivity in radical reactions and open new avenues for advancing both racemic and asymmetric radical chemistry.This dissertation discusses recent contributions from our group toward the use of PCET for the homolytic activation of strong N-H bonds of various sulfur(VI) amine donors. Chapter 2 describes the development of an intermolecular anti-Markovnikov hydroamination of alkenes with sulfonamides, sulfamides, and sulfamates. The discovery of a perfluorinated alkoxide base was key for the development of this method, as we propose that it imparts additional thermochemical driving force for the PCET activation of N-H bonds that were previously inaccessible under this manifold. This transformation ultimately enables the general fragment coupling of two readily accessible substrate classes for the efficient synthesis of diverse secondary N-alkyl sulfur(VI) derivatives. Chapter 3 highlights the progress towards the desymmetrization of unprotected sulfonimidamide starting materials. We demonstrate proof-of-concept for this reaction, supporting our hypothesis that post-PCET hydrogen bonding interactions can be leveraged for asymmetric radical chemistry in intermolecular settings. Taken together, these works illustrate how fundamental understanding of PCET mechanisms can be used to guide reaction design, offering new radical-based routes to valuable nitrogen-containing compounds as well as new solutions for outstanding synthetic challenges.
- 일반주제명
- Organic chemistry
- 일반주제명
- Chemistry
- 일반주제명
- Computational chemistry
- 일반주제명
- Molecular chemistry
- 키워드
- Catalysis
- 키워드
- Hydroamination
- 키워드
- Photochemistry
- 기타저자
- Princeton University Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-12B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■00520260202103509
■006m o d
■007cr#unu||||||||
■020 ▼a9798280748460
■035 ▼a(MiAaPQ)AAI32003171
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a547
■1001 ▼aLin, Angela.▼0(orcid)0009-0007-7533-2762
■24510▼aFunctionalization of Nitrogenous Sulfur(VI) Compounds Enabled by Proton-Coupled Electron Transfer
■260 ▼a[Sl]▼bPrinceton University▼c2025
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2025
■300 ▼a137 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-12, Section: B.
■500 ▼aAdvisor: Knowles, Robert R.
■5021 ▼aThesis (Ph.D.)--Princeton University, 2025.
■520 ▼aProton-coupled electron transfer (PCET) is a redox process in which a proton and an electron are transferred to two site-separated acceptors in either a concerted or stepwise fashion. This mechanism is present in a variety of important biological redox processes including photosynthesis, respiration, and nitrogen fixation, as well as inorganic contexts for the development of energy conversion technologies. More recently, concerted PCET has emerged as a powerful tool for small molecule activation, enabling the homolytic cleavage of native C-H, O-H, and N-H bonds to generate radical intermediates that can be leveraged for new synthetic transformations. Its unique thermodynamic and kinetic features offer opportunities to control chemoselectivity in radical reactions and open new avenues for advancing both racemic and asymmetric radical chemistry.This dissertation discusses recent contributions from our group toward the use of PCET for the homolytic activation of strong N-H bonds of various sulfur(VI) amine donors. Chapter 2 describes the development of an intermolecular anti-Markovnikov hydroamination of alkenes with sulfonamides, sulfamides, and sulfamates. The discovery of a perfluorinated alkoxide base was key for the development of this method, as we propose that it imparts additional thermochemical driving force for the PCET activation of N-H bonds that were previously inaccessible under this manifold. This transformation ultimately enables the general fragment coupling of two readily accessible substrate classes for the efficient synthesis of diverse secondary N-alkyl sulfur(VI) derivatives. Chapter 3 highlights the progress towards the desymmetrization of unprotected sulfonimidamide starting materials. We demonstrate proof-of-concept for this reaction, supporting our hypothesis that post-PCET hydrogen bonding interactions can be leveraged for asymmetric radical chemistry in intermolecular settings. Taken together, these works illustrate how fundamental understanding of PCET mechanisms can be used to guide reaction design, offering new radical-based routes to valuable nitrogen-containing compounds as well as new solutions for outstanding synthetic challenges.
■590 ▼aSchool code: 0181.
■650 4▼aOrganic chemistry
■650 4▼aChemistry
■650 4▼aComputational chemistry
■650 4▼aMolecular chemistry
■653 ▼aCatalysis
■653 ▼aHydroamination
■653 ▼aPhotochemistry
■653 ▼aProton-coupled electron transfer
■653 ▼aAsymmetric radical chemistry
■690 ▼a0490
■690 ▼a0431
■690 ▼a0219
■690 ▼a0485
■71020▼aPrinceton University▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-12B.
■790 ▼a0181
■791 ▼aPh.D.
■792 ▼a2025
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17357421▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
