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Studies on the Photochemical [2+2] Cycloadditions of Unactivated Olefins
![Studies on the Photochemical [2+2] Cycloadditions of Unactivated Olefins](/Users/Baul/Images/book.png)
Studies on the Photochemical [2+2] Cycloadditions of Unactivated Olefins
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202103136
- ISBN
- 9798311952552
- DDC
- 600
- 서명/저자
- Studies on the Photochemical [2+2] Cycloadditions of Unactivated Olefins
- 발행사항
- [Sl] : Stanford University, 2023
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2023
- 형태사항
- 313 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-12, Section: B.
- 주기사항
- Advisor: Burns, Noah.
- 학위논문주기
- Thesis (Ph.D.)--Stanford University, 2023.
- 초록/해제
- 요약[2+2] cycloadditions are arguably the most powerful reactions for constructing cyclobutanes which are prominent motifs in natural products and are becoming increasingly common pharmacophores in medicinal chemistry. Despite the growing number of [2+2] methodologies, virtually all of them rely on the cyclization of at least one activated π partner. An exception to this rule is the Kochi-Salomon reaction, which is able to cyclize aliphatic olefins in the presence of simple Cu(I) catalysts. Introduced over 50 years ago, it has seen very little in the way of methodological development and still suffers from a number of drawbacks including the need for moisture- and air-sensitive reagents, a limited substrate scope and a lack of stereocontrol. This thesis describes strategies to address these shortcomings starting with our efforts at rendering the Kochi-Salomon reaction enantioselective, first using weakly coordinating chiral counterions and then using chiral diene ligands. Although ultimately unsuccessful, these attempts provided valuable insight into Cu-catalyzed [2+2] photocycloadditions which led to the development of aqueous amine-tolerant cyclizations of unactivated olefins. Basic amines, hitherto incompatible in these types of reactions, may be protonated then cyclized in water, an unlikely solvent, using some of the most standard reagents available in any chemistry lab. This discussion is followed by a series of smaller ventures into further developments of the Kochi-Salomon reaction, including strategies to exert diastereocontrol and efforts to cyclize sulfur-containing substrates and quaternary ammonium substrates. The final chapter details the development of a scalable route to anti-[3]-ladderdiene. While not related to the Kochi-Salomon reaction, this strained molecule fits well into the realm of cyclobutanes which is central to this thesis.
- 일반주제명
- Metals
- 일반주제명
- Sulfur
- 일반주제명
- Oxidation
- 일반주제명
- Reagents
- 일반주제명
- Hydrogenation
- 일반주제명
- Catalysis
- 일반주제명
- Solvents
- 일반주제명
- Organic chemistry
- 기타저자
- Stanford University.
- 기본자료저록
- Dissertations Abstracts International. 86-12B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■020 ▼a9798311952552
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■035 ▼a(MiAaPQ)Stanfordmq145pf1607
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a600
■1001 ▼aMansson, Carl Magnus Fabian.
■24510▼aStudies on the Photochemical [2+2] Cycloadditions of Unactivated Olefins
■260 ▼a[Sl]▼bStanford University▼c2023
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2023
■300 ▼a313 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-12, Section: B.
■500 ▼aAdvisor: Burns, Noah.
■5021 ▼aThesis (Ph.D.)--Stanford University, 2023.
■520 ▼a[2+2] cycloadditions are arguably the most powerful reactions for constructing cyclobutanes which are prominent motifs in natural products and are becoming increasingly common pharmacophores in medicinal chemistry. Despite the growing number of [2+2] methodologies, virtually all of them rely on the cyclization of at least one activated π partner. An exception to this rule is the Kochi-Salomon reaction, which is able to cyclize aliphatic olefins in the presence of simple Cu(I) catalysts. Introduced over 50 years ago, it has seen very little in the way of methodological development and still suffers from a number of drawbacks including the need for moisture- and air-sensitive reagents, a limited substrate scope and a lack of stereocontrol. This thesis describes strategies to address these shortcomings starting with our efforts at rendering the Kochi-Salomon reaction enantioselective, first using weakly coordinating chiral counterions and then using chiral diene ligands. Although ultimately unsuccessful, these attempts provided valuable insight into Cu-catalyzed [2+2] photocycloadditions which led to the development of aqueous amine-tolerant cyclizations of unactivated olefins. Basic amines, hitherto incompatible in these types of reactions, may be protonated then cyclized in water, an unlikely solvent, using some of the most standard reagents available in any chemistry lab. This discussion is followed by a series of smaller ventures into further developments of the Kochi-Salomon reaction, including strategies to exert diastereocontrol and efforts to cyclize sulfur-containing substrates and quaternary ammonium substrates. The final chapter details the development of a scalable route to anti-[3]-ladderdiene. While not related to the Kochi-Salomon reaction, this strained molecule fits well into the realm of cyclobutanes which is central to this thesis.
■590 ▼aSchool code: 0212.
■650 4▼aMetals
■650 4▼aSulfur
■650 4▼aOxidation
■650 4▼aReagents
■650 4▼aHydrogenation
■650 4▼aCatalysis
■650 4▼aSolvents
■650 4▼aOrganic chemistry
■690 ▼a0490
■71020▼aStanford University.
■7730 ▼tDissertations Abstracts International▼g86-12B.
■790 ▼a0212
■791 ▼aPh.D.
■792 ▼a2023
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17357134▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
