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Cascade Palladium-Catalyzed Stereoselective Synthesis of Polycyclic Nitrogen Heterocycles Via Reactions of Allylanilines =
Cascade Palladium-Catalyzed Stereoselective Synthesis of Polycyclic Nitrogen Heterocycles Via Reactions of Allylanilines =
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202103349
- ISBN
- 9798314857854
- DDC
- 547
- 서명/저자
- Cascade Palladium-Catalyzed Stereoselective Synthesis of Polycyclic Nitrogen Heterocycles Via Reactions of Allylanilines =
- 발행사항
- [Sl] : University of Michigan, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 127 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-11, Section: B.
- 주기사항
- Advisor: Wolfe, John P.
- 학위논문주기
- Thesis (Ph.D.)--University of Michigan, 2024.
- 초록/해제
- 요약Metal-catalyzed alkene difunctionalization reactions have been targeted and developed by chemists as a quintessential class of important and efficient transformations for both academic research and industry efforts. Specifically, many chemists have discovered and improved methods of metal-catalyzed diamination and carboamination reactions of unactivated alkenes to prepare nitrogen heterocycles that appear in natural products and drug candidates. The Wolfe Lab at University of Michigan has developed a series of methods for the synthesis of nitrogen-containing heterocycles through palladium-catalyzed alkene carboamination reactions. In these transformations, alkenes bearing tethered amine nucleophiles are coupled with aryl or alkenyl halide electrophiles to rapidly generate nitrogen heterocycles from readily available starting materials. These reactions are valuable tools that can be used in drug discovery and chemical biology to produce a diverse library of compounds containing common pharmacophores. However, the optimization of these transformations can be challenging due to competing side reactions, as the intermediates in the catalytic processes can frequently react in more than one way. This can often be controlled by using very specific catalysts or ligands to minimize side reactions and provide optimal yields and stereoselectivities for products. This Ph.D. dissertation describes the development of a new tandem intra/intermolecular N-arylation/alkene carboamination reaction between 2-allylaniline derivatives and 1,2-dihalobenzene electrophiles that generate polycyclic nitrogen heterocycles. These transformations generate two carbon-nitrogen bonds and one carbon-carbon bond, leading to the formation of two rings in a single process. These reactions form biologically relevant dihydroindoloindole derivative ring systems that are of considerable interest and utility. This method is a valuable tool that can be used in drug discovery and chemical biology to produce a diverse archive of molecules containing common scaffolds. The transformations provide the heterocyclic products in good yield with up to 19:1 diastereoselectivity and allow for the construction of a rarely-described class of nitrogen heterocycles from substrates prepared in in only 1-2 steps from commercially available materials. This dissertation describes the background behind this work along with the synthesis of starting materials, reaction optimization, ligand effects, exploration of the scope of the chemistry, and isolation/purification of the products. The mechanism of the tandem reactions, which is analogous to previously described N-arylation and alkene carboamination reactions, is also presented.
- 일반주제명
- Organic chemistry
- 일반주제명
- Chemistry
- 키워드
- Alkene
- 키워드
- Carboamination
- 키워드
- Cascade
- 키워드
- Organometallic
- 키워드
- Palladium
- 키워드
- Synthesis
- 기타저자
- University of Michigan Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-11B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■006m o d
■007cr#unu||||||||
■020 ▼a9798314857854
■035 ▼a(MiAaPQ)AAI31636929
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a547
■1001 ▼aCulberson, Matthew R.▼0(orcid)0000-0001-8372-1177
■24510▼aCascade Palladium-Catalyzed Stereoselective Synthesis of Polycyclic Nitrogen Heterocycles Via Reactions of Allylanilines =
■260 ▼a[Sl]▼bUniversity of Michigan▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a127 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-11, Section: B.
■500 ▼aAdvisor: Wolfe, John P.
■5021 ▼aThesis (Ph.D.)--University of Michigan, 2024.
■520 ▼aMetal-catalyzed alkene difunctionalization reactions have been targeted and developed by chemists as a quintessential class of important and efficient transformations for both academic research and industry efforts. Specifically, many chemists have discovered and improved methods of metal-catalyzed diamination and carboamination reactions of unactivated alkenes to prepare nitrogen heterocycles that appear in natural products and drug candidates. The Wolfe Lab at University of Michigan has developed a series of methods for the synthesis of nitrogen-containing heterocycles through palladium-catalyzed alkene carboamination reactions. In these transformations, alkenes bearing tethered amine nucleophiles are coupled with aryl or alkenyl halide electrophiles to rapidly generate nitrogen heterocycles from readily available starting materials. These reactions are valuable tools that can be used in drug discovery and chemical biology to produce a diverse library of compounds containing common pharmacophores. However, the optimization of these transformations can be challenging due to competing side reactions, as the intermediates in the catalytic processes can frequently react in more than one way. This can often be controlled by using very specific catalysts or ligands to minimize side reactions and provide optimal yields and stereoselectivities for products. This Ph.D. dissertation describes the development of a new tandem intra/intermolecular N-arylation/alkene carboamination reaction between 2-allylaniline derivatives and 1,2-dihalobenzene electrophiles that generate polycyclic nitrogen heterocycles. These transformations generate two carbon-nitrogen bonds and one carbon-carbon bond, leading to the formation of two rings in a single process. These reactions form biologically relevant dihydroindoloindole derivative ring systems that are of considerable interest and utility. This method is a valuable tool that can be used in drug discovery and chemical biology to produce a diverse archive of molecules containing common scaffolds. The transformations provide the heterocyclic products in good yield with up to 19:1 diastereoselectivity and allow for the construction of a rarely-described class of nitrogen heterocycles from substrates prepared in in only 1-2 steps from commercially available materials. This dissertation describes the background behind this work along with the synthesis of starting materials, reaction optimization, ligand effects, exploration of the scope of the chemistry, and isolation/purification of the products. The mechanism of the tandem reactions, which is analogous to previously described N-arylation and alkene carboamination reactions, is also presented.
■590 ▼aSchool code: 0127.
■650 4▼aOrganic chemistry
■650 4▼aChemistry
■653 ▼aAlkene
■653 ▼aCarboamination
■653 ▼aCascade
■653 ▼aOrganometallic
■653 ▼aPalladium
■653 ▼aSynthesis
■690 ▼a0490
■690 ▼a0485
■71020▼aUniversity of Michigan▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-11B.
■790 ▼a0127
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17357352▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
