서브메뉴
검색
Handling Fluorinated Gases As Solid Reagents Using Metal-Organic Frameworks to Enable Fluorovinylation And Fluoroalkylation Reactions
Handling Fluorinated Gases As Solid Reagents Using Metal-Organic Frameworks to Enable Fluorovinylation And Fluoroalkylation Reactions
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202104829
- ISBN
- 9798293825288
- DDC
- 540
- 서명/저자
- Handling Fluorinated Gases As Solid Reagents Using Metal-Organic Frameworks to Enable Fluorovinylation And Fluoroalkylation Reactions
- 발행사항
- [Sl] : Cornell University, 2025
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2025
- 형태사항
- 512 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 87-04, Section: A.
- 주기사항
- Advisor: Milner, Phillip.
- 학위논문주기
- Thesis (Ph.D.)--Cornell University, 2025.
- 초록/해제
- 요약Fluorinated organic compounds are ubiquitous in pharmaceuticals and agrochemicals because they typically exhibit improved lipophilicity, binding affinity, and metabolic stability relative to their non-fluorinated counterparts. Despite their significance, selective and efficient fluorovinylation and fluoroalkylation protocols remain underdeveloped. Fluorinated commodity chemicals such as vinylidene fluoride (VDF), trifluoropropene (TFP), hexafluoropropene (HFP), and trifluoromethyl iodide (TFMI) represent intuitive fluorovinylation and fluoroalkylation reagents. However, their gaseous nature at room temperature and pressure (RTP) limits their practical use. We report that fluorinated gases can be stored within a magnesium-based metal-organic framework (MOF), enabling their handling as solid reagents for the first time. Encapsulation of the gas-MOF reagents within wax facilitates their stable storage in air at RT for up to two months without any loss in performance. Employing these gas-MOF reagents, we discovered that VDF undergoes Pd-catalyzed defluorinative couplings with (hetero)arylboronic acids to yield α-fluorostyrenes. Alternatively, the gem-difluorovinylated analogues can be accessed by converting VDF to a 2,2-difluorovinylzinc chloride intermediate that engages in Negishi couplings with (hetero)aryl halides to deliver β,β-difluorostyrenes. Furthermore, we uncovered a defluorinative coupling of VDF with NH-heteroarenes, producing novel N-fluorovinylated heterocycles. Demonstrating the generality of this delivery strategy to other gaseous reagents, TFP participates in Heck couplings with aryl halides to furnish β-trifluoromethylstyrenes, while TFMI undergoes Fe-catalyzed oxidative trifluoromethylations of (hetero)arenes. Given the successful delivery of a range of fluorinated gases using MOFs, this strategy provides a generalizable and user-friendly platform for discovering new reactions involving (fluorinated) gaseous reagents.
- 일반주제명
- Chemistry
- 일반주제명
- Chemical engineering
- 키워드
- Heck couplings
- 키워드
- Agrochemicals
- 기타저자
- Cornell University Chemistry and Chemical Biology
- 기본자료저록
- Dissertations Abstracts International. 87-04A.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
008260126s2025 us c eng d■001000017359068
■00520260202104829
■006m o d
■007cr#unu||||||||
■020 ▼a9798293825288
■035 ▼a(MiAaPQ)AAI32170390
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a540
■1001 ▼aKeasler, Kaitlyn Taylor.▼0(orcid)0000-0003-4805-9602
■24510▼aHandling Fluorinated Gases As Solid Reagents Using Metal-Organic Frameworks to Enable Fluorovinylation And Fluoroalkylation Reactions
■260 ▼a[Sl]▼bCornell University▼c2025
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2025
■300 ▼a512 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 87-04, Section: A.
■500 ▼aAdvisor: Milner, Phillip.
■5021 ▼aThesis (Ph.D.)--Cornell University, 2025.
■520 ▼aFluorinated organic compounds are ubiquitous in pharmaceuticals and agrochemicals because they typically exhibit improved lipophilicity, binding affinity, and metabolic stability relative to their non-fluorinated counterparts. Despite their significance, selective and efficient fluorovinylation and fluoroalkylation protocols remain underdeveloped. Fluorinated commodity chemicals such as vinylidene fluoride (VDF), trifluoropropene (TFP), hexafluoropropene (HFP), and trifluoromethyl iodide (TFMI) represent intuitive fluorovinylation and fluoroalkylation reagents. However, their gaseous nature at room temperature and pressure (RTP) limits their practical use. We report that fluorinated gases can be stored within a magnesium-based metal-organic framework (MOF), enabling their handling as solid reagents for the first time. Encapsulation of the gas-MOF reagents within wax facilitates their stable storage in air at RT for up to two months without any loss in performance. Employing these gas-MOF reagents, we discovered that VDF undergoes Pd-catalyzed defluorinative couplings with (hetero)arylboronic acids to yield α-fluorostyrenes. Alternatively, the gem-difluorovinylated analogues can be accessed by converting VDF to a 2,2-difluorovinylzinc chloride intermediate that engages in Negishi couplings with (hetero)aryl halides to deliver β,β-difluorostyrenes. Furthermore, we uncovered a defluorinative coupling of VDF with NH-heteroarenes, producing novel N-fluorovinylated heterocycles. Demonstrating the generality of this delivery strategy to other gaseous reagents, TFP participates in Heck couplings with aryl halides to furnish β-trifluoromethylstyrenes, while TFMI undergoes Fe-catalyzed oxidative trifluoromethylations of (hetero)arenes. Given the successful delivery of a range of fluorinated gases using MOFs, this strategy provides a generalizable and user-friendly platform for discovering new reactions involving (fluorinated) gaseous reagents.
■590 ▼aSchool code: 0058.
■650 4▼aChemistry
■650 4▼aChemical engineering
■653 ▼aHexafluoropropene
■653 ▼aTrifluoromethyl iodide
■653 ▼aHeck couplings
■653 ▼aAgrochemicals
■690 ▼a0485
■690 ▼a0542
■690 ▼a0635
■71020▼aCornell University▼bChemistry and Chemical Biology.
■7730 ▼tDissertations Abstracts International▼g87-04A.
■790 ▼a0058
■791 ▼aPh.D.
■792 ▼a2025
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17359068▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
