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Approaches to Valuable Halogenated Products Using Radical-Polar Crossover Catalysis or Halogen Transfer to Arynes
Approaches to Valuable Halogenated Products Using Radical-Polar Crossover Catalysis or Hal...
Approaches to Valuable Halogenated Products Using Radical-Polar Crossover Catalysis or Halogen Transfer to Arynes

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자료유형  
 학위논문 서양
최종처리일시  
20250211152839
ISBN  
9798342715676
DDC  
547
저자명  
Gavin, Joshua T.
서명/저자  
Approaches to Valuable Halogenated Products Using Radical-Polar Crossover Catalysis or Halogen Transfer to Arynes
발행사항  
[Sl] : University of Minnesota, 2024
발행사항  
Ann Arbor : ProQuest Dissertations & Theses, 2024
형태사항  
223 p
주기사항  
Source: Dissertations Abstracts International, Volume: 86-05, Section: B.
주기사항  
Advisor: Roberts, Courtney C.
학위논문주기  
Thesis (Ph.D.)--University of Minnesota, 2024.
초록/해제  
요약Molecules with halogen atoms have many applications. In direct applications, halogenated molecules are seen in many marketed pharmaceuticals and continue to represent a growing proportion year-to-year. They also find applications in agrochemicals, polymers, and materials, and the unique properties halogenation imparts to products has been difficult to replicate by other means. Additionally, halogen-containing molecules have indirect applications for many more products because a halogen-free chemical may succeed from a synthetic intermediate containing a halogen atom. Through reactions such as Pd-catalyzed couplings, halogenated materials have become a regular feature in molecular syntheses. Thus, the synthesis of halogen-containing molecules is a vital part toward supporting the growth of the pharmaceuticals, agrochemicals, and materials industries. New methods to access these products in a more efficient manner benefits many industries. This dissertation discusses two distinct strategies to synthesize valuable halogenated products. First, the application of redox-active ligands with transition-metal catalysis is considered especially with early transition metals. The combination of redox-active ligands with relatively redox-innocent early transition metals enabled a method for synthesis of gem-difluorostyrenes. This process occurs via radical-polar crossover, a mechanism new to early-transition metals. Second, synthesis of halogen-containing products was shown by exploiting known reactivity of arynes. This method involves functionalization with amine nucleophiles followed by a rapid halogen-transfer that competes with other undesirable pathways.
일반주제명  
Organic chemistry
일반주제명  
Inorganic chemistry
일반주제명  
Molecular chemistry
키워드  
Aryne
키워드  
Catalysis
키워드  
Early transition metals
키워드  
Halogen
기타저자  
University of Minnesota Chemistry
기본자료저록  
Dissertations Abstracts International. 86-05B.
전자적 위치 및 접속  
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MARC

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■1001  ▼aGavin,  Joshua  T.
■24510▼aApproaches  to  Valuable  Halogenated  Products  Using  Radical-Polar  Crossover  Catalysis  or  Halogen  Transfer  to  Arynes
■260    ▼a[Sl]▼bUniversity  of  Minnesota▼c2024
■260  1▼aAnn  Arbor▼bProQuest  Dissertations  &  Theses▼c2024
■300    ▼a223  p
■500    ▼aSource:  Dissertations  Abstracts  International,  Volume:  86-05,  Section:  B.
■500    ▼aAdvisor:  Roberts,  Courtney  C.
■5021  ▼aThesis  (Ph.D.)--University  of  Minnesota,  2024.
■520    ▼aMolecules  with  halogen  atoms  have  many  applications.  In  direct  applications,  halogenated  molecules  are  seen  in  many  marketed  pharmaceuticals  and  continue  to  represent  a  growing  proportion  year-to-year.  They  also  find  applications  in  agrochemicals,  polymers,  and  materials,  and  the  unique  properties  halogenation  imparts  to  products  has  been  difficult  to  replicate  by  other  means.  Additionally,  halogen-containing  molecules  have  indirect  applications  for  many  more  products  because  a  halogen-free  chemical  may  succeed  from  a  synthetic  intermediate  containing  a  halogen  atom.  Through  reactions  such  as  Pd-catalyzed  couplings,  halogenated  materials  have  become  a  regular  feature  in  molecular  syntheses.  Thus,  the  synthesis  of  halogen-containing  molecules  is  a  vital  part  toward  supporting  the  growth  of  the  pharmaceuticals,  agrochemicals,  and  materials  industries.  New  methods  to  access  these  products  in  a  more  efficient  manner  benefits  many  industries.  This  dissertation  discusses  two  distinct  strategies  to  synthesize  valuable  halogenated  products.  First,  the  application  of  redox-active  ligands  with  transition-metal  catalysis  is  considered  especially  with  early  transition  metals.  The  combination  of  redox-active  ligands  with  relatively  redox-innocent  early  transition  metals  enabled  a  method  for  synthesis  of  gem-difluorostyrenes.  This  process  occurs  via  radical-polar  crossover,  a  mechanism  new  to  early-transition  metals.  Second,  synthesis  of  halogen-containing  products  was  shown  by  exploiting  known  reactivity  of  arynes.  This  method  involves  functionalization  with  amine  nucleophiles  followed  by  a  rapid  halogen-transfer  that  competes  with  other  undesirable  pathways.
■590    ▼aSchool  code:  0130.
■650  4▼aOrganic  chemistry
■650  4▼aInorganic  chemistry
■650  4▼aMolecular  chemistry
■653    ▼aAryne
■653    ▼aCatalysis
■653    ▼aEarly  transition  metals
■653    ▼aHalogen
■690    ▼a0490
■690    ▼a0488
■690    ▼a0431
■71020▼aUniversity  of  Minnesota▼bChemistry.
■7730  ▼tDissertations  Abstracts  International▼g86-05B.
■790    ▼a0130
■791    ▼aPh.D.
■792    ▼a2024
■793    ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17164169▼nKERIS▼z이  자료의  원문은  한국교육학술정보원에서  제공합니다.

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