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Unlocking carbene reactivity by metallaphotoredox α-elimination.
Boyle, Benjamin T; Dow, Nathan W; Kelly, Christopher B; Bryan, Marian C; MacMillan, David W C.
Afiliación
  • Boyle BT; Merck Center for Catalysis, Princeton University, Princeton, NJ, USA.
  • Dow NW; Merck Center for Catalysis, Princeton University, Princeton, NJ, USA.
  • Kelly CB; Discovery Process Research, Janssen Research & Development, Spring House, PA, USA.
  • Bryan MC; Therapeutics Discovery, Janssen Research & Development, Spring House, PA, USA.
  • MacMillan DWC; Merck Center for Catalysis, Princeton University, Princeton, NJ, USA. dmacmill@princeton.edu.
Nature ; 631(8022): 789-795, 2024 Jul.
Article en En | MEDLINE | ID: mdl-38843825
ABSTRACT
The ability to tame high-energy intermediates is important for synthetic chemistry, enabling the construction of complex molecules and propelling advances in the field of synthesis. Along these lines, carbenes and carbenoid intermediates are particularly attractive, but often unknown, high-energy intermediates1,2. Classical methods to access metal carbene intermediates exploit two-electron chemistry to form the carbon-metal bond. However, these methods are usually prohibitive because of reagent safety concerns, limiting their broad implementation in synthesis3-6. Mechanistically, an alternative approach to carbene intermediates that could circumvent these pitfalls would involve two single-electron

steps:

radical addition to metal to forge the initial carbon-metal bond followed by redox-promoted α-elimination to yield the desired metal carbene intermediate. Here we realize this strategy through a metallaphotoredox platform that exploits iron carbene reactivity using readily available chemical feedstocks as radical sources and α-elimination from six classes of previously underexploited leaving groups. These discoveries permit cyclopropanation and σ-bond insertion into N-H, S-H and P-H bonds from abundant and bench-stable carboxylic acids, amino acids and alcohols, thereby providing a general solution to the challenge of carbene-mediated chemical diversification.
Asunto(s)

Texto completo: 1 Colección: 01-internacional Banco de datos: MEDLINE Asunto principal: Fotoquímica / Ácidos Carboxílicos / Alcoholes / Técnicas de Química Sintética / Aminoácidos / Hierro / Metano Idioma: En Revista: Nature Año: 2024 Tipo del documento: Article País de afiliación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Banco de datos: MEDLINE Asunto principal: Fotoquímica / Ácidos Carboxílicos / Alcoholes / Técnicas de Química Sintética / Aminoácidos / Hierro / Metano Idioma: En Revista: Nature Año: 2024 Tipo del documento: Article País de afiliación: Estados Unidos