Native functionality in triple catalytic cross-coupling: sp3 C–H bonds as latent nucleophiles

• Autores: Megan H. Shaw, Valerie W. Shurtleff, Jack A. Terrett
• Localización: Science, ISSN 0036-8075, Vol. 352, Nº 6291, 2016, págs. 1304-1308
• Idioma: inglés
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• Resumen

  • The use of sp3 C–H bonds—which are ubiquitous in organic molecules—as latent nucleophile equivalents for transition metal–catalyzed cross-coupling reactions has the potential to substantially streamline synthetic efforts in organic chemistry while bypassing substrate activation steps. Through the combination of photoredox-mediated hydrogen atom transfer (HAT) and nickel catalysis, we have developed a highly selective and general C–H arylation protocol that activates a wide array of C–H bonds as native functional handles for cross-coupling. This mild approach takes advantage of a tunable HAT catalyst that exhibits predictable reactivity patterns based on enthalpic and bond polarity considerations to selectively functionalize α-amino and α-oxy sp3 C–H bonds in both cyclic and acyclic systems.