title: Native functionality in triple catalytic cross-coupling: sp³ C-H bonds as latent nucleophiles.
abstract: The use of sp(3) 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 sp(3) C-H bonds in both cyclic and acyclic systems.
authors.affiliation: Merck Center for Catalysis at Princeton University, Princeton, NJ 08544, USA.
authors.forename: Megan H
authors.initials: MH
authors.lastname: Shaw
authors.affiliation: Merck Center for Catalysis at Princeton University, Princeton, NJ 08544, USA.
authors.forename: Valerie W
authors.initials: VW
authors.lastname: Shurtleff
authors.affiliation: Merck Center for Catalysis at Princeton University, Princeton, NJ 08544, USA.
authors.forename: Jack A
authors.initials: JA
authors.lastname: Terrett
authors.affiliation: Merck Center for Catalysis at Princeton University, Princeton, NJ 08544, USA.
authors.forename: James D
authors.initials: JD
authors.lastname: Cuthbertson
authors.affiliation: Merck Center for Catalysis at Princeton University, Princeton, NJ 08544, USA. dmacmill@princeton.edu.
authors.forename: David W C
authors.initials: DW
authors.lastname: MacMillan