Frustrated Radical Pairs in Organic Synthesis.

Autor: Ju M; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States., Lu Z; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States., Novaes LFT; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States., Martinez Alvarado JI; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States., Lin S; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2023 Sep 13; Vol. 145 (36), pp. 19478-19489. Date of Electronic Publication: 2023 Sep 01.
DOI: 10.1021/jacs.3c07070
Abstrakt: Frustrated radical pairs (FRPs) describe the phenomenon that two distinct radicals─which would otherwise annihilate each other to form a closed-shell covalent adduct─can coexist in solution, owing to steric repulsion or weak bonding association. FRPs are typically formed via spontaneous single-electron transfer between two sterically encumbered precursors─an oxidant and a reductant─under ambient conditions. The two components of a FRP exhibit orthogonal chemical properties and can often act in cooperativity to achieve interesting radical reactivities. Initially observed in the study of traditional frustrated Lewis pairs, FRPs have recently been shown to be capable of homolytically activating various chemical bonds. In this Perspective, we will discuss the discovery of FRPs, their fundamental reactivity in chemical bond activation, and recent developments of their use in synthetic organic chemistry, including in C-H bond functionalization. We anticipate that FRPs will provide new reaction strategies for solving challenging problems in modern organic synthesis.
Databáze: MEDLINE