title: Triiodide-Mediated δ-Amination of Secondary C-H Bonds.
abstract: The Cδ -H amination of unactivated, secondary C-H bonds to form a broad range of functionalized pyrrolidines has been developed by a triiodide (I3 (-) )-mediated strategy. By in situ 1) oxidation of sodium iodide and 2) sequestration of the transiently generated iodine (I2 ) as I3 (-) , this approach precludes undesired I2 -mediated decomposition which can otherwise limit synthetic utility to only weak C(sp(3) )-H bonds. The mechanism of this triiodide-mediated cyclization of unbiased, secondary C(sp(3) )-H bonds, by either thermal or photolytic initiation, is supported by NMR and UV/Vis data, as well as intercepted intermediates.
authors.affiliation: Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, 43210, USA.
authors.forename: Ethan A
authors.initials: EA
authors.lastname: Wappes
authors.affiliation: Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, 43210, USA.
authors.forename: Stacy C
authors.initials: SC
authors.lastname: Fosu
authors.affiliation: Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, 43210, USA.
authors.forename: Trevor C
authors.initials: TC
authors.lastname: Chopko
authors.affiliation: Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, 43210, USA. nagib.1@osu.edu.
authors.forename: David A
authors.identifier: 0000-0002-2275-6381
authors.initials: DA
authors.lastname: Nagib
mesh_terms: D000586:Amination; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D007454:Iodides / Q000737:chemistry*; D015394:Molecular Structure; D011759:Pyrrolidines / Q000737:chemistry*
chemical_list: D000588:Amines; D007454:Iodides; D011759:Pyrrolidines
keywords: C−H functionalization; amination; hydrogen atom transfer; radical chemistry; triiodide