title: Reactions of the cumyloxyl radical with secondary amides. The influence of steric and stereoelectronic effects on the hydrogen atom transfer reactivity and selectivity.
abstract: A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from secondary alkanamides to the cumyloxyl radical was carried out in acetonitrile. HAT predominantly occurs from the N-alkyl α-C-H bonds, and a >60-fold decrease in kH was observed by increasing the steric hindrance of the acyl and N-alkyl groups. The role of steric and stereoelectronic effects on the reactivity and selectivity is discussed in the framework of HAT reactions from peptides.
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università "Tor Vergata" , Via della Ricerca Scientifica, 1 I-00133 Rome, Italy.
authors.forename: Michela
authors.initials: M
authors.lastname: Salamone
authors.forename: Federica
authors.initials: F
authors.lastname: Basili
authors.forename: Riccardo
authors.initials: R
authors.lastname: Mele
authors.forename: Marco
authors.initials: M
authors.lastname: Cianfanelli
authors.forename: Massimo
authors.initials: M
authors.lastname: Bietti
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D000473:Alkanes / Q000737:chemistry*; D000577:Amides / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D007700:Kinetics; D015394:Molecular Structure; D010455:Peptides / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D000473:Alkanes; D000577:Amides; D010455:Peptides; D006859:Hydrogen; C032159:acetonitrile