title: A mechanistic study on the amidation of esters mediated by sodium formamide.
abstract: Kinetic and computational studies on the amidation of esters with mixtures of formamide and sodium methoxide are described. Rate studies are consistent with a fast deprotonation of formamide followed by two reversible acyl transfers affected by solvent participation. MP2 calculations suggest that the first acyl transfer between the ester and sodium formamide is rate-determining. The transition structures leading to the formation and collapse of the first tetrahedral intermediate are calculated to be isoenergetic.
authors.affiliation: Chemical Development, Bristol-Myers Squibb Company, One Squibb Drive, New Brunswick, New Jersey 08903, United States. antonio.ramirez1@bms.com
authors.forename: Antonio
authors.initials: A
authors.lastname: Ramirez
authors.forename: Boguslaw
authors.initials: B
authors.lastname: Mudryk
authors.forename: Lucius
authors.initials: L
authors.lastname: Rossano
authors.forename: Srinivas
authors.initials: S
authors.lastname: Tummala
mesh_terms: D004952:Esters; D005559:Formamides / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D007700:Kinetics; D000432:Methanol / Q000737:chemistry*; D008958:Models, Molecular; D012964:Sodium / Q000737:chemistry*; D012997:Solvents
chemical_list: D004952:Esters; D005559:Formamides; D007477:Ions; D012997:Solvents; D012964:Sodium; D000432:Methanol