title: Mild and chemoselective lactone ring-opening with (TMS)ONa. Mechanistic studies and application to sweroside derivatives.
abstract: Mild and chemoselective opening of lactones with sodium trimethylsilanolate in high yields and aprotic solvents is described. Kinetic studies demonstrate that the B(Ac)2 mechanistic pathway is followed. Nucleophilic attack of silanolate onto the carbonyl of the lactone moiety is the rate-determining step. NaOH present as an impurity accelerates the reaction. The method was further applied to the base-sensitive and stable lactones derived from highly functionalized iridoid derivatives.
authors.affiliation: Laboratoire de Pharmacognosie, Faculté des Sciences Pharmaceutiques et Biologiques, Université Paris Descartes, Sorbonne Paris Cité, UMR/CNRS No. 8638 , 4 Avenue de l'Observatoire, F-75006 Paris, France.
authors.forename: Hugues
authors.initials: H
authors.lastname: Lemoine
authors.forename: Dean
authors.initials: D
authors.lastname: Marković
authors.forename: Brigitte
authors.initials: B
authors.lastname: Deguin
mesh_terms: D057888:Iridoid Glucosides / Q000737:chemistry*; D007700:Kinetics; D007783:Lactones / Q000737:chemistry*; D015394:Molecular Structure; D012964:Sodium / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D013237:Stereoisomerism; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
chemical_list: D057888:Iridoid Glucosides; D007783:Lactones; D012997:Solvents; D014297:Trimethylsilyl Compounds; D012964:Sodium; C049412:sweroside