title: Tandem Addition of Phosphite Nucleophiles Across Unsaturated Nitrogen-Containing Systems: Mechanistic Insights on Regioselectivity.
abstract: The addition of phosphite nucleophiles across linear unsaturated imines is a powerful and atom-economical methodology for the synthesis of aminophosphonates. These products are of interest from both a biological and a synthetic point of view: they act as amino acid transition state analogs and Horner-Wadsworth-Emmons reagents, respectively. In this work the reaction between dialkyl trimethylsilyl phosphites and α,β,γ,δ-diunsaturated imines was evaluated as a continuation of our previous efforts in the field. As such, the first conjugate 1,6-addition of a phosphite nucleophile across a linear unsaturated N-containing system is reported herein. Theoretical calculations were performed to rationalize the observed regioselectivites and to shed light on the proposed mechanism.
authors.affiliation: SynBioC Research Group, Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University , Coupure Links 653, 9000 Ghent, Belgium.
authors.forename: Wouter
authors.initials: W
authors.lastname: Debrouwer
authors.affiliation: Center for Molecular Modeling, Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.
authors.forename: Dietmar
authors.initials: D
authors.lastname: Hertsen
authors.affiliation: SynBioC Research Group, Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University , Coupure Links 653, 9000 Ghent, Belgium.
authors.forename: Thomas S A
authors.initials: TS
authors.lastname: Heugebaert
authors.affiliation: Department of Chemistry, Bogazici University , Bebek, Istanbul, 34342 Turkey.
authors.forename: Esma Birsen
authors.initials: EB
authors.lastname: Boydas
authors.affiliation: Center for Molecular Modeling, Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.
authors.forename: Veronique
authors.initials: V
authors.lastname: Van Speybroeck
authors.affiliation: Center for Molecular Modeling, Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.|Department of Chemistry, Bogazici University , Bebek, Istanbul, 34342 Turkey.
authors.forename: Saron
authors.initials: S
authors.lastname: Catak
authors.affiliation: SynBioC Research Group, Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University , Coupure Links 653, 9000 Ghent, Belgium.
authors.forename: Christian V
authors.identifier: 0000-0003-4393-5327
authors.initials: CV
authors.lastname: Stevens