title: Influence of base and structure in the reversible covalent conjugate addition of thiol to polycyclic enone scaffolds.
abstract: The energetics of thiol addition and elimination reactions to bicyclic enones derived from an indole core structure were explored using (1)H NMR and density functional theory (DFT) calculations. The agreement between experiment and theory is excellent, and the combined results reveal that even minor changes in the conformation of the enone, substituents on the scaffold, and the use of different bases have a signficant influence on product distribution. A potential application of these principles is in the rational design of new reversible covalent enzyme inhibitors.
authors: Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
authors: Christopher J
authors: CJ
authors: Rosenker
authors: Elizabeth H
authors: EH
authors: Krenske
authors: K N
authors: KN
authors: Houk
authors: Peter
authors: P
authors: Wipf
mesh_terms: D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D007211:Indoles; D007659:Ketones; D013438:Sulfhydryl Compounds