title: Malonic acid half oxyesters and thioesters: solvent-free synthesis and DFT analysis of their enols.
abstract: A much improved synthetic route to malonic acid half thioesters (MAHTs) and oxyesters (MAHOs), the easy incorporation of deuterium labeling expecially in MAHTs, and an unexpectedly large difference in enolization chemistry between MAHTs and MAHOs are reported. Density functional theory calculations explore the origins of this difference and identify an additional MAHT molecular orbital which increases delocalization between sulfur and the enol in both cisoid and transoid forms.
authors.affiliation: School of Chemistry, University of East Anglia, Norwich Research Park, NR4 7TJ, UK. s.bew@uea.ac.uk
authors.forename: Sean P
authors.initials: SP
authors.lastname: Bew
authors.forename: G Richard
authors.initials: GR
authors.lastname: Stephenson
authors.forename: Jacques
authors.initials: J
authors.lastname: Rouden
authors.forename: Luis A
authors.initials: LA
authors.lastname: Martinez-Lozano
authors.forename: Haseena
authors.initials: H
authors.lastname: Seylani
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D008314:Malonates / Q000737:chemistry*; D011789:Quantum Theory; D013457:Sulfur Compounds / Q000737:chemistry*
chemical_list: D000438:Alcohols; D008314:Malonates; D013457:Sulfur Compounds; C030290:malonic acid