title: Capricious selectivity in electrophilic deuteration of methylenedioxy substituted aromatic compounds.
abstract: Ring deuteration via the SEAr mechanism, which is usually problem-free, is found to be troublesome with methylenedioxy substituent aromatics. We report a case where the deuteration not only partially fails at one of the ortho positions but also is completely prevented by a conformation dependent effect at the other o-position. Such selectivity discrepancies are important due to the widespread occurrence of methylenedioxy substituted natural products. Density functional theory calculations were used to elucidate the exchange reaction mechanism in 1,2-dialkoxybenzenes.
authors.affiliation: Department of Chemistry, University of Helsinki , P.O. Box 55, FIN-00014 Helsinki, Finland.
authors.forename: Monika
authors.initials: M
authors.lastname: Pohjoispää
authors.forename: Raúl
authors.initials: R
authors.lastname: Mera-Adasme
authors.forename: Dage
authors.initials: D
authors.lastname: Sundholm
authors.forename: Sami
authors.initials: S
authors.lastname: Heikkinen
authors.forename: Tapio
authors.initials: T
authors.lastname: Hase
authors.forename: Kristiina
authors.initials: K
authors.lastname: Wähälä
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D004149:Dioxoles / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009930:Organic Chemicals; D011789:Quantum Theory
chemical_list: D001555:Benzene Derivatives; D004149:Dioxoles; D009930:Organic Chemicals; C040539:1,3-benzodioxole