title: Electroreductive dimerization of coumarin and coumarin analogues at carbon cathodes.
abstract: Electrochemical reduction of coumarin (1), 6-methylcoumarin (2), 7-methylcoumarin (3), 7-methoxycoumarin (4), and 5,7-dimethoxycoumarin (5) at carbon cathodes in dimethylformamide containing 0.10 M tetra-n-butylammonium tetrafluoroborate has been investigated by means of cyclic voltammetry and controlled-potential (bulk) electrolysis. Cyclic voltammograms for reduction of 1-5 exhibit two irreversible cathodic peaks: (a) the first peak arises from one-electron reduction of the coumarin to form a radical-anion intermediate, which is protonated by the medium to give a neutral radical; (b) although most of this radical undergoes self-coupling to yield a hydrodimer, reduction of the remaining radical (ultimately to produce a dihydrocoumarin) causes the second cathodic peak. At a potential corresponding to the first voltammetric peak, bulk electrolysis of 1-5 affords the corresponding hydrodimer as a mixture of meso and dl diastereomers. Although the meso form dominates, the dl-to-meso ratio varies, due to steric effects arising from substituents on the aromatic ring. Electroreduction of an equimolar mixture of 1 and 4 gives, along with the anticipated symmetrical hydrodimers, an unsymmetrical product derived from the two coumarins. A mechanistic scheme involving both radical-anion and radical intermediates is proposed to account for the formation of the various products.
authors.affiliation: †Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
authors.forename: Erick M
authors.initials: EM
authors.lastname: Pasciak
authors.affiliation: †Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
authors.forename: Jonathan T
authors.initials: JT
authors.lastname: Rittichier
authors.affiliation: †Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
authors.forename: Chun-Hsing
authors.initials: CH
authors.lastname: Chen
authors.affiliation: ‡Department of Chemistry, The University of Jordan, Amman 11942, Jordan.
authors.forename: Mohammad S
authors.initials: MS
authors.lastname: Mubarak
authors.affiliation: †Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
authors.forename: Michael S
authors.initials: MS
authors.lastname: VanNieuwenhze
authors.affiliation: †Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
authors.forename: Dennis G
authors.initials: DG
authors.lastname: Peters
mesh_terms: D002244:Carbon / Q000737:chemistry*; D003374:Coumarins / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D019281:Dimerization; D055664:Electrochemical Techniques; D004566:Electrodes; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction
chemical_list: D003374:Coumarins; D002244:Carbon