89548-97-0Relevant academic research and scientific papers
Charge Separation on Molecular Basis: Chemoselectivity, Regio-, and Stereoselectivity of C-C Bond Formation as Probes for Electron-Transfer Processes
Aurbach, Irmgard,Ponti, Pier Paolo,Salbeck, Erika,Schmuck, Heike,Daub, Joerg
, p. 1101 - 1108 (2007/10/02)
Lithium 8-(dimethylamino)heptafulven-8-olate (1), containing the cross-conjugated heptafulvene structural unit, was investigated with respect to SET (single-electron transfer)-type and polar mechanisms in reactions with methyl iodide and with the carbonyl compounds benzaldehyde (2a), benzophenone (2b), methyl phenylglyoxylate (2c), benzil (2d), and 4-nitrobenzaldehyde (2e).The selectivity of product formation was used as a mechanistic probe.Experimentally, two reaction pathways with different chemoselectivity were observed: Oxidative dimerisation of the heptafulvene 1 accompanied by reduction of the carbonyl compound and "aldol-type" reactions.The specific outcome depends on the electronic properties of the carbonyl compounds.A qualitative correlation between the reduction potentials of the carbonyl compounds and the products formed has been found.
