ChemInform Abstract: Ethylenic Compounds as Probes for the Study of Donor‐Acceptor Interaction

Abstract

ChemInform Abstract (73 refs.).

Unequivocal SRN1 Route of Vinyl Halides with a Multitude of Competing Pathways: Reactivity and Structure of the Vinyl Radical Intermediate

“…Consequently, E - 26 • - ⇌ Z - 26 •- isomerization is slower than the cleavage of the radical anion. Configurational equilibration of vinylic radical anions had been documented, with rate constants of 10 1 −10 5 s -1 . If the radical anion of the substrate bears fissible bond(s), fragmentation can compete with its configurational equilibration (Scheme ).…”

Radical Mechanisms in the Metallocenes

“…The cation radicals of the ferrocenyl ethylene are not subject to the cis-to-trans isomerization process. The calculations show that the cation radical center is only in the iron atom, not in the ethylene bond [62]. Therefore, one-electron oxidation of ferrocenyl ethylene occurs at the iron atom.…”

Acyloxylation of 1-Methoxycyclohex-1-ene and Other Enol Ethers with Dimethyl Peroxydicarbonate

“…The first step of pathway B is suggested to be the consequence of an one-electron oxidation of electron rich enol ether 1a to its cation radical (cf. olefin radical cation formations 15) ) followed by deprotonation to give a 2-methoxyallyl radical which is oxidized to its cation. The higher 1-Methoxy-1-cycloalkenes 1a, 13a-c 18) , in particular 1a 19) , 1-trimethylsiloxy-1-cyclohexene (1b) 20) , dimethyl peroxy-dicarbonate (2c) 21) .…”