Electron-Transfer Substitution Reactions: Stereochemistry

Article abstract of DOI:10.1021/jo00233a001

Substitution of the aliphatic nitro group of optically active 2-(p-nitrophenyl)-2-nitrobutane (II) by sodium azide, sodium thiophenoxide, sodium benzenesulfinate, and the lithium salt of 2-nitropropane invariably occurs with complete loss of optical activity.Furthermore, levorotatory II is racemized by sodium nitrite.These facts support the view that substitution reactions in p-nitrocumyl systems proceed via the electron-transfer chain mechanism of eq 2-5.