Nathan Kornblum

Electron-transfer substitution reactions: Facilitation by the cyano group

Abstract It is now clear that a cyane group facilitate electron-transfer substitution reactions. of particular interest is the demonstration that electron-transfer chain substitution at a staturated carbon atom has been achieved in the absence of a nitro group.

The leaving group as a factor in the alkylation of the 2-nitropropane anion

Abstract The course of the reaction of the lithium salt of 2-nitropropane with p-O2N−C6H4 −CH2X is governed by the nature of X. Thus, with p-nitrobenzyl chloride a 95 % yield of the carbon alkylate (IV) is obtained whereas the use of p-nitrobenzyl iodide results in an 81 % yield of p-nitrobenzaldehyde.

SUBSTITUTION AND ELIMINATION REACTIONS WHICH PROCEED VIA RADICAL ANION INTERMEDIATES

Substitution at a saturated carbon atom may occur by a multistage pathway involving radical anions and radicals as intermediates. Aside from the intrinsic interest which attaches to a new type of substitution process, these reactions are noteworthy for providing new and powerful means of synthesis: they occur readily under mild conditions, they give excellent yields of pure products and, in contrast to SN2 displacements, they are rather insensitive to steric hindrance. Radical anion processes are, therefore, extraordinarily valuable for the synthesis of highly branched structures. A new olefin synthesis which makes available tetrasubstituted olefins, both symmetrical and unsymmetrical, is also described; it provides pure products, free of isomeric olefins, and in excellent yields.