ISSN:
0570-0833
Keywords:
Substitution
;
Radical ions
;
Intermediates
;
Synthetic methods
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A new type of substition process at a saturated carbon atom is described. These reactions, which proceed via a chain sequence in which radical anions and free radicals are intermediates, are noteworthy for providing novel 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. As a consequence, radical anion processes are especially valuable for the preparation of highly branched structures. Many inorganic and organic anions readily enter into these displacements and, indeed, amines are also effective. Systems which undergo substitutions via this electron transfer mechanism include benzylic, cumylic, strictly aliphatic, and heterocyclic molecules. It is of interest that a number of groups which do not behave as leaving groups in SN2 displacements are readily displaced at room temperature from a satureted carbon atom via the radical anion-free radical pathway, e.g., nitro, azide, sulfone, and ether groups.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/anie.197507341
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