Reactions of carbon radicals generated by 1,5-transposition of reactive centers

• Main Author: Čeković Živorad
• Format: Article
• Language: English
• Published: Serbian Chemical Society 2005-01-01
• Series: Journal of the Serbian Chemical Society
• Subjects: radical reactions; 1; 5-transposition of radicals; hydrogen transfer; groups migration; intramolecular functionalization; cδ-c bond formation
• Online Access: http://www.doiserbia.nb.rs/img/doi/0352-5139/2005/0352-51390503287C.pdf

Radical intermediates can undergo specific reactions, such as intramolecular rearrangements, i.e., the transpositions of radical centers, which are not known in classical ionic organic reactions. 1,5-Transposition of a radical center to a non-activated carbon atom are of great synthetic importance. It can be successfully applied for the introduction of different functional groups (oxygen, nitrogen, sulfur, halogens) onto a carbon atom remote from the present functional group. In addition to functionalization of a remote non-activated carbon atom, the formation of new C-C bonds on the δ-carbon atom have also been achieved. 1,5-Transposition of the radical centers takes place from alkoxyl, aminyl and carbon radicals to a remote carbon atom. Relocation of the radical centers preferentially involves 1,5-transfer of a hydrogen atom, although migrations of some other groups are known. The reactions of the carbon radical generated by 1,5-relocation of the radical center are presented and their synthetic applications are reviewed.