УДК 547


CAGE AND POLYCLIC TERTIARY ALCOHOLS IN RETRO BARBIER FRAGMENTATION REACTION


Cherednichenko A.S., Shamota T.V., Kushko A.O.

National Technical University of Ukraine

«Kiev Polytechnic Institute»,

Kiev, Ukraine


Development of the efficient methods of directed carbon skeleton building is a actual problem of modern organic synthesis. Among traditional approaches domino-processes application proceeding under the action of reagents system is the most widespread approach for solution of such problems.

We showed the possibility of carbon skeleton formation by means of oxidative fragmentation of tertiary alcohols, adamantane and tetrahydrobicyclopentadiene derivatives under action of bromine in alkaline medium.



Study of reaction mixture composition showed that Barbier retro-reaction proceeds with C-C bond cleavage within carbon skeleton and is not practically directed to connected with skeleton substitute elimination.

For tertiary alcohols, such as tetrahydrobicyclopentadiene derivatives – C-C bond cleavage proceeds inside of bicyclic structure simultaneously in two directions resulting in two isomeric bromoketones mixture in 70:30 ratio, which were separated by column chromatography method and were identified.  


Referenc:

       1. Domino Reactions in Organic Synthesis. Lutz F. Tietze, Gordon Brasche, and Kersten M. Gericke, WILEY-VCH Verlag GmbH, Weinheim, 2006.