Chemical consequences of the ground-state conformations of cyclooctyl rings. Examples of reactivity differences in α-hydroxy and α, α' -dihydroxy eightmembered cyclic ketones

Evans Chemical Laboratories, The Ohio State University, Columbus, Ohio 43210, U.S.A.

E-mail : paquette.1 @osu.edu                   Fax: 614-292-1685

Manuscript received 10 December 2003

A program directed toward the elucidation of various conformational factors that control reactivity differences in cyclooctyl and cyclooctenyl systems is described. This overview reports on the divergent reactivity observed in the alkylation of saturated and unsaturated α-ketols. When the eight-membered ring is saturated, only C-alkylation operates. In contrast, the presence of a C5-C6 double bond allows only for O-alkylation. The central issues associated with the stereochemical course of the α,α'-dihydroxylation of cyclooctanone are also presented, as are possible complications brought on by operation of the α-ketol rearrangement. Finally, the structural requirements for the generation of a novel epoxycarbonate derivative are outlined.