Experimental and AM1 calculational studies of the deprotonation of bicyclo[2.2.2]octane-2,5-dione and bicyclo[2.2.2]octane-2,6-dione: a study of homoconjugation, inductive, and steric effects on the rates and diastereoselectivities of α enolization
Abstract:The kinetics of NaOD-catalyzed HID exchange (enolization) at C3 u to the carbonyl group of bicyclo[2.2.2loctane-2,5-dione ( I ) and bicyclo[2.2.2]octane-2.6-dione (2) have been studied in 60:40 (v/v) dioxane-D,O at 25.0°C. The second-order rate constants for exchange are (9.7 + 1.5) x lo-' and (3.4 t 1.2)x lo-' L mol-' s-I for 1 and 2, respectively. Thus, 1, exchanges 76 times faster than bicyclo[2.2.2]octan-2-one (3) ( k = (1.27 + 0.02) x L mol-I s ' ) , but the 2,6-dione 2 unexpectedly is much less react… Show more
Set email alert for when this publication receives citations?
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.