Base-catalyzed fragmentation of 2, 3-dioxabicyclo [2.2. 1] heptane, the bicyclic peroxide nucleus of prostaglandin endoperoxides: large secondary deuterium kinetic …

MG Zagorski, RG Salomon

Index: Zagorski, Michael G.; Salomon, Robert G. Journal of the American Chemical Society, 1984 , vol. 106, # 6 p. 1750 - 1759

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Citation Number: 15

Abstract

Abstract: The influence of deuterium substitution on the rates of base-catalyzed rearrangements of 2, 3-dioxabicyclo [2.2. 11 heptane (1) is examined. The kinetic isotope effect observed previously with 1, 4, 5, 6, 7, 7-hexadeuterio-1 (k~/k~= 7-8) is much larger than that observed with 1-deuterio-1 (kH/kD= 3-4) during fragmentation to levulinaldehyde. This reveals a large cumulative secondary deuterium isotope effect which accompanies ...