121654-21-5Relevant articles and documents
Corner Attack on endo- and exo-Tricyclo2,4>oct-6-ene by Deuterium and Mercuric Ions: The Effect of Electrophile on Reaction Course
Coxon, James M.,Steel, Peter J.,Whittington, Barry I.
, p. 3702 - 3709 (1989)
Reaction of endo-tricyclo2,4>oct-6-ene (1) with mercuric acetate in methanol gave 2b as the major product of reaction after stereospecific reduction with sodium-mercury amalgam in sodium deuteroxide, along with 3b and 4b.In contrast 4-endo-deuterio-2-endo-methoxybicyclooct-6-ene (2b) is formed as a minor product from acid-catalyzed reaction of endo-tricyclo2,4>oct-6-ene (1) with methanol-d1.Methoxymercuration of exo-tricyclo2,4>oct-6-ene (8) occurs at the double bond to give 7-exo-(acetoxymercurio)-6-exo-methoxy-exo-tricyclo2,4>octane (9c; 89percent).Acid-catalyzed addition of methanol to exo-tricyclo2,4>oct-6-ene (8) gave 6-exo-methoxy-exo-tricyclo2,4>octane (9a; 15percent) and 6-exo-methoxytricyclo2,7>octane (11) in a process involving corner attack of the electrophile.This tricyclic compound rearranges to 5-exo-methoxybicyclooct-2-ene (10a; 55percent).The preference for corner attack by mercuric ion and deuteron with C2-C4 bond cleavage in the reactions of 1 and 8 is rationalized and the competition between reaction at cyclopropane and addition to the double bond discussed.
