Kinetic deuterium isotope and electronic effects in the silver(I) promoted type $gamma$ isomerization of 1-alkyltricyclo[4.1.0.0$sup 2$ $sup 7$]heptanes. Mechanistic analysis of the formation of bicyclo[3.2.0]hept-6-enes
The Ag(I)-catalyzed isomerization of l-carbomethoxytricycloSTA4.1.0.0/ sup 2,7! heptane follows second-order kinetics and proceeds (slowly) to give mainly 2-carbomethoxy-1,3-cycloheptadiene. The marked changeover in product distribution relative to related compounds with alkyl groups at C/sub 1/ is attributed to an electronic effect which operates however to decelerate chiefly the type gamma rearrangement pathway. Deuterium isotope effects have been determined for syn-3-methoxy-1-methyltricyclo(4.1.0.0/sup 2,7!heptane carrying isotopic label at C/sub 2/ and at C/sub 7/. In the latter instance, the formation of 6- and 7-methylbicycloheptenes is affected identically (k/sub H//k/ sub D/ = 1.45). Deuterium substitution at C/sub 2/, in c ontrast, partitions the interaction mechanisms so as to enhance the production of the 6-methyl isomer (k/ sub H//k/sub D/ = 0.87) and retard formation of the 7-methyl derivative (k/sub H// k/sub D/ = 1.17). These observations have been incorporated with previous results to provide detailed mecharistic interpretations of the generalized type alpha and gamma rearrangements- (auth)
- Research Organization:
- Ohio State Univ., Columbus
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-29-015346
- OSTI ID:
- 4344751
- Journal Information:
- J. Amer. Chem. Soc., v. 96, no. 1, pp. 224-233, Journal Name: J. Amer. Chem. Soc., v. 96, no. 1, pp. 224-233; ISSN JACSA
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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