Ruthenium-catalyzed [2 + 2] cycloadditions between 7-substituted norbornadienes and alkynes: an experimental and theoretical study.
The ruthenium-catalyzed [2 + 2] cycloadditions of 7-substituted norbornadienes with an alkyne have been investigated. The cycloadditions were found to be highly regio- and stereoselective, giving only the anti-exo cycloadducts as the single regio- and stereoisomers in good yields. The results on the relative rate of different 7-substituted norbornadienes in the Ru-catalyzed [2 + 2] cycloadditions with an alkyne indicated that the reactivity of the alkene component decreases dramatically as the alkene becomes more electron deficient. Ab initio computational studies on the ruthenium-catalyzed [2 + 2] cycloadditions provided important information about the geometries and the arrangements of the four different groups on the Ru in the initial Ru-alkene-alkyne pi-complex, 14, and in the metallacyclopentene 15. Based on our computational studies, we also found that the first carbon-carbon bond formed in the [2 + 2] cycloaddition is between the C(5) of the alkene and the C(b) (the acetylenic carbon attached to the ester group) of the alkyne 8. Our computational studies on the potential energy profiles of the cycloadditions showed that the activation energy relative to the reactants for the oxidative addition step is in the range of 9.3-9.8 kcal/mol. The activation energy relative to the metallacyclopentene for the reductive elimination step is much higher than for the oxidative addition step (in the range of 25.9-27.6 kcal/mol).
Jordan
Robert W
RW
Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Guelph, Guelph, Ontario, Canada N1G 2W1.
Khoury
Peter R
PR
Goddard
John D
JD
Tam
William
W
D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry; D001952:Bridged-Ring Compounds / Q000138:chemical synthesis; D002384:Catalysis; D003198:Computer Simulation; D003500:Cyclization; D008958:Models, Molecular; D008968:Molecular Conformation; D009636:Norbornanes / Q000138:chemical synthesis* / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D013816:Thermodynamics
D000480:Alkynes; D001952:Bridged-Ring Compounds; D009636:Norbornanes; D012428:Ruthenium