Origins of Differences in Reactivities of Alkenes, Alkynes, and Allenes in [Rh(CO)2Cl]2-Catalyzed (5 + 2) Cycloaddition Reactions with Vinylcyclopropanes
Journal of the American Chemical Society2008Vol. 130(8), pp. 2378–2379
Citations Over TimeTop 10% of 2008 papers
Abstract
Rhodium dimer [Rh(CO)2Cl]2 efficiently catalyzes the intra- and intermolecular (5 + 2) reactions of vinylcyclopropanes with alkynes and allenes, but not alkenes. This difference in reactivity is attributed to the difficulty of reductive elimination for the alkene. The computed reductive elimination transition structures show that the participation of the second π-orbital in acetylene and allene reduces the barrier by 9∼15 kcal/mol, compared to ethylene, for which no such interactions are possible.
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