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13C and 2H Kinetic Isotope Effects and the Mechanism of Lewis Acid-Catalyzed Ene Reactions of Formaldehyde

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Department of Chemistry, Texas A & M University, College Station, Texas 77843
Cite this: J. Org. Chem. 2000, 65, 3, 895–899
Publication Date (Web):January 14, 2000
Copyright © 2000 American Chemical Society

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    Abstract Image

    13C and 2H kinetic isotope effects were determined for the ene reaction of formaldehyde with 2-methyl-2-butene at natural abundance catalyzed by diethylaluminum chloride. The reactive methyl group exhibits a k12C/k13C of 1.006−1.009 and a kH/kD of ≈1.22−1.23. The latter represents a combination of primary and secondary effects and is consistent with a significant primary deuterium isotope effect. A very close correspondence of the other isotope effects with the equilibrium isotope effects predicted for formation of a model intermediate cation is observed. An intermolecular deuterium isotope effect of 2.0−2.5 was observed under several reaction conditions in the Lewis acid-catalyzed reaction of formaldehyde with d0/d12-tetramethylethylene. The results are interpreted as supporting the reversible formation of an essentially classical open cation followed by rate-limiting proton transfer.

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