Isotope effects and the mechanism of deoxygenation of epoxides with dichlorocarbene Academic Article uri icon


  • The deoxygenation of styrene oxide with dichlorocarbene is studied by a combination of isotope effects and theoretical calculations. A normal 13C isotope effect of 1.016 is observed for the α-carbon of the styrene oxide but a surprising inverse isotope effect of 0.995 is observed at the β-carbon. This is indicative of a highly asynchronous process in which the Cα-O bond is broken without any progress in the breakage of Cβ-O bond. Theoretical calculations support this interpretation. This coarctate reaction is formally concerted as it avoids involving a high-energy intermediate, but it appears uninfluenced by transition state aromaticity. © 2005 Published by Elsevier Ltd.

author list (cited authors)

  • Singleton, D. A., & Wang, Z.

citation count

  • 9

publication date

  • March 2005