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

abstract

• 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 -carbon of the styrene oxide but a surprising inverse isotope effect of 0.995 is observed at the -carbon. This is indicative of a highly asynchronous process in which the C-O bond is broken without any progress in the breakage of C-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.

authors

• Singleton, Daniel

published proceedings

• TETRAHEDRON LETTERS

author list (cited authors)

• Singleton, D. A., & Wang, Z. H.

citation count

• 9

complete list of authors

• Singleton, DA||Wang, ZH

publication date

• January 2005

publisher

• Elsevier  Publisher

published in

• Tetrahedron Letters: the international journal for the rapid publication of all preliminary communications in organic chemistry  Journal

keywords

• Coarctate
• Deoxygenation
• Epoxide
• Isotope Effects
• Mechanism

Digital Object Identifier (DOI)

• 10.1016/j.tetlet.2005.01.153

start page

• 2033

end page

• 2036

volume

• 46

issue

• 12

URL

• http%3A%2F%2Fdx.doi.org%2F10.1016%2Fj.tetlet.2005.01.153