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Molecules 2009, 14(9), 3229-3236; doi:10.3390/molecules14093229

Theoretical Studies of [2,3]-Sigmatropic Rearrangements of Allylic Selenoxides and Selenimides

Department of Chemistry and Biochemistry, Old Dominion University, Hampton Blvd., Norfolk, VA 23529, USA
Author to whom correspondence should be addressed.
Received: 6 August 2009 / Revised: 24 August 2009 / Accepted: 26 August 2009 / Published: 28 August 2009
(This article belongs to the Special Issue Selenium and Tellurium Chemistry)
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Density-functional theory is used to model the endo and exo transition states for [2,3]-sigmatropic rearrangement of allylic aryl-selenoxides and -selenimides. The endo transition state is generally preferred for selenoxides if there is no substitution at the 2 position of the allyl group. Based upon the relative energies of the endo and exo transition states, enantioselectivity of rearrangements is expected to be greatest for molecules with substitutions at the 1- or (E)-3- position of the allyl group. Ortho substitution of a nitro group on the ancillary selenoxide phenyl ring reduces the activation barriers, increases the difference between the endo and exo activation barriers and shifts the equilibrium toward products.
Keywords: [2,3]-sigmatropic rearrangements; selenoxides; selenium; density-functional theory [2,3]-sigmatropic rearrangements; selenoxides; selenium; density-functional theory
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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MDPI and ACS Style

Bayse, C.A.; Antony, S. Theoretical Studies of [2,3]-Sigmatropic Rearrangements of Allylic Selenoxides and Selenimides. Molecules 2009, 14, 3229-3236.

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