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.
Original Publication Citation
Bayse, C.A., & Antony, S. (2009). Theoretical studies of 2,3 -sigmatropic rearrangements of allylic selenoxides and selenimides. Molecules, 14(9), 3229-3236. doi: 10.3390/molecules14093229
Bayse, Craig A. and Antony, Sonia, "Theoretical Studies of 2,3 -Sigmatropic Rearrangements of Allylic Selenoxides and Selenimides" (2009). Chemistry & Biochemistry Faculty Publications. 16.