jo981190n_si_001.pdf (1.18 MB)
Theoretical Study of the Effects of Structure and Substituents on Reactivity in Allylboration
journal contribution
posted on 1998-10-21, 00:00 authored by Kiyoyuki Omoto, Hiroshi FujimotoTo clarify the structural factors controlling the reactivity of allylboron derivatives in allylboration,
we have carried out a theoretical analysis by applying the ab initio MO method. Electrophilicity
of the boron center in several types of allylboron models has been estimated by projecting out the
unoccupied reactive orbital that has the maximum amplitude on a boron p-type atomic orbital
chosen specifically. Two important factors, the electron-accepting level and vacancy of the orbital
of the reaction site, have been included for the purpose of comparing the relative reactivity of those
molecules. The theoretically estimated electrophilicity of the boron center is mostly in agreement
with experimental observations for allylborons with different chiral auxiliary structures, indicating
that electron delocalization from the oxygen of an attacking aldehyde to the boron of an allylboron
reagent dominates the reaction. The activation energies of the reaction have been calculated by
locating the complex and the transition states on the potential surfaces to compare with the
experimental results and the theoretically estimated electrophilicity.