Abstract
The orbital phase refers to the relationship between orbitals that originates from their wave character. We show here that the orbital phase essentially determines the diastereoselectivity of the following three organic reactions. 1) Torquoselectivity of the electrocyclicring-opening reaction of 3-substituted cyclobutenes; 2) Contradictory torquoselectivity of the retro-Nazarov reaction; 3) Diastereoselectivity in electrophilic addition to substituted ethylenes.
Highlights
Many theories have been proposed to explain the diastereoselectivity of organic reactions [1] [2] [3] [4]
More overlap and a smaller HOMO-LUMO gap between the molecules result in greater stabilization, which lowers the energy of the transition state and accelerates the reaction. The latter approach focuses on the symmetry of the molecular orbital
Our orbital phase theory should be able to properly explain the torquoselectivities, since it can describe the characteristic features of a series of calculation results
Summary
Many theories have been proposed to explain the diastereoselectivity of organic reactions [1] [2] [3] [4]. More overlap and a smaller HOMO-LUMO gap between the molecules result in greater stabilization, which lowers the energy of the transition state and accelerates the reaction The latter approach focuses on the symmetry of the molecular orbital. With our orbital phase theory, the cyclic orbital interaction of σC-C-π*C=C-σC-Rand σ*C-C-πC=C-σC-R-satisfies the phase continuity requirements (Figure 3) [10] They produce considerable stabilization of the transition state, controlling the torquoselectivity. Our orbital phase theory should be able to properly explain the torquoselectivities, since it can describe the characteristic features of a series of calculation results. -20 -1.1 -1.0 -0.9 -0.8 -0.7 -0.6 σ-bond orbital energy/a.u
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