Stereoinduction by distortional asymmetry

Abstract

Stereoselective chemical synthesis requires the two faces of a π bond to be differentiated. Theoretically sound qualitative models for understanding stereoinduction seem to break down in sterically unbiased cyclic systems. Presented here as the distortional asymmetry model is new insight that identifies circumstances where distortional ground state contributions are highly asymmetric and thereby contribute significantly to face selectivity. Out-of-plane distortional potential calculations, transition state calculations and molecular orbital analysis agree with experimental data that cannot otherwise be attributed to steric, torsion, polar or emergent transition state stabilizing effects. The model is readily understood in terms of reaction theory. The explanatory power of the model is also discussed.