NUCLEOPHILIC CLEAVAGES OF ONE-ELECTRON SIGMA-BONDS ARE PREDICTED TO PROCEED WITH STEREOINVERSION

: The valence-bond curve crossing model is used to analyze the stereochemistry of nucleophilic displacements on one-electron σ bonds. The model predicts that the stereochemistry of cleavage of one-electron a bond by nucleophiles will be governed by the a* orbital of the one-electron bonds. As a result such nucleophilic cleavages are predicted to proceed with inversion of stereochemistry at the center of attack. This prediction is in accord with recent experimental findings. © 1990, American Chemical Society. All rights reserved.