Computationally guided stereocontrol of the combined C-H functionalization/Cope rearrangement.

The combined C—H functionalization/Cope rearrangement (CHCR) is a highly diastereoselective process that typically proceeds through a chair transition state. A recent computational study of a model system for the CHCR reaction revealed that a boat transition state was only slightly less favored than a chair transition state. Guided by these computational results, this study describes the design of substrates that would react by means of a boat transition state. The resulting C—H functionalization products are the opposite diastereomeric series to what had been previously obtained with this chemistry.