2,3-sigmatropic Rearrangement - Stereoselectivity

Stereoselectivity

2,3-Sigmatropic rearrangements can offer high stereoselectivity. At the newly formed double bond there is a strong preference for formation of the E-alkene or trans isomer product. The stereochemistry of the newly formed C-C bond is harder to predict. It can be inferred from the five-membered ring transition state. Generally, the E-alkene will favor the formation of anti product, while Z-alkene will favor formation of syn product.

Diastereoselectivity can be high for Z-alkene with alkynyl, alkenl, or aryl anion-stabilizing group. Diastereoselectivity is usually lower with E-alkenes. Hydrocarbon groups will prefer exo orientation in the envelope-like transition state. Anion-stabilizing group will prefer the endo orientation in transition state.