Sigmatropic rearangements
Analysis using FMO theory
Ms. Anita
1,3-alkyl shift: Stereochemistry of the migrating alkyl group. HMO of allyl radical and carbon free radical
The migrating carbon originally bonded through its positive lobe but for the reaction to occur it must go through the negative lobe and form a sigma bond. It is clear from the transition state diagram that inversion occurs.
So in thermal suprafacial [1,3]-migration Configuration of the migrating group will undergo inversion.
1,5-alkyl shift: Stereochemistry of the migrating alkyl group. HMO of allyl radical and carbon free radical
The migrating carbon originally bonded through its positive lobe, in the tranistion state and the product this is retained. It is clear from the transition state diagram that retention occurs.
So in thermal suprafacial [1,5]-migration, Configuration of the migrating group will be retention.