Heterocycle synthesis based on allylic alcohol transposition using traceless trapping groups.
Allylic alcohols undergo transposition reactions in the presence of Re2 O7 whereby the equilibrium can be dictated by trapping one isomer with a pendent electrophile. Additional ionization can occur when the trapping group is an aldehyde or ketone, thus leading to cyclic oxocarbenium ion formation. Terminating the process through bimolecular nucleophilic addition into the intermediate provides a versatile method for the synthesis of diverse oxygen-containing heterocycles. Understanding the relative rates of the steps in the sequence leads to the design of reactions which create multiple stereocenters with good to excellent levels of control.
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260 (USA).
Youwei
Y
Xie
Paul E
PE
Floreancig
allylic compounds; carbocations; diastereoselectivity; isomerization; oxygen heterocycles