Transmetallation with palladium(II) of an organomercurial arising from mercury(II)-mediated cyclopropane cleavage. Tuning of the palladium reactivity and a novel, intramolecular redox reaction

Abstract

The cleavage of the fused-ring cyclopropane hydroxy derivative 1 by means of Hg^II is highly stereoselective and gives a rearranged organomercurial 3, transmetallation of which with Pd^II can be controlled by ligands to afford either lactol 4 or acid 8; the latter compound is formed via an intramolecular insertion of Pd into the C–H bond (6→7), as evidenced by isotopic labelling.