Counterion-directed approach to the Diels-Alder paradigm:cascade synthesis of tricyclic fused cyclopropanes

Kiss E, Campbell CD, Driver RW, Jolliffe JD, Lang R, Sergieiva T, Okovytyy S, Paton RS, Smith MD

An approach to the intramolecular Diels-Alder reaction has led to a cascade synthesis of complex carbocycles composed of three fused rings and up to five stereocentres with complete stereocontrol. Computational analysis reveals that the reaction proceeds via a Michael-Michael-cyclopropanation-epimerization cascade, in which size and coordination of the counterion is key.

Keywords:

cations

,

heterocycles

,

density-functional calculations

,

cycloadditions

,

diastereoselectivity