Tether-directed remote functionalization of fullerenes C60 and C70

The article provides an overview of the work on regio- and, in the occurrence, stereoselective tether-directed remote functionalization of fullerenes in the Diederich group, from the initial stages in 1994 to the present. All bisaddition patterns Of C-60, except cis-1, have been realized with high selectivities, mainly by Bingel-type macrocyclizations. Particular emphasis is placed on the stereoselective generation of the inherently chiral cis-3, trans-3, and trans-2 addition patterns. Besides, one of the rare examples of direct threefold tether-directed cyclopropanation Of C-60 is presented and the spacer-controlled derivatization Of C-70 is reviewed.