Si‐Tethered Bis‐ and Tris‐Malonates for the Regioselective Preparation of Fullerene Multi‐Adducts

Abstract

AbstractBis‐ and tris‐malonates constructed around a silicon atom have been prepared by reaction of malonate derivatives bearing an alcohol function with di‐tert‐butylsilyl bis(trifluoromethanesulfonate) andtert‐butyl(trichloro)silane, respectively. These compounds have been used for the regioselective bis‐ and tris‐functionalization of C60underBingelconditions. By changing the nature of the linker between the central Si atom and the reactive malonate groups, the malonate precursors have been optimized to produce specific bis‐ and tris‐adducts with excellent regioselectivity. A complete understanding of the electronic and stereochemical factors governing the regioselectivity has been obtained by combining computational studies with a complete analysis of the by‐products formed during the reactions of the Si‐tethered tris‐malonates with C60. Finally, desilylation reactions of the resulting fullerene bis‐ and tris‐adducts have been carried out to generate the corresponding acyclic fullerene bis‐ and tris‐adducts bearing alcohol functions.