Synthesis of Enantiopure T-Symmetrical [6:0]-Hexakis Adducts of C60 Equipped with 1,2-Glycol Substituted cyclo-Monomalonate Addends.

The synthesis of T-symmetrical [6:0]-hexakis adducts of C60 bearing enantiopure cyclo-monomalonate addends equipped with 1,2-glycol groups masked as isopropylidene acetals is presented. The deprotection of the acetals afforded functional fullerene building blocks bearing six 1,2-glycol moieties in an octahedral geometry as connection sites with appropriate linear organic spacers targeting 3D chiral extended networks with cubic building units. Evaluation of the experimental results revealed the advantageous synthetic accessibility to hexakis adduct (-)-9 which carries six homochiral C12 cyclo-monomalonate addends.

An unexpected stereoisomerism in enantiomerically pure trisadducts of C60 with an inherently chiral trans-3,trans-3,trans-3 addition pattern.

We have synthesized and isolated two C2-symmetric enantiomerically pure trisadducts of C60 with an inherently chiral trans-3,trans-3,trans-3 addition pattern with the aid of an enantiopure cyclo-tris-malonate tether. An unexpected stereoisomerism was observed which was attributed to the spatial arrangement of spacers in the tether.

Remote functionalization of C60 with enantiomerically pure cyclo-[2]-malonate tethers bearing C12 and C14 spacers: synthetic access to bisadducts of C60 with the inherently chiral trans-3 addition pattern.

In this Article, we describe the synthesis of two optically pure diols bearing a 1,2-diol moiety masked as an isopropylidene acetal group and long alkyl chains comprised of 12 and 14 carbon atoms, respectively. The synthetic methodology that was developed offers a general way for the synthesis of optically pure diols with long alkyl chains. Diols (-)-4 and (-)-9 were subjected to a condensation reaction with malonyl dichloride to afford two cyclo-[2]-malonate tethers that were separated by column chromatography in optically pure form.

One-pot regioselective synthesis and X-ray crystal structure of a stable [60]fullerene trisadduct with the e(edge),e(face),trans-1 addition pattern.

The Bingel functionalisation of C(60) with a structurally novel tether equipped with three reactive malonate groups afforded a C(2v)-symmetrical e(edge),e(face),trans-1 trisadduct in a complete regioselective manner and in an excellent yield of 65%. The [60]fullerene trisadduct showed pronounced ability to crystallise and gave X-ray quality single crystals for analysis.

A facile access to enantiomerically pure [60]fullerene bisadducts with the inherently chiral trans-3 addition pattern.

The Bingel reaction between C(60) and an enantiopure bismalonate tether equipped with two acetonide moieties led to the synthesis and successful column chromatographic isolation of the enantiomerically pure (f,s)C and (f,s)A bisadducts with the inherently chiral trans-3 addition pattern. Acidic deprotection of the acetonide groups gave access to novel chiral fullerene compounds which combine the inherent chirality of the fullerene core with the functional glycol groups located on the tether.