A Topochemically Controlled, Regiospecific Fullerene Bisfunctionalization

Abstract

An unprecedented solid‐state reaction of a fullerene monoadduct leads to the antipodal fullerene bisadduct 1. This regiospecific transfer of anthracene appears to be driven by an increase in entropy.

C60 Hexakisadducts with an Octahedral Addition Pattern − A New Structure Motif in Organic Chemistry

“…All these methods are based on the use of oligoadducts with an incomplete octahedral addition pattern as starting materials. These precursor molecules can be obtained, for example, by successive and regioselectively favoured e-additions, [1c] by topologically controlled solid state reactions [26] or by tether functionalization methods. [2b,2c] Mixed hexakisadducts with up to four different types of addends, including some with inherently chiral addition patterns, have been synthesized.…”

“…The final step was the deprotection of the dendritic termini. [22] Kräutler and co-workers developed a topochemically controlled, solid-state group-transfer synthesis [26,35] to obtain the trans-1-bisanthracene adduct 56, which can serve as starting material for the synthesis of type II [4:2] addition pattern compounds, in which two addends are bound at the poles and four are attached at the equatorial belt (Scheme 14). The first step was a regiospecific thermolysis of crystalline monoadduct 55 to give a (1:1) mixture of C 60 and the trans-1-bisadduct 56.…”

The Orthogonal (e,e,e)‐Tris‐Adduct of 9,10‐Dimethylanthracene with C60‐Fullerene: A Hidden Cornerstone of Fullerene Chemistry. Preliminary Communication

“…The underlying need for regiocontrol has provoked extensive studies on i) the patterns of the inherent reactivity of [5,6]fullerene C 60 (1) and its mono-adducts [8] [20], as well as complementary investigations on ii) how the reactions at the C-sphere can be directed further from outside [6] [8]. Tetherdirected remote functionalization [6] [21] and topochemical control in the solid state [22] have opened new ways to achieve highly selective multiple addition reactions [8]. In addition, the use of protection-group strategies was developed to direct the incoming addends to the desired sites of attachment [8].…”

“…3), but the molecules did not show shape-complementary intermolecular contacts. Shape-complementary, regular intermolecular contacts between concave [4 þ 2] cycloaddends and the convex fullerene sphere of a neighbor [5,6]fullerene molecule have been observed in a variety of crystal structures with C 60 : e.g., in the [4 þ 2] cycloadducts of 1 with cyclohexa-1,3-diene [22], in mono-and bis- adducts with anthracene [30] [31], and in cocrystals of C 60 and triptycene [32] and with biconcave porphyrins [33].…”

Crystal engineering a linear polymer of C60 fullerene via supramolecular pre-organization

“…An unusual addend transfer reaction, not favored in solution, has been observed in the solid state with a Diels-Alder anthracene/C 60 adduct. 2 A derivatized fullerene has been shown to assemble spontaneously into macroscopic rods and vesicles. 3 Pressure-induced dimerization of C 60 to produce C 120 is more efficient in a co-crystallate than in the bulk.…”