A Highly Regioselective Approach to Multiple Adducts of C60 Governed by Strain Minimization of Macrocyclic Malonate Addends

✍ Scribed by Uwe Reuther; Torsten Brandmüller; Wolfgang Donaubauer; Frank Hampel; Andreas Hirsch

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: English
• Weight: 522 KB
• Volume: 8
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/1521-3765(20020517)8:10<2261::aid-chem2261>3.0.co;2-c

✦ Synopsis

New macrocyclic malonates 2-5 have been prepared by reaction of malonyl dichloride with alkanediols. Reactions of these cyclo-[n]-alkylmalonates with C60 are highly regioselective. The macrocycles containing identical alkyl spacers selectively form bis- and trisadducts of C60 with rotational symmetry. The addition pattern of the regioselectively formed oligoadducts is determined by the size of the alkyl spacer within the macrocyclic malonate. A variety of bis-, tris-, tetra-, and hexaadducts have been synthesized to show the scope of this approach. "Exotic" addition patterns such as trans-4,trans-4,trans-4, which has been synthesized and completely characterized for the first time, are also accessible by this method. The regioselectivity is ruled by the even distribution of the strain within the macrocyclic malonates containing spacer alkane chains of identical lengths: addition patterns with rotational symmetry provide exactly identical distances of the malonate oxygen atoms and are thus exclusively formed by this method. In contrast, when macrocycles with two different alkyl spacer lengths are used, such as 9 and 10, the reaction exclusively yields C(s)-symmetric bisadducts.