Addition of Diazomethanes, Diazoacetates and Diazoamides

Significantly, purified mixtures of isomers of A and C equilibrate, in most cases, quantitatively to the ring-closed [6,6]-ring bridged cycloadducts A after refluxing in toluene for several hours. This implies that cycloadducts A are the thermodynamically most stable isomers [110,118,129]. Beside the thermal treatment [110, 

The electronic absorption spectra of Cgo and [5,6] and [6,6] methano-bridged cycloadducts (monoadducts) exhibit almost the same features in the UV region, consisting of three dominant bands at 325, 259 and 219 nm [103, 106, 108, 126, 

An enantiopure dimer 149 with a l,l -binaphthyl-bridge was prepared via the bis-tosylhydrazone (see Table 4.4, page 130/131) [122], The electronic properties of these dimers, such as the electronic absorphon spectra and cyclic voltammetry, are indistinguishable from those of other methano-bridged fullerenes. CV-data show clearly that the two CgQ-imits of the binaphthyl-dimer are reduced independently [122], 

Even an oligopeptide has been attached to (Table 4.3, compound 130) [111]. This was achieved by a coupling reaction of the carboxylic group in the side chain of the cyclopropane ring as well. First, the tert-butylcarboxylate 129 was synthesized by the reaction of the corresponding diazomethylbenzoate with Cgg. After hydrolysis with trifluoromethanesulfonic acid, the acyl chloride was generated by treatment with oxalyl chloride. Finally, in a one-step procedure the fullerene peptide 130 was obtained by the reaction with the N-deprotected pentapeptide H-(L-Ala-Aib)2-L-Ala-OMe. 

In search of a convenient procedure for preparing diazo substrates for the cycloaddition to Cgg, Wudl introduced the base-induced decomposition of tosyl-hydrazones [116]. This procedure allows the in situ generation of the diazo compoimd without the requirement of its purification prior to addition to Cgg. Since they are rapidly trapped by the fullerene, even unstable diazo compounds can be successfully used in the 1,3-dipolar cycloaddition. In a one-pot reaction the tosyUiydrazone is converted into its anion with bases such as sodium methoxide or butylHfhium, which after decomposition readily adds to Cgg (at about 70 °C). This method was first proven to be successful with substrate 142. Some more reactions that indicate the versatility of this procedure are shown in Table 4.4. Reaction of 142 with CgQ under the previously described conditions and subsequent deprotection of the tert-butyl ester leads to [6,6]-phenyl-C5j-butyric acid (PCBA) that can easily be functionalized by esterification or amide-formation [116]. PCBA was used to obtain the already described binaphthyl-dimer (obtained from 149 by twofold addition) in a DCC-coupling reaction [122]. 

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