Methyl 1,2-Dihydrofullerenecarboxylate

Win, W. W.; Kao, Mei-Yu; Eiermann, Matthias; McNamara, J. J.; Wudl, F.; Pole, David L.; Kassam, K.; Warkentin, John

doi:10.1021/jo00099a011

Cited by 50 publications

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“…Because of its dipolar character, 6 has a high nucleophilicity; therefore, it is not surprising that 6 reacts readily with the electrophilic C 60 , as in the reaction of the dimethoxy carbene [18] and C 60 . [19] We have demonstrated that carbene 6 can be generated by the [2+3] cycloaddition of cyclotetrasilene 4 with CS 2 by trapping 6 with C 60 as a chemical probe. NMR spectroscopic measurements and X-ray crystallographic analysis verify that 7 is a methanofullerene (a 6,6-adduct of C 60 ).…”

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S‐Heterocyclic Carbene with a Disilane Backbone

et al. 2005

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S‐Heterocyclic Carbene with a Disilane Backbone

et al. 2005

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“…Previously, the usual route to C 60 RH compounds proceeded from reaction between C 60 and organometallic compounds RM (M ¼ Li, MgBr), 19,21 which precludes the presence of functional groups such as esters in the structure of RM. On the other hand, the synthesis of C 60 RH derivatives in which the R group bears an ester functionality, as in C 60 (CO 2 Me)(H) 22 and C 60 -(CH 2 CO 2 Et)(H), 5, 23 requires very particular experimental conditions.…”

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confidence: 99%

Easy access to unprecedented mixed functionalized dihydrofullerenes C60RH and C60RR′: the C602– anion route

et al. 2003

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Functionalized mixed dihydrofullerenes C 60 RH and C 60 RR 0 are easily obtained from reactions between C 60 2À anion and halo derivatives RX and R 0 X. The key step consists in the selective reaction of the intermediate [C 60 R] À ion, as soon as it is formed, with either CF 3 CO 2 H or R 0 X. This process is made possible thanks to the very fast single electron transfer (SET) reaction between C 60 2À and RX. Functionalized dihydrofullerenes C 60 RH thus prepared are also shown to be very good starting compounds for obtaining various C 60 RR 0 derivatives.The continuously expanding interest in the chemistry of C 60 , 1 since the production of this compound on the macroscopic scale, 2 arises in particular from the outstanding properties exhibited by C 60 organoderivatives in various fields such as photovoltaïsm, 3 nonlinear optics, 4 artificial photosynthesis, 5 organic materials, 6 biology and medicine. 7 In most cases so far, the functionalization of C 60 , due to its electron-deficient polyolefinic character, 8 is achieved through two main pathways: 9 nucleophilic additions, as exemplified by the Bingel cyclopropanation reaction, 10 and cycloadditions among which [4 + 2] Diels-Alder and pyrrolidino[60]fullerene formation 11 processes are most often used. Recently the latter synthesis strategy was extended to the formation of isoxazolo[60]fullerenes 12a and pyrazolino[60]fullerenes. 12b On the other hand, as might be expected, reactions of organic electrophiles are rare and require very specific conditions. 13 In this context, our interest was first focused on the reaction of C 60 2À anion 14 with organic electrophiles, following first results reported by Kadish et al. 15 Recently we have shown that C 60 2À anion can be easily and selectively generated in acetonitrile from reduction of C 60 by means of excess sodium methanethiolate. Then, after addition of monoiodo-or diiodoalkanes, RI or I(CH 2 ) n I (n ¼ 3, 4), into this medium the expected alkylation of C 60 2À took place easily, leading to the corresponding adducts C 60 R 2 or fused cycloadducts C 60 (CH 2 ) n in very good yields. 16 Compared to the results of Kadish et al., two points emerged from our work: the very simple chemical generation of C 60 2À anion and the much higher regioselectivity observed in the formation of the adducts C 60 Me 2 , the 1,2-:1,4-isomer molar ratio being 9:1 instead of 1.4:1. We also extended our process to various halogenated derivatives possessing another functional group, thus giving rise to new functionalized C 60 derivatives, such as the fused cyclopentanone C 60 (CH 2 ) 2 CO, which can be used as new building blocks in C 60 chemistry. 17 These results prompted us to study the following problem: would it be possible, starting from C 60 2À anion, to obtain mixed adducts C 60 RR 0 in which the R and R 0 groups may be different functional groups? So far, to our knowledge, only mixed alkylation of C 60 2À has been reported in the literature. 18 It was shown in this work that C 60 ( t Bu)(CH 2 Ph) and C 60 ( t Bu)(H) co...

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“…These bond lengths are ascribed to the conjugative donation of the lone‐pair electrons on the sulfur atoms into the vacant p π orbital at the carbene center (Scheme ). Because of its dipolar character, 6 has a high nucleophilicity; therefore, it is not surprising that 6 reacts readily with the electrophilic C 60 , as in the reaction of the dimethoxy carbene18 and C 60 19…”

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confidence: 99%