Addition of Benzyne to Gd@C₈₂

Biomedical Activities of Endohedral Metallofullerene Optimized for Nanopharmaceutics

“…Therefore, the water-soluble gadolinium-containing endohedral fullerenes are expected to be the promising next-generation of MRI contrast agents. The polyhydroxylated gadolinium metallofullerenols, Gd@C 82 (OH) x , have been studied as high efficient contrast agents for MRI,38 and the size of Gd@C 82 (OH) x aggregated in aqueous solution is closely related to their high efficiency as a MRI agent 39…”

Nitrated Benzyne Derivatives of La@C82: Addition of NO2 and Its Positional Directing Effect on the Subsequent Addition of Benzynes

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Cycloadduct derivatives of EMFs that contain closed five-or six-membered rings between the substituent and the fullerene cage have been synthesized using, for example, 1,3-dipolar additions or Diels-Alder reactions. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Cycloadduct derivatives of EMFs that contain closed five-or six-membered rings between the substituent and the fullerene cage have been synthesized using, for example, 1,3-dipolar additions or Diels-Alder reactions.…”

“…[16] There are few reports of singly bonded derivatives of EMFs; some recent examples include the benzyl adducts of La@C 82 [17] and Sc 3 N@C 80 . [19] It has long been expected that EMFs would have different chemical properties to empty fullerenes owing to the presence of the metal core which has strong interactions with the carbon shell; however, such findings are rare. [19] It has long been expected that EMFs would have different chemical properties to empty fullerenes owing to the presence of the metal core which has strong interactions with the carbon shell; however, such findings are rare.…”

“…Benzyne is generated by the diazotization of anthranilic acid with isoamyl nitrite (1), [19] which reacts in situ with La@C 82 . Multiple adducts are unavoidable, even at 0 8C (Supporting Information, Figure S1).…”

Reactions of endohedral metallofullerenes with azomethine ylides: an efficient route toward metallofullerene-pyrrolidines

“…Since exohedral functionalization of EMFs would bring them many new applications, much interest has been focused on this subject [5]. Nowadays, most published results on the exohedral modification of metallofullerenes were based on the corresponding reactions of C 60 , such as polyhydroxylation [6], silanization [7], Diels-Alder reaction [8], Bingel reaction [9] and the addition of diazo compounds or benzyne to metallofullerenes [10]. Despite the relatively low yields of metallofullerenes, exohedral functionalization of EMFs has produced several new materials such as MRI contrast agents and therapeutic radiopharmaceuticals [9,11].…”