Selective addition of H2O to fullerene C60 catalyzed by Ti, Zr, and Hf catalysts

1,4-Fullerenols C60ArOH: Synthesis and Functionalization

“…Monohydroxylated fullerenols with the general form of C 60 ROH are much less investigated, and only a few such compounds have been isolated and characterized until now. − Iyoda and co-workers synthesized C 60 R F OH by the reaction of C 60 with (R F CO) 2 O . Irngartinger et al prepared 1,2-C 60 (CN)OH via N−O bond cleavage of [60]fullereno[1,2 d ]isoxazole, which was generated by the addition of fulminic acid to C 60 .…”

“…Tajima and co-workers recently reported the synthesis of 1-hydroxyl-2-(1,3,5-trimethylphenyl)-1,2-dihydro[60]fullerene (1,2-C 60 ArOH) by the nucleophilic substitution of C 60 O in the presence of BF 3 ·Et 2 O . More recently, Tuktarov et al described the preparation of 1,2-C 60 HOH by the reaction of C 60 with water catalyzed with Cp 2 MCl 2 . Evidently, much more monohydroxylated fullerenols C 60 ROH with different functional groups and addition patterns are demanded due to their scarcity and the utility of the hydroxy group. − …”

“…More recently, Tuktarov et al described the preparation of 1,2-C 60 HOH by the reaction of C 60 with water catalyzed with Cp 2 MCl 2 . Evidently, much more monohydroxylated fullerenols C 60 ROH with different functional groups and addition patterns are demanded due to their scarcity and the utility of the hydroxy group. − …”

Fullerenes

“…97 1-hydroxy-1,2-dihydro-C 60 -fullerene has been obtained by selective addition of water to C 60 , catalyzed by CP 2 MCl 2 (M = Ti, Zr, Hf) catalysts. 98 Milky white, water-soluble polyhydroxy C 60 fullerenes fullerenols with 36-40 hydroxyl groups, along with 8-9 secondary bound water molecules, have been synthesised using the hydrogen peroxide heating method. 99 Methano-C 60 -fullerene carboxylic acid was activated by esterification with N-hydroxysuccinimide or pentafluorophenol and the active esters were isolated and characterized.…”

Palladium-Catalyzed Reaction of [60]Fullerene with Aroyl Compounds via Enolate-Mediated sp2 C–H Bond Activation and Hydroxylation

“…However, the synthesis of fullerenols with structural diversity is relatively underdeveloped. Relatively few monohydroxylated fullerenols have been investigated, and only a few such compounds have been obtained by the single-electron transfer reaction of C 60 with (R F CO 2 )­O, N–O bond cleavage of [60]­fullereno­[1,2 d ]­isoxazole in the presence of triethylamine, hydrolysis of chlorofullerenes, nucleophilic substitution reaction of C 60 O with aromatic compounds in the presence of BF 3 ·Et 2 O, aminolysis of an unsubstituted [60]­fullerene-fused lactone, reaction of C 60 with water catalyzed with Cp 2 MCl 2 , reaction of C 60 with 4-substituted phenylhydrazine hydrochlorides in the presence of NaNO 2 , or C 60 with acid chlorides promoted by Fe­(ClO 4 ) 3 . Among the reported monohydroxylated fullerenols (C 60 ROH), only three were formed in 1,4-addition mode. ,, To the best of our knowledge, Pd-catalyzed monohydroxylated fullerenols have not been investigated.…”