Cycloaddition of phosphorylnitrile oxide to C60

Cycloaddition Reactions of Butadiene and 1,3‐Dipoles to Curved Arenes, Fullerenes, and Nanotubes: Theoretical Evaluation of the Role of Distortion Energies on Activation Barriers

“…[13][14][15] C 60 reacts with different nitrile oxides forming [6,6]fullerene-isoxazolines, where in this case the retro-cycloaddition was also possible. [16][17][18] There are no experimental results for the addition of simple nitrones to fullerenes as they are very unstable; however, the addition of N-silyloxynitrones to C 60 has been investigated. [19] The 1,3-dipolar cycloadditions of diazomethane, nitrile oxide, and nitrone to C 60 were studied Keywords: cycloaddition · density functional calculations · Diels-Alder reactions · distortion/interaction theory · Marcus theory · ONIOM Abstract: Diels-Alder cycloadditions of butadiene and 1,3-dipolar cycloadditions of azomethine ylide, fulminic acid, and the parent nitrone to polyacenes, fullerenes, and nanotubes have been investigated with density functional theory and ONIOM methods.…”

Cycloadditions

“…Isoxazoline derivatives of C 60 such as 250 (Scheme 4.40) are accessible by 1,3-dipolar cycloadditions of nitrile oxides to [6,6] double bonds of the fullerene [2, 278,[291][292][293][294][295][296][297][298][299][300][301][302][303][304][305]. The nitrile oxides 249 with R = methyl, ethyl, ethoxycarbonyl and anthryl are generated in situ from the corresponding nitroalkane, phenyl isocyanate and triethylamine.…”

“…Isoxazolines of C 60 and C 70 [293][294][295] with R = Ph, alkyl, 4-C 6 H 4 OCH 3, 4-C 6 H 4 CHO, amino acid [305], dialkoxyphosphoryl [296,297] or ferrocene [298] have been synthesized in ca. Hydroxymoyl chlorides are accessible by the reaction of aldoximes with chlorinating agents such as NCS (N-chlorosuccinimide).…”

Synthesis and electrochemical properties of N-isocyanurate-substituted aziridino[1,6][60]fullerene, an unusual product of cycloaddition to the 5,6-junction of fullerene

“…8 The sp 3 carbon signals of the fullerene fragment of a phosphorylated isoxazoline derivative of fullerene were also detected in the same field (d 124.7 and 104.1 ppm). 9 The assignment of the signal at d 120.21 ppm to the sp 3 carbon of the fullerene fragment in the 13 C NMR spectrum of compound 2 excludes the azahomofullerene structure of this compound, which might be an isomer of 3 with a different orientation of the substituent at nitrogen of the fullerene fragment. Note that the probability of separating such isomers is low because of the fast inversion at N at ambient temperature.…”