Fullerene derivatives reaction with amines

Figure 15.9 The reaction of the amine-blocked derivative of 3-hydroxypropylamine with ethylmalonyl chloride gives an ethylmalonate-protected-amine compound, which can be used in the Bingel reaction to create an amine group on a fullerene surface. Reaction with Cfl in the presence of I2 and DBU gives the cyclopropanation product that can be deprotected with TFA to yield the free amine.

Kim KM, Park HJ, Kim JN, Yoo HJ, Yoon UC (2013) Photoaddition reactions of fullerene C60 with alpha-silyl tert-amines leading to new fullerene derivatives. In ref [18], 523... 

Another route to fabricate fullerene doped monoliths has been shown by Peng et al. (2001), which successfully prepared crack free, transparent fullerene glasses oflarge dimensions (up to 60 mm) from sol-gel mixtures of aminated Cgo derivatives and tetraethyl orthosilicate (TEOS). The aminated fullerene derivatives have been synthesized by amination reactions of Ceo with 6-amino-l-hexanol, cyclohexylamine, 2-(2-aminoethoxy)ethanol, and 3-aminopropyltriethoxysilane to prepare derivatives with the molecular structures H C6o[NH(CH2)6oH]jt, H C6o(NH-cyc/o-C6Hn)je, Hjj,C6o[NH(CH2CH2o)2H], and H (C6o[NH(CH2)3Si(OCH2CH3)3]i . A silica network with covalently bonded amine fullerene derivatives has been obtained, as shown in Figure 23-3. 

Fullerene derivatives occupy a privileged position in chemistry as they have many potential applications in materials and biomolecules. Recently, Wang and You reported a FeClj-catalyzed synthesis of oxazolidino[4,5 l,2] [60]fullerenes via the intermolecular tandem reaction of [60] fullerene with ferf-butyl Af-substituted carbamates to access through the direct amination between the C(sp )-H bonds and the N-H bonds (Scheme 9.5) [7]. 

Figure 15.5 A trityl-protected pyrrolidine derivative of Cgg can be prepared by the reaction of N-trityl-oxazolidinone with a fullerene. Deprotection of the trityl group using methanesulfonic acid gives the secondary amine, which can be used in further conjugation reactions.

Topics which have formed the subjects of reviews this year include excited state chemistry within zeolites, photoredox reactions in organic synthesis, selectivity control in one-electron reduction, the photochemistry of fullerenes, photochemical P-450 oxygenation of cyclohexene with water sensitized by dihydroxy-coordinated (tetraphenylporphyrinato)antimony(V) hexafluorophosphate, bio-mimetic radical polycyclisations of isoprenoid polyalkenes initiated by photo-induced electron transfer, photoinduced electron transfer involving C o/CjoJ comparisons between the photoinduced electron transfer reactions of 50 and aromatic carbonyl compounds, recent advances in the chemistry of pyrrolidino-fullerenes, ° photoinduced electron transfer in donor-linked fullerenes," supra-molecular model systems,and within dendrimer architecture,photoinduced electron transfer reactions of homoquinones, amines, and azo compounds, photoinduced reactions of five-membered monoheterocyclic compounds of the indigo group, photochemical and polymerisation reactions in solid Qo, photo- and redox-active [2]rotaxanes and [2]catenanes, ° reactions of sulfides and sulfenic acid derivatives with 02( Ag), photoprocesses of sulfoxides and related compounds, semiconductor photocatalysts,chemical fixation and photoreduction of carbon dioxide by metal phthalocyanines, and multiporphyrins as photosynthetic models. 

---