Preparation of a 12-Membered Open-Cage Fullerendione through Silane/Borane-Promoted Formation of Ketal Moieties and Oxidation of a Vicinal Fullerendiol

• Published in: Journal of organic chemistry Vol. 76; no. 16; pp. 6743 - 6748
• Main Authors: Zhang, Gang, Zhang, Qianyan, Jia, Zhenshan, Liang, Sisi, Gan, Liangbing, Li, Yuliang
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 19.08.2011; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Fullerenes and related materials; diamonds, graphite; Kinetics and mechanisms; Materials science; Organic chemistry; Physical Sciences; Physics; Reactivity and mechanisms; Science & Technology; Specific materials; MILD; SILANE ALCOHOLYSIS; ACID; PEROXIDES; MOLECULAR-HYDROGEN; C-60; SILYL ETHERS; ALKYL BROMIDES; DERIVATIVES; EFFICIENT; Chemical rearrangement; Catalytic reaction; Cage compound; Molecular structure; Deprotection; Organic siloxane; Organic silane; Hemiacetal; X ray diffraction; Characterization; Fullerene; Acetal; Chlorides; Fullerenes; Hydroxyl group; Reaction mechanism; Boron Organic compounds; Oxidation; Organic borane; Spectrophotometry; Chemical synthesis; Organic peroxide; Methanol; Crystalline structure
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo201143k

[60]Fullerene mixed peroxide C60 (OH)(Cl)(OOtBu) reacts with PhMe2SiH/B(C6F5)3 to give oxahomofullerene. Mechanistic investigation indicates that the hydroxyl group in the central pentagon ring is essential to convert the tert-butylperoxo group into a ketal moiety. Migration of the silyl group and transformation of the siloxy group into a phenyl group are observed in the deprotection of the fullerene bound siloxy group. A 12-membered open-cage fullerendione was obtained through oxidation of a [6,6]-fullerendiol. This orifice could be closed to form ketal/hemiketal moieties by BF3-catalyzed reaction with methanol. All of the new fullerene derivatives were characterized by spectroscopic data, and structure of the open-cage fullerendione was also confirmed by single-crystal X-ray analysis.