Synlett 2016; 27(14): 2123-2127
DOI: 10.1055/s-0035-1561424
cluster
© Georg Thieme Verlag Stuttgart · New York

Synthesis of C58 Open-Cage Fullerene Derivatives

Yuming Yu
a  Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. of China   Email: gan@pku.edu.cn
b  CAS Key Laboratory for Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. of China
,
Liang Xu
a  Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. of China   Email: gan@pku.edu.cn
,
Xinchen Huang
a  Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. of China   Email: gan@pku.edu.cn
,
Sisi Liang
a  Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. of China   Email: gan@pku.edu.cn
,
Liangbing Gan*
a  Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. of China   Email: gan@pku.edu.cn
c  State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, P. R. of China
› Author Affiliations
Further Information

Publication History

Received: 30 January 2016

Accepted after revision: 10 March 2016

Publication Date:
06 April 2016 (online)


Abstract

Several analogous C58 open-cage fullerene derivatives have been prepared through silver acetate mediated decarboxylation of the corresponding C59 open-cage precursors. These C58 open-cage fullerene derivatives can trap one water molecule under mild conditions as shown by spectroscopic data and single-crystal X-ray analysis.

Supporting Information

 
  • References and Notes


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  • 11 General Procedure for the Preparation of Compounds 2a–d CF3CO2Ag (30 equiv of 1) was added into a solution of compound 1 (0.1 mmol) in distilled toluene (30 mL). The mixture was stirred at r.t., and progress of the reaction was monitored by TLC. After all the starting material 1 has been converted into a new complex with the silver salt (around 10–30 min), the mixture was then stirred vigorously at 100 °C. When the reaction was completed (about 3 d), the reaction solution was cooled to r.t. and directly chromatographed on a silica gel column and eluted with toluene–EtOAc (20:1). The second red band was collected and evaporated to give compound 2. Yields range from 40–45%. Characterization Data for 2c 1H NMR (400 MHz, CDCl3): δ = 8.41 (s, 1 H), 8.32 (s, 1 H), 8.19 (d, J = 7.8 Hz, 2 H), 7.42 (d, J = 7.8 Hz, 2 H), 2.80–2.61 (m, 2 H), 1.87–1.63 (m, 2 H), 1.50–1.36 (m, 4 H), 0.96 (t, J = 6.9 Hz, 3 H). 13C NMR (125 MHz, CDCl3): δ = 188.54, 188.46, 185.32, 164.75, 150.36, 150.28, 149.74, 149.67, 149.66, 149.64, 149.35, 148.84, 148.81, 148.60, 148.49, 147.62, 146.75, 146.66, 146.59, 146.57, 146.33, 146.29, 146.19 (2 C), 146.10, 145.95, 145.94, 145.80, 145.58, 145.56, 144.07, 143.97, 143.72 (2 C), 143.60, 143.46, 142.95, 142.81 (2 C), 142.80 (2 C), 142.00, 141.67, 141.14, 140.13, 139.27, 138.65, 138.58, 137.66, 137.55, 137.05, 136.70 (2 C), 136.52, 135.08, 134.19, 134.14, 133.75, 131.55, 129.16 (2 C), 125.28, 120.84 (2 C), 35.63, 31.56, 31.34, 22.64, 14.10. FT-IR (microscope): 3394, 2923, 2852, 1739, 1676, 1596, 1560, 1517, 1494, 1463, 1411, 1314, 1247, 1133, 1120, 800, 732 cm–1. ESI-HRMS: m/z calcd for C69H18NO4 [M + H+]: 924.1230; found: 924.1241.
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  • 13 Single crystals of 2b suitable for X-ray diffraction were obtained by slow evaporation of its solution in a mixture of CH2Cl2 and hexane. Crystal Data C67H13NO4 (M = 895.78), orthorhombic, space group Pbca (no. 61), a = 18.1272(12) Å, b = 14.2835(9) Å, c = 33.019(2) Å, V = 8549.4(9) Å3, Z = 8, T = 180.01(11) K, μ(Mo Kα) = 0.087 mm–1, D calc = 1.392 g mm–3, 22202 reflections measured (5.7 ≤ 2θ ≤ 52.04), 8359 unique (R int = 0.0646) which were used in all calculations. The final R 1 was 0.0989 [>2σ(I)] and wR 2 was 0.2945 (all data). CCDC 1445320 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
  • 14 Single crystals of H2O@2b were obtained as above for 2b: Formula: C67H15NO5 (M = 913.80). Orthorhombic, space group Pbca (no. 61), a = 18.1277(4) Å, b = 14.3029(2) Å, c = 32.9881(5) Å, V = 8553.1(3) Å3, Z = 8, T = 180.15 K, μ(Cu Kα) = 0.723 mm–1, D calc = 1.419 g mm–3, 31623 reflections measured (7.246 ≤ 2θ ≤ 126.44), 6947 unique (R int = 0.0418) which were used in all calculations. The final R 1 was 0.0826 [I > 2σ(I)] and wR 2 was 0.2426 (all data). CCDC 1445363 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.