Synlett 2019; 30(12): 1462-1468
DOI: 10.1055/s-0037-1611862
letter
© Georg Thieme Verlag Stuttgart · New York

A Photocatalyst-Free, SET-Mediated Photochemical Approach for the Synthesis of Dumbbell-Like Amine-Functionalized Bis-C60 Fullerene through C–C Bond Formation

Amol Balu Atar*
Further Information

Publication History

Received: 30 March 2019

Accepted after revision: 17 April 2019

Publication Date:
07 June 2019 (eFirst)

Abstract

A novel method for the synthesis of dumbbell-like amine-functionalized bis-C60 fullerene from simple bis-α-silyl tertiary benzyl amines and C60 fullerene is described. The photoreactions between bis-α-silyl tertiary benzyl amines and C60 furnished single-bonded bis-aminomethyl-1,2-dihyrofullerenes and double-bonded 1,2,5-trisubstituted bis-fulleropyrrolidines through 1,3-dipolar cycloaddition reactions of azomethine ylides under mild conditions.

Supporting Information

 
  • References and Notes

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  • 23 General Procedure for Synthesis of Secondary N-Trimethylsilylmethyl-N-benzylamines 6–9: The corresponding primary amine 14 (1, 5823 mg; 2, 6586 mg; 3, 6801 mg; 4, 7455 mg, 54.35 mmol) was taken in acetonitrile (120 mL), and K2CO3 (11266 mg, 81.52 mmol) was added under argon. The reaction mixture was heated at 70 °C for 1 h and iodomethyltrimethylsilane 5 (9697 mg, 45.29 mmol) was added dropwise. The reaction mixture was stirred for 7 h at 70 °C. After completion of reaction (monitored by TLC), the mixture was concentrated in vacuo to give residues that were partitioned between water and CH2Cl2. The CH2Cl2 layers were dried and concentrated in vacuo to afford residues that were subjected to silica gel column chromatography (EtOAc/hexane = 1:1) to yield the corresponding secondary N-trimethylsilylmethyl-N-benzylamines 6 (8197 mg, 78%), 7 (9580 mg, 85%), 8 (6317 mg, 55%), and 9 (9712 mg, 80%). The spectral data matched exactly with reported data.
  • 24 Bhadani A, Endo T, Sakai K, Sakai H, Abe M. Colloid. Polym. Sci. 2014; 292: 1685
  • 25 General Procedure for Synthesis of Bis-α-trimethylsilyl-Substituted Tertiary Amines 13–16: The corresponding secondary amine 69 (6, 1160 mg; 7, 1244 mg; 8, 1268 mg; 9, 1340 mg, 6 mmol) was taken in acetonitrile (120 mL), and K2CO3 (1243 mg, 9 mmol) was added under argon. The reaction mixture was heated at 70 °C for 1 h and 2,2′-oxy-bis(ethane-2,1-diyl)bis(2-bromoacetate) (12; 1043 mg, 3 mmol) was added dropwise. The reaction mixture was stirred for 7 h at 70 °C. After completion of reaction (monitored by TLC), the mixture was concentrated in vacuo to give residues that were partitioned between water and CH2Cl2. The CH2Cl2 layers were dried and concentrated in vacuo to afford residues that were subjected to silica gel column chromatography (diethyl ether/hexane = 1:8) to yield the corresponding symmetrical molecules 13 (1288 mg, 75%), 14 (1442 mg, 80%), 15 (1095 mg, 60%), and 16 (1481 mg, 78%). 2,2′-Oxybis(ethane-2,1-diyl)bis(2-(benzyl((trimethylsilyl)methyl)amino)acetate): 1H NMR: δ = 0.08 (s, 18 H), 2.23 (s, 4 H), 3.32 (s, 4 H), 3.66 (t, J = 12.30 Hz, 4 H), 3.78 (s, 4 H), 4.34 (t, J = 12.24 Hz, 4 H), 7.37–7.21 (m, 10 H); 13C NMR: δ = –1.5, 41.4, 45.6, 56.7, 61.3, 63.5, 126.9, 128.1, 128.7, 139.2, 170.8.
  • 26 Detailed experimental procedures and characterization data are given in the Supporting Information. General Procedure for Photoreactions of C60 with Bis-α-trimethylsilyl-Substituted Tertiary Benzyl Amines: Preparative photochemical reactions were conducted with a 450 W Hanovia medium vapor pressure mercury lamp surrounded by a flint glass filter (>300 nm) in a water-cooled quartz immersion well surrounded by a solution consisting of 10% EtOH–toluene of C60 (201.78 mg, 0.28 mmol), and bis-α-trimethylsilyl-substituted tertiary amines 1316 (13, 320.81 mg; 14, 336.52 mg; 15, 340.96 mg; 16, 354.44 mg, 0.56 mmol). Each solution was purged with nitrogen before and during irradiation, which was carried out for the time periods given for each substance below. The photoproducts were concentrated, and the generated residues were triturated with CHCl3 to recover C60. The triturates were concentrated in vacuo to generate residues that were subjected to silica gel column chromatography (eluants given below) to obtain the photoproducts. Photoreaction of C60 with 13: In N2-saturated conditions: 90 min irradiation, 89% conversion, column chromatography (CS2/CHCl3, 5:1) to yield 17 (256 mg, 49%) and 21 (22 mg, 4%). O2-saturated conditions: 120 min irradiation, 90% conversion, column chromatography (CS2/CHCl3, 5:1) to yield 17 (10 mg, 2%) and 21 (286 mg, 51%). Compound 17: 1H NMR: δ = 3.76 (t, J = 9.45 Hz, 4 H), 4.00 (s, 4 H), 4.48–4.53 (m, 8 H), 4.76 (s, 4 H), 6.90 (s, 2 H), 7.30–7.42 (m, 6 H), 7.62 (d, J = 6.60 Hz, 4 H); 13C NMR: δ = 41.6, 55.7, 58.0, 59.8, 64.17, 67.3, 68.4, 127.8, 128.7, 129.4, 136.0, 136.1, 138.15, 140.0, 140.2, 141.6 (2C), 141.7, 141.9, 142.0, 142.3, 142.5 (2C), 143.2, 144.4, 144.6, 145.3 (3C), 145.4, 145.8, 146.1 (2C), 146.3 (2C), 146.8, 147.2, 147.3, 154.3, 154.7, 171.1; HRMS (FAB): m/z [M + 1] calcd for C144H35N2O5: 1872.8212; found: 1872.9016. Compound 21: 1H NMR: δ = 0.51 (s, 18 H), 3.57–3.68 (m, 4 H), 4.37–4.45 (m, 2 H), 4.47–4.55 (m, 2 H), 4.60 (d, J = 12.15 Hz, 2 H), 5.28 (d, J = 12.18 Hz, 2 H), 5.39 (s, 2 H), 5.51 (s, 2 H), 7.28–7.48 (m, 6 H), 7.65 (d, J = 6.30 Hz, 4 H); 13C NMR: δ = 0.7, 41.3, 56.2, 64.5, 70.0, 77.2, 77.6, 77.9, 127.8, 128.6, 128.9, 134.9, 135.5, 135.6, 136.3, 138.7, 139.2, 139.6, 139.7, 140.1, 141.6, 141.7, 141.8, 141.9, 142.0, 142.1 (2C), 142.2, 142.3, 142.4, 142.6, 142.7, 143.0, 143.1, 144.2, 144.3, 144.4, 144.5, 144.9, 145.1, 145.2, 145.3, 145.5, 145.8, 145.9, 146.1 (2C), 146.2, 146.6, 146.9, 147.0, 152.4, 154.7, 156.4, 156.9, 170.3; HRMS (FAB): m/z [M + 1] calcd. for C150H47N2O5SiO2: 2013.1516; found: 2013.2318.