Pentagon-Fused Sumanenes on the Aromatic Peripheries en Route to the Bottom-Up Synthesis of Fullerenes

Hironobu Nakazawa; Yuta Uetake; Yumi Yakiyama; Hidehiro Sakurai

doi:10.1055/a-1992-0487

Synlett, Table of Contents

Synlett 2023; 34(04): 374-378
DOI: 10.1055/a-1992-0487

letter

Pentagon-Fused Sumanenes on the Aromatic Peripheries en Route to the Bottom-Up Synthesis of Fullerenes

Hironobu Nakazawa

^aDivision of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

,

Yuta Uetake

^aDivision of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

,

Yumi Yakiyama

^aDivision of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

,

Hidehiro Sakurai ∗

^aDivision of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

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Abstract

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Abstract

Bowl-shaped π-conjugated sumanenyltriamines were successfully synthesized in a one-step reaction from bromomethylsumanene. This molecule represents an example of hemiazafullerene (C₅₄N₆ fragment) with six isolated pentagons. Its single-crystal X-ray structural analysis showed the formation of one-dimensional columnar structures incorporating chloroform. The hemifullerene (C30 fragment) was also synthesized when the nucleophile was changed to dimethylmalonate.

Key words

hemiazafullerene - hemifullerene - sumanene - curved π-conjugated molecules

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References

References and Notes

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19 General Procedures for the Synthesis of 2 To a reaction vial equipped with a magnetic stir bar were added 1 (40.0 mg, 49.1 μmol, 100 mol%) and solvent (4.0 mL). To this was added amine 3 (900 mol%) and the mixture was stirred at 80 °C for 10 min. After cooling to room temperature, H₂O was added and the mixture was extracted with EtOAc. The combined organic extract was washed with brine and dried over Na₂SO₄. After filtration, the filtrate was concentrated under reduced pressure. The residue was purified by silica-gel column chromatography to give sumanenyltriamines 2.
20 2,6,10-Tributyl-3,4,5,7,8,9,11,12-octahydro-1H-tricyclopenta[4,5:8,9:12,1]triphenyleno[2,3-c:6,7-c′:10,11-c′′]tripyrrole (2a): The crude product was purified by silica gel column chromatography (MeOH/CHCl₃ = 1:10) to give 2a (10.2 mg, 18.3 μmol, 37%) as a brownish solid. Mp 198 °C (dec); TLC: R_f = 0.52 (MeOH/CHCl₃ = 1:10). IR (KBr): 2955, 2927, 2871, 2789, 2743, 1682, 1458, 1330, 1152 cm⁻¹; ¹H NMR (400 MHz, CDCl₃): δ = 4.45 (d, J = 19.2 Hz, 3 H), 3.98 (d, J = 11.9 Hz, 6 H), 3.70 (d, J = 11.9 Hz, 6 H), 3.28 (d, J = 19.2 Hz, 3 H), 2.69 (t, J = 7.3 Hz, 6 H), 1.55 (tt, J = 7.3, 6.6 Hz, 6 H), 1.38 (tq, J = 7.3, 6.6 Hz, 6 H), 0.93 (t, J = 7.3 Hz, 9 H). ¹³C NMR (100 MHz, CDCl₃): δ = 147.77 (6C), 142.15 (6C), 136.22 (6C), 57.80 (6C), 56.33 (3C), 38.84 (3C), 31.18 (3C), 20.76 (3C), 14.26 (3C). HRMS (ESI⁺): m/z calcd for C₃₉H₄₅N₃ [M + H]⁺: 556.3686; found: 556.3667
21 Hexamethyl 3,4,5,7,8,9,11,12-Octahydrohexacyclopenta-[b, def,h,jkl,n,pqr]triphenylene-2,2,6,6,10,10(1H)-hexacarboxylate (4a): To a test tube equipped with a magnetic stir bar were added 1 (10.0 mg, 12.3 μmol, 100 mol%), K₂CO₃ (20.3 mg, 147 μmol, 1200 mol%), and THF (1.5 mL). To this was added dimethyl malonate (4.9 μL, 36.8 μmol, 350 mol%) and the mixture was stirred at 80 °C for 48 h. After cooling to room temperature, H₂O was added and the reaction mixture was extracted with EtOAc. The combined organic extract was washed with brine and dried over Na₂SO₄. After filtration, the filtrate was concentrated under reduced pressure. The residue was purified by silica-gel column chromatography (EtOAc/CHCl₃/n-hexane = 10:5:7) followed by GPC (CHCl₃) to give 4a (3.1 mg, 4.2 μmol, 34%) as a colorless solid. Mp 246 °C (dec); TLC: R_f = 0.61 (EtOAc/CHCl₃/n-hexane = 10:5:7). IR (KBr): 3461, 3001, 2953, 2845, 1736, 1434, 1282, 1242, 1201, 1161, 1070 cm⁻¹. ¹H NMR (400 MHz, CDCl₃): δ = 4.48 (d, J = 19.4 Hz, 3 H), 3.82 (s, 9 H), 3.73 (d, J = 16.7 Hz, 6 H), 3.62 (s, 9 H), 3.38 (d, J = 16.7 Hz, 6 H), 3.29 (d, J = 19.4 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 172.41 (3C), 172.04 (3C), 147.43 (6C), 143.57 (6C), 135.82 (6C), 60.36 (3C), 53.31 (3C), 53.13 (3C), 39.20 (3C), 39.04 (6C). HRMS (ESI⁺): m/z calcd for C₄₂H₃₆O₁₂ [M + Na]⁺: 755.2099; found: 755.2092.

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