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

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

Publication History

Received: 20 November 2022

Accepted after revision: 02 December 2022

Accepted Manuscript online:
02 December 2022

Article published online:
03 January 2023

• References and Notes

• 1a Kroto HW, Heath JR, O’Brien SC, Curl RF, Smalley RE. Nature 1985; 318: 162
• 1b Kroto HW, Allaf AW, Balm SP. Chem. Rev. 1991; 91: 1213
• 2a Pradeep T, Vijayakrishnan V, Santra AK, Rao CN. R. J. Phys. Chem. 1991; 95: 10564
• 2b Yu R, Zhan M, Cheng D, Yang S, Liu Z, Zheng L.-S. J. Phys. Chem. 1995; 99: 1818
• 2c Ying ZC, Hettich RL, Compton RN, Haufler RE. J. Phys. B: At., Mol. Opt. Phys. 1996; 29: 4935
• 2d Rockenbauer A, Csμnyi G, Fülçp F, Garaj S, Korecz L, Lukμcs R, Simon F, Forró L, Pekker S, Jμnossy A. Phys. Rev. Lett. 2005; 94: 066603
• 3 Hummelen JC, Knight B, Pavlovich J, Gonzalez R, Wudl F. Science 1995; 269: 1554
• 4a Hirsch A, Nuber B. Acc. Chem. Res. 1999; 32: 795
• 4b Hirsch A, Brettreich M, Wudl F. In, Fullerenes: Chemistry and Reactions . Wiley; Weinheim: 2005
• 4c Vostrowsky O, Hirsch A. Chem. Rev. 2006; 106: 5191
• 4d Rotas G, Tagmatarchis N. Chem. Eur. J. 2016; 22: 1206
• 4e Hashikawa Y, Murata Y. J. Am. Chem. Soc. 2017; 139: 18468
• 5a Bunz UH. F, Rubin Y, Tobe Y. Chem. Soc. Rev. 1999; 28: 107
• 5b Scott LT, Boorum MM, McMahon BJ, Hagen S, Mack J, Blank J, Wegner H, de Meijere A. Science 2002; 295: 1500
• 5c Otero G, Biddau G, Sánchez-Sánchez C, Caillard R, López MF, Rogero C, Palomares FJ, Cabello N, Basanta MA, Ortega J, Méndez J, Echavarren AM, Pérez R, Gómez-Lor B, Martín-Gago JA. Nature 2008; 454: 865
• 6a Fowler PW, Sandal JP. B, Austin SJ, Manolopoulos DE, Lawrenson PD. M, Smallwood JM. Synth. Met. 1996; 77: 97
• 6b Chen ZF, Ma KQ, Pan YM, Zhao XZ, Tang AQ, Feng JK. J. Chem. Soc., Faraday Trans. 1998; 94: 2269
• 6c Ostrowski S, Jamroz MH, Rode JE, Dobrowolski JC. J. Phys. Chem. A 2012; 116: 631
• 6d Huang H, Zhang G, Wang D, Xin N, Liang S, Wang N, Gan L. Angew. Chem. Int. Ed. 2013; 52: 5037
• 7 Haddon RC. J. Am. Chem. Soc. 1987; 109: 1676
• 8a Fowler PW, Manolopoulos DE. An Atlas of Fullerenes . Clarendon; Oxford: 1995
• 8b Jackson EA, Steinberg BD, Bancu M, Wakamiya A, Scott LT. J. Am. Chem. Soc. 2007; 129: 484
• 9a Wu YT, Siegel JS. Chem. Rev. 2006; 106: 4843
• 9b Sygula A. Eur. J. Org. Chem. 2011; 1611
• 9c Tan Q, Higashibayashi S, Karanjit S, Sakurai H. Nat. Commun. 2012; 3: 891
• 9d Yokoi H, Hiraoka Y, Hiroto S, Sakamaki D, Seki S, Shinokubo H. Nat. Commun. 2012; 6: 8215
• 9e Ito S, Tokimaru Y, Nozaki K. Angew. Chem. Int. Ed. 2015; 54: 7256
• 9f Tsefrikas VM, Greene AK, Scott LT. Org. Chem. Front. 2017; 4: 688
• 9g Tokimaru Y, Ito S, Nozaki K. Angew. Chem. Int. Ed. 2018; 57: 9818
• 9h Saito M, Shinokubo H, Sakurai H. Mater. Chem. Front. 2018; 2: 635
• 9i Wang W, Hanindita F, Hamamoto Y, Li Y, Ito S. Nat. Commun. 2022; 13: 1498
• 9j Sakurai H, Nakazawa H. In Handbook of Fullerene Science and Technology . Springer; Singapore: 2022: 45-79
• 10a Kroto HW. Nature 1987; 329: 529
• 10b Schmalz TG, Seitz WA. D, Klein J, Hite GE. J. Am. Chem. Soc. 1988; 110: 1113
• 11 Sakurai H, Daiko T, Hirao T. Science 2003; 301: 1878
• 12 Hishikawa H, Okabe Y, Tsuruoka R, Higashibayashi S, Ohtsu H, Kawano M, Yakiyama Y, Sakurai H. Chem. Lett. 2017; 46: 1556
• 13 Nakazawa H, Uetake Y, Yakiyama Y, Sakurai H. Asian J. Org. Chem. 2022; e202200585 DOI: 10.1002/ajoc.202200585.
• 14 Forbes IT, Johnson CN, Thompson M. J. Chem. Soc., Perkin Trans. 1 1992; 275
• 15 Sakurai H, Daiko T, Sakane H, Amaya T, Hirao T. J. Am. Chem. Soc. 2005; 127: 11580
• 16 Richard WB. Chem. Rev. 1991; 91: 893
• 17 Frank HA, Peter AW, Peter TA. G. Acta Crystallogr., Sect. B: Struct. Sci. 2013; 69: 379
• 18a Hoffmann R. Acc. Chem. Res. 1971; 4: 1
• 18b Gleiter R. Angew. Chem. Int. Ed. Engl. 1974; 13: 696
• 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.