Synthesis of Unexpected trans-meso Macrocycle from Novel Unsymmetrical Tetraphenylene

Abstract

A highly unsymmetrical trisubstituted tetraphenylene was designed and synthesized as a novel superamolecular scaffold for an unexpected trans-meso tetraphenylene macrocycle, whose structure was unequivocally characterized by an X-ray crystallographic analysis. With the defined and electron-rich aromatic cavity, this macrocycle could be further modified to be a potential host for organic cations with biological interest.

Key words

tetraphenylene - nonplanar hydrocarbon - macrocycle - host-guest chemistry - cation π interactions

• References and Notes

• 1a Rapson WS, Shuttleworth RG, Niekerk JN. J. Chem. Soc. 1943; 326
• 1b Irngartinger H, Reibel WR. K. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 1981; 37: 1724
• 1c Mak TC. W, Wong HN. C. Top. Curr. Chem. 1987; 140: 141
• 1d Polycyclic Arenes and Heteroarenes: Synthesis, Properties and Applications. Miao Q. Wiley-VCH; Weinheim: 2015
• 2a Peng H.-Y, Lam CK, Mak TC. W, Cai Z, Ma W.-T, Li Y.-X, Wong HN. C. J. Am. Chem. Soc. 2005; 127: 9603
• 2b Lin F, Peng HY, Chen JX, Chik DT. W, Cai Z, Wong KM. C, Yam VW. W, Wong HN. C. J. Am. Chem. Soc. 2010; 132: 16383
• 2c Chen J.-X, Han J.-W, Wong HN. C. Org. Lett. 2015; 17: 4296
• 3a Huang H, Hau C.-K, Law CC. M, Wong HN. C. Org. Biomol. Chem. 2009; 7: 1249
• 3b Hau C.-K, He H, Lee AW. M, Chik DT. W, Cai Z, Wong HN. C. Tetrahedron 2010; 66: 9680
• 4a Lim DS. W, Anderson EA. Synthesis 2012; 44: 983
• 4b Wen J.-F, Hong W, Yuan K, Mak TC. W, Wong HN. C. J. Org. Chem. 2003; 68: 8918
• 4c Cui J.-F, Chen C, Gao X, Cai Z, Han J.-W, Wong HN. C. Helv. Chim. Acta 2012; 95: 2604
• 4d Sygula A, Fronczek FR, Sygula R, Rabideau PW, Olmstead MM. J. Am. Chem. Soc. 2007; 129: 3842
• 4e Deng C.-L, Xiong X.-D, Chik DT. W, Cai Z, Peng X.-S, Wong HN. C. Chem. Asian J. 2015; 10: 2342
• 5a Rathore R, Magueres PL, Lindeman SV, Kochi JK. Angew. Chem. Int. Ed. 2000; 39: 809
• 5b Ogasawara J, Igarashi T, Sano S. US 20050112407, 2005
• 6a Wuckert E, Hägele C, Giesselmann F, Baro A, Laschat S. Beilstein J. Org. Chem. 2009; 5: 57
• 6b Hägele C, Wuckert E, Laschat S, Giesselmann F. ChemPhysChem 2009; 10: 1291
• 6c Hau CK, Chui SS. Y, Lu W, Che CM, Cheng PS, Mark TC. M, Miao Q, Wong HN. C. Chem. Sci. 2011; 2: 1068
• 6d Nielsen C, Brock-Nannestad T, Reenberg T, Hammershoj P, Christensen J, Stouwdam J, Pittelkow M. Chem. Eur. J. 2010; 16: 13030

For reviews, see:
• 7a Brotin T, Dutasta J.-P. Chem. Rev. 2009; 109: 88
• 7b Hardie MJ. Chem. Soc. Rev. 2010; 39: 516

For recent examples, see:
• 8a Chatelet B, Joucla L, Padula D, Di Bari L, Pilet G, Robert V, Dufaud V, Dutasta J.-P, Martinez A. Org. Lett. 2015; 17: 500
• 8b Schmitt A, Robert V, Dutasta J.-P, Martinez A. Org. Lett. 2014; 16: 237
• 8c Li M.-J, Huang C.-H, Lai C.-C, Chiu S.-H. Org. Lett. 2012; 14: 6146
• 8d Wang L, Wang G.-T, Zhao X, Jiang X.-K, Li Z.-T. J. Org. Chem. 2011; 76: 3531
• 8e Canevet D, Gallego M, Isla H, de Juan A, Pérez EM, Martín N. J. Am. Chem. Soc. 2011; 133: 3184

For reviews, see:
• 9a Markopoulos G, Henneicke L, Shen J, Okamoto Y, Jones PG, Hopf H. Angew. Chem. Int. Ed. 2012; 51: 12884
• 9b Kuck D. Chem. Rev. 2006; 106: 4885

For recent examples, see:
• 10a Bredenkötter B, Grzywa M, Alaghemandi M, Schmid R, Herrebout W, Bultinck P, Volkmer D. Chem. Eur. J. 2014; 20: 9100
• 10b Klotzbach S, Beuerle F. Angew. Chem. Int. Ed. 2015; 54: 10356
• 10c Wei J, Li Z.-M, Jin X.-J, Yao X.-J, Cao X.-P, Chow H.-F, Kuck D. Chem. Asian J. 2015; 10: 1150
• 10d Wang T, Zhang Y.-F, Hou Q.-Q, Xu W.-R, Cao X.-P, Chow H.-F, Kuck D. J. Org. Chem. 2013; 78: 1062
• 10e Klotzbach S, Scherpf T, Beuerle F. Chem. Commun. 2014; 50: 12454
• 10f Xu W.-R, Xia G.-J, Chow H.-F, Cao X.-P, Kuck D. Chem. Eur. J. 2015; 21: 12011
• 11a Chen C.-F. Chem. Commun. 2011; 47: 1674
• 11b Ma Y.-X, Han Y, Chen C.-F. J. Incl. Phenom. Macrocycl. Chem. 2014; 79: 261
• 11c Chen C.-F, Ma Y.-X. Iptycenes Chemistry: From Synthesis to Applications . Springer; Heidelberg: 2013
• 11d Han Y, Meng Z, Ma Y.-X, Chen C.-F. Acc. Chem. Res. 2014; 47: 2026
• 11e Mastalerz M. Synlett 2013; 24: 781
• 11f Chong JH, MacLachlan MJ. Chem. Soc. Rev. 2009; 38: 3301
• 12 Keyworth CW, Chan KL, Labram JG, Anthopoulos TD, Watkins SE, MaKiernan M, White AJ. P, Holmes AB, Williams CK. J. Mater. Chem. 2011; 21: 11800
• 13 Collibee SE, Yu J. Tetrahedron Lett. 2005; 46: 4453
• 14 Pialat A, Liégault B, Taillefer M. Org. Lett. 2013; 15: 1764
• 15 All attempts to obtain suitable single crystals on the two products have been unsuccessful due to their amorphous powder form. Thus, the less polar one 17 was selected to undergo some derivations. Consequently, we obtained a low-quality crystal suitable for X-ray analysis, which indirectly proved this compound. This result indicated that the more polar bisphenol 1a was the desired tetraphenylene scaffold. See Supporting Information for details.
• 16a Daze KD, Hof F. Acc. Chem. Res. 2013; 46: 937
• 16b Ma JC, Dougherty DA. Chem. Rev. 1997; 97: 1303
• 16c Salonen LM, Ellermann M, Diederich F. Angew. Chem. Int. Ed. 2011; 50: 4808
• 16d Pena PV, Davrazou F, Shi XB, Walter KL, Verkhusha VV, Gozani O, Zhao R, Kutateladze TG. Nature (London, U.K.) 2006; 442: 100
• 16e Mahadevi AS, Sastry GN. Chem. Rev. 2013; 113: 2100
• 17 Experimental Procedure for the Synthesis of 20 Under an argon atmosphere, a mixture of 18 (13 mg, 0.035 mmol), 19 (20 mg, 0.035 mmol), and Cs₂CO₃ (114 mg, 0.35 mmol) in dry MeCN (10^–2 M, 4 mL) was stirred at 90 °C for 48 h. The mixture was cooled to room temperature, and the solvent was removed. The crude residue was dissolved in a mixture of CH₂Cl₂ and water. The organic layer was separated, washed with water and then brine, dried over Na₂SO₄, and concentrated under reduced pressure. The crude product was purified by column chromatography over silica gel (10 g, eluting with PE–CH₂Cl₂, 5:2) to give the product 20 (3 mg, 10%) as a white solid. R_f = 0.21 (PE–CH₂Cl₂, 5:2); mp >250 °C. ¹H NMR (400 MHz, CD₂Cl₂): δ = 7.55 (dd, J = 8.0, 1.7 Hz, 2 H), 7.38 (d, J = 1.8 Hz, 2 H), 7.29–7.24 (m, 6 H), 7.16 (dd, J = 7.4, 1.7 Hz, 2 H), 7.07–6.97 (m, 10 H), 6.61 (d, J = 2.4 Hz, 2 H), 6.57 (d, J = 2.4 Hz, 2 H), 4.48–4.44 (m, 4 H), 4.30 (br s, 4 H). ¹³C NMR (100 MHz, CD₂Cl₂): δ = 158.2, 157.7, 146.3, 143.2, 142.9, 141.3, 140.8, 140.6, 134.8, 133.3, 132.9, 131.3, 130.8, 130.3, 130.2, 129.4, 129.4, 128.1, 127.6, 119.0, 116.8, 116.3, 113.7, 113.0, 111.3, 67.3. ESI-MS: m/z = 797 [M + Na]⁺. ESI-HRMS: m/z calcd for C₅₄H₃₄N₂O₄Na [M + Na]⁺: 797.2411; found: 797.2401.
• 18 X-ray Crystallographic Data for 20 C₅₄H₃₄N₂O₄, M = 774.88, monoclinic, P2(1)/c, a = 10.7287(5) Å, b = 23.4747(11) Å, c = 10.5235(5) Å, α = 90°, β = 106.5140(10)°, γ = 90°, T = 173(2) K, V = 2541.0(2) A³, Z = 2, ρ_calc (mg mm^–3): 1.243, absorption coefficient = 0.082 mm^–1, F(000) = 1000, crystal size: 0.50 × 0.40 × 0.30 mm, 2θ range for data collection: 1.73 to 25.25°, reflections collected: 58557, independent reflections: 4601 [R(int) = 0.0229], data/restraints/parameters: 4601/0/325, goodness-of-fit on F ²: 1.075, final R indexes [I > = 2σ (I)]: R1 = 0.0432, wR2 = 0.1261, final R indexes [all data]: R1 = 0.0478, wR2 = 0.1323, largest diff. peak and hole: 0.405 and –0.342 e A^–3. CCDC-1476587 contains the supplementary crystallographic data for 20. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.