Synlett 2016; 27(14): 2095-2100
DOI: 10.1055/s-0035-1561480
cluster
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Unexpected trans-meso Macrocycle from Novel Unsymmetrical Tetraphenylene

Chun-Lin Deng
a  Department of Chemistry & State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, P. R. of China   Email: hncwong@cuhk.edu.hk
,
Sam C. K. Hau
c  Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Kowloon, Hong Kong SAR, P. R. of China
,
Xiao-Shui Peng
a  Department of Chemistry & State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, P. R. of China   Email: hncwong@cuhk.edu.hk
b  Shenzhen Municipal Key Laboratory of Chemical Synthesis of Medicinal Organic Molecules & Shenzhen Center of Novel Functional Molecules, Shenzhen Research Institute, The Chinese University of Hong Kong, No. 10, 2nd Yuexing Road, Shenzhen 518507, P. R. of China
,
Henry N. C. Wong*
a  Department of Chemistry & State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, P. R. of China   Email: hncwong@cuhk.edu.hk
b  Shenzhen Municipal Key Laboratory of Chemical Synthesis of Medicinal Organic Molecules & Shenzhen Center of Novel Functional Molecules, Shenzhen Research Institute, The Chinese University of Hong Kong, No. 10, 2nd Yuexing Road, Shenzhen 518507, P. R. of China
› Author Affiliations
Further Information

Publication History

Received: 03 May 2016

Accepted after revision: 21 May 2016

Publication Date:
23 June 2016 (online)

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.

Supporting Information

 
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  • 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. Rf = 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, ρcalc (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.