Synlett 2012; 23(10): 1467-1472
DOI: 10.1055/s-0031-1291045
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Macrocycles with Anthracene Units and Amide Bonds; Potential Building Blocks for 1D and 2D Constructions

Animesh Saha
ETH Zürich, Department of Materials, Laboratory of Polymer Chemistry, Wolfgang-Pauli Str. 10, HCI J541, 8093 Zürich, Switzerland, Fax: +41(44)6331395   eMail: sakamoto@mat.ethz.ch   eMail: ads@mat.ethz.ch
,
Jeroen van Heijst
ETH Zürich, Department of Materials, Laboratory of Polymer Chemistry, Wolfgang-Pauli Str. 10, HCI J541, 8093 Zürich, Switzerland, Fax: +41(44)6331395   eMail: sakamoto@mat.ethz.ch   eMail: ads@mat.ethz.ch
,
Junji Sakamoto*
ETH Zürich, Department of Materials, Laboratory of Polymer Chemistry, Wolfgang-Pauli Str. 10, HCI J541, 8093 Zürich, Switzerland, Fax: +41(44)6331395   eMail: sakamoto@mat.ethz.ch   eMail: ads@mat.ethz.ch
,
A. Dieter Schlüter*
ETH Zürich, Department of Materials, Laboratory of Polymer Chemistry, Wolfgang-Pauli Str. 10, HCI J541, 8093 Zürich, Switzerland, Fax: +41(44)6331395   eMail: sakamoto@mat.ethz.ch   eMail: ads@mat.ethz.ch
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Publikationsverlauf

Received: 31. Januar 2012

Accepted after revision: 28. März 2012

Publikationsdatum:
25. Mai 2012 (online)


Abstract

A collection of novel m-terphenyl and mixed m-terphenyl-anthracene building blocks were synthesised on scales between several 100 mg and a few grams. Proper connection of some of these building blocks utilising amide coupling chemistry afforded macrocycles containing two and three anthracene units. These macrocycles were obtained as virtually pure compounds on 14 and 24 mg scales, respectively. Their UV/Vis and fluorescence spectra are reminiscent of the parent anthracene, which renders them potential candidates for various applications including sensing and molecular constructions.

Supporting Information

 
  • References


    • For example, see:
    • 1a Moore JS. Acc. Chem. Res. 1997; 30: 402
    • 1b Höger S. Chem.–Eur. J. 2004; 10: 1320
  • 2 Ghadiri MR. Adv. Mater. 1995; 7: 675
  • 3 Sakamoto J, van Heijst J, Lukin O, Schlüter AD. Angew. Chem. Int. Ed. 2009; 48: 1030

    • For examples, see:
    • 4a Barboiu M, Vaughan G, Graff R, Lehn J.-M. J. Am. Chem. Soc. 2003; 125: 10257
    • 4b Bauer T, Zheng Z, Renn A, Enning R, Stemmer A, Sakamoto J, Schlüter AD. Angew. Chem. Int. Ed. 2011; 50: 7879

      For examples, see:
    • 5a Yamamoto T, Fukushima T, Yamamoto Y, Kosaka A, Jin W, Ishii N, Aida T. J. Am. Chem. Soc. 2006; 128: 14337
    • 5b Münzenberg C, Rossi A, Feldman K, Fiolka R, Stemmer A, Kita-Tokaczyk K, Meier W, Sakamoto J, Lukin O, Schlüter AD. Chem.–Eur. J. 2008; 14: 10797
  • 6 Kissel P, Schlüter AD, Sakamoto J. Chem.–Eur. J. 2009; 15: 8955
  • 7 Kissel P, Erni R, Schweizer WB, Rossell MD, King BT, Bauer T, Götzinger S, Schlüter AD, Sakamoto J. Nat. Chem. 2011; 4: 287
  • 8 Moran JR, Ericson JL, Dalcanale E, Bryant JA, Knobler CB, Cram DJ. J. Am. Chem. Soc. 1991; 113: 5707
  • 9 Ariga K, Terasaka Y, Sakai D, Tsuji H, Kikuchi J. J. Am. Chem. Soc. 2000; 122: 7835
  • 10 Nelson JC, Saven JG, Moore JS, Wolynes PG. Science 1997; 277: 1793
  • 11 Kissel P, van Heijst J, Enning R, Stemmer A, Schlüter AD, Sakamoto J. Org. Lett. 2010; 12: 2778
  • 12 Amrheim P, Shivanyuk A, Johnson DW, Rebek JJr. J. Am. Chem. Soc. 2002; 124: 10349
  • 13 For examples, see: Yang Y, Feng W, Hu J, Zou S, Gao R, Yamato K, Kline M, Cai Z, Gao Y, Wang Y, Li Y, Yang Y, Yuan L, Zeng XC, Gong B. J. Am. Chem. Soc. 2011; 113: 18590
    • 14a Becker H.-D. Chem. Rev. 1993; 93: 145
    • 14b Bouas-Laurent H, Desvergne J.-P, Castellan A, Lapouyade R. Chem. Soc. Rev. 2000; 29: 43
    • 14c Bouas-Laurent H, Desvergne J.-P, Castellan A, Lapouyade R. Chem. Soc. Rev. 2001; 30: 248
  • 15 Rogers ME, Averill BA. J. Org. Chem. 1986; 51: 3308
  • 16 Kissel P, Breitler S, Reinmüller V, Lanz P, Federer L, Schlüter AD, Sakamoto J. Eur. J. Org. Chem. 2009; 2953

    • For examples, see:
    • 17a Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
    • 17b Suzuki A. J. Organomet. Chem. 1999; 576: 147
    • 17c Miyaura N. Top. Curr. Chem. 2002; 219: 11
  • 18 Open-chain oligomers are likely to be present because the 1H NMR spectra of crude mixtures showed signals that did not belong to cycles but absorbed at similar chemical shifts. No attempts were made to isolate non-cyclic products
  • 19 Synthesis of macrocycle 1 from 11 and 13: Compounds 11 (258.6 mg, 0.26 mmol) and 13 (230.0 mg, 0.26 mmol) was dissolved in a mixture of anhydrous DMF (500 mL) and anhydrous CH2Cl2 (28 mL). HOBt (356.0 mg, 2.64 mmol), DMAP (3.2 mg, 0.026 mmol), and DIPEA (853.0 mg, 6.6 mmol) were added successively under N2 and the mixture was cooled to 0 °C. EDC·HCl (506.0 mg, 2.64 mmol) was added and the mixture was warmed to r.t. overnight. The reaction was then stirred at r.t. under N2 for 21 d. After the reaction was over, solvent was removed under reduced pressure. The crude reaction mixture was purified by using Sephadex LH-20 as packing material and DMF as the eluent, and finally by reverse-phase chromatog-raphy (C18 as stationary phase; MeOH–DMF, 9:1) to give 1 (24.0 mg, 5%) as a yellow solid. 1H NMR (500 MHz, DMSO-d 6, 50 °C): δ = 10.54 (s, 6 H, NH), 9.33 (s, 3 H), 8.72 (s, 3 H), 8.21 (d, J = 8.5 Hz, 6 H), 7.96 (s, 6 H), 7.72 (d, J = 6.0 Hz, 6 H), 7.52 (t, J = 7.0 Hz, 6 H), 7.43 (s, 9 H), 7.23–7.12 (m, 18 H), 4.70–4.65 (m, 6 H, benzyl and THP), 4.47 (d, J = 12.0 Hz, 3 H, benzyl), 3.80–3.77 (m, 3 H, THP), 3.44–3.42 (m, 3 H, THP), 1.71–1.42 (m, 18 H, THP). 13C NMR (75 MHz, DMSO-d 6, 25 °C): δ = 167.1, 140.7, 140.4, 139.7, 139.49, 139.42, 135.0, 131.0, 130.4, 129.0, 128.0, 127.3, 125.8, 125.0, 124.9, 124.0, 122.2, 119.2, 118.4, 97.3, 68.0, 61.3, 30.1, 24.9, 19.0. HRMS (FT-MALDI, DCTB): m/z [M + Na]+ calcd for C120H96N6O12: 1835.6978; found: 1835.6990