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Synthesis of a Dinuclear Copper NHC Complex Bearing a Rigid π-Conjugated Cyclic Framework

Abstract

Macrocyclic dinuclear complexes have been gaining popularity in the design of homogeneous catalysts. Herein, we report the design of such a complex featuring catalytically active sites fixed inside the ring and its synthesis using a cross-coupling reaction.

Keywords

macrocycle - N-heterocyclic carbene ligand - dinuclear complex - Glaser reaction - Sonogashira coupling - cyclization

• References and Notes

• 1a Wiester MJ. Ulmann PA. Mirkin CA. Angew. Chem. Int. Ed. 2011; 50: 114
• 1b Lifschitz AM. Rosen MS. McGuik M. Mirkin CA. J. Am. Chem. Soc. 2015; 137: 7252
• 2 Matsunaga S. Shibasaki M. Synthesis 2013; 45: 421
• 3 Bratko I. Gómez M. Dalton Trans. 2013; 10664
• 4 Raynel M. Ballester P. Vidal-Ferran A. Leeuwen PW. N. M. Chem. Soc. Rev. 2014; 43: 1734
• 5 Li H. Yao ZJ. Liu D. Jin GX. Coord. Chem. Rev. 2015; 239-294: 139
• 6a Ready JM. Jacobsen EN. J. Am. Chem. Soc. 2001; 123: 2687
• 6b Ready JM. Jacobsen EN. Angew. Chem. Int. Ed. 2002; 123: 1374
• 6c Loy RN. Jacobsen EN. J. Am. Chem. Soc. 2009; 131: 2786
• 7a Gianneschi NC. Bertin PA. Nguyen ST. Mirkin CA. Zakharov LN. Rheingold AL. J. Am. Chem. Soc. 2003; 125: 10508
• 7b Gianneschi NC. Nguyen ST. Mirkin CA. J. Am. Chem. Soc. 2005; 127: 1644
• 7c Oliveri CG. Gianneschi NC. Nguyen ST. Mirkin CA. Stern CL. Wawrzak Z. Pink M. J. Am. Chem. Soc. 2006; 128: 16286
• 7d Hyo JY. Heo J. Mirkin CA. J. Am. Chem. Soc. 2007; 129: 14182
• 7e Hyo JY. Mirkin CA. J. Am. Chem. Soc. 2008; 130: 11590
• 8a Mackay LG. Wylie RS. Sanders JK. M. J. Am. Chem. Soc. 1994; 116: 3141
• 8b Walter CJ. Sanders JK. M. Angew. Chem. Int. Ed. Engl. 1995; 34: 217
• 8c Clyde-Watson Z. Vidal-Ferran A. Twyman LJ. Walter CJ. McCallien DW. J. Fanni S. Bampos N. Wylie RS. Sanders JK. M. New J. Chem. 1998; 22: 493
• 8d Totten RK. Ryan P. Kang B. Lee SJ. Broadbelt LJ. Snurr RQ. Hupp JT. Nguyen ST. Chem. Commun. 2012; 4178
• 8e Kang B. Kurutz JW. Youm K.-T. Totten RK. Hupp JT. Nguyen ST. Chem. Sci. 2012; 3: 1938
• 9 Huang SL. Lin YJ. Hor TS. A. Guo ZW. Jin GX. J. Am. Chem. Soc. 2013; 135: 8125
• 10 Yamaguchi Y. Kobayashi S. Miyamura S. Okamoto Y. Wakamiya T. Matsubara Y. Yoshida ZI. Angew. Chem. Int. Ed. 2004; 43: 366
• 11 Ohkoda Y. Asaishi A. Namiki T. Hashimoto T. Yamada M. Shirai K. Katagami Y. Sugaya T. Tadokoro M. Satake A. Chem. Eur. J. 2015; 21: 11745
• 12a Kuritani M. Tashiro S. Shionoya M. Inorg. Chem. 2012; 51: 1508
• 12b Kuritani M. Tashiro S. Shionoya M. Chem. Asian J. 2013; 8: 1368
• 12c Omoto K. Tashiro S. Kuritani M. Shionoya M. J. Am. Chem. Soc. 2014; 136: 17946
• 13 Baxter PN. W. Chem. Eur. J. 2003; 9: 5011
• 14a Ma C. Lo A. Abdolmaleki A. MacLachlan MJ. Org. Lett. 2004; 6: 3841
• 14b Ma CT. L. MacLachlan MJ. Angew. Chem. Int. Ed. 2005; 44: 4178
• 15a Nabeshima T. Bull. Chem. Soc. Jpn. 2010; 83: 969
• 15b Akine S. Sunaga S. Taniguchi T. Miyazaki H. Nabeshima T. Inorg. Chem. 2007; 46: 2959
• 15c Nabeshima T. Yamamura M. Pure Appl. Chem. 2013; 85: 763
• 15d Yamashita A. Watanabe A. Akine S. Nabeshima T. Nakano M. Yamamura T. Kajiwara T. Angew. Chem. Int. Ed. 2011; 50: 4016
• 15e Akine S. Sunaga S. Nabeshima T. Chem. Eur. J. 2011; 17: 6853
• 15f Yamamura M. Miyazaki H. Iida M. Akine S. Nabeshima T. Inorg. Chem. 2011; 50: 5315
• 15g Akine S. Kagiyama S. Nabeshima T. Inorg. Chem. 2007; 46: 9525
• 15h Akine S. Kagiyama S. Nabeshima T. Inorg. Chem. 2010; 49: 2010
• 15i Akine S. Tadokoro T. Nabeshima T. Inorg. Chem. 2012; 51: 11478
• 15j Akine S. Matsumoto T. Nabeshima T. Angew. Chem. Int. Ed. 2016; 55: 960
• 15k Akine S. Utsuno F. Piao S. Orita H. Tsuzuki S. Nabeshima T. Inorg. Chem. 2016; 55: 810
• 15l MacLachlan MJ. Pure Appl. Chem. 2006; 78: 873
• 15m Frischemann PD. Gallan AJ. Chong JH. MacLachlan MJ. Inorg. Chem. 2008; 47: 101
• 15n Hui JK.-H.. MacLachlan M. J.. Chem. Commun. 2006; 2480
• 16a Lee SY. Na SJ. Kwon HY. Lee BY. Kang SO. Organometallics 2004; 23: 5382
• 16b Lee BY. Kwon HY. Lee SY. Na SJ. Han S. Yun H. Lee H. Park Y.-W. J. Am. Chem. Soc. 2005; 127: 3031
• 16c Na SJ. Joe DJ. Sujith S. Han WS. Kang SO. Lee BY. J. Organomet. Chem. 2006; 691: 611
• 17a Furst MR. L. Cazin CS. J. Chem. Commun. 2010; 6924
• 17b Bidal YD. Lesieur M. Melaimi M. Cordes DB. Slawin AM. Z. Bertrand G. Cazin CS. J. Chem. Commun. 2015; 51: 4778
• 18 Synthesis of 10 Compound 6 (1.16 g, 2.73 mmol), 9 (577 mg, 903 μmol), Pd(PPh₃)₄ (62.8 mg, 54.4 μmol), and CuI (1.60 mg, 0.903 μmol) were dissolved in DMF (40.0 mL) and degassed Et₃N (2.04 mL) under Ar. After the solution was stirred overnight at 100 °C, CH₂Cl₂, Et₂O, and H₂O were added to the solution and the organic layer was separated and dried over MgSO₄, and then filtered. The solvent was removed by evaporation, and the residue was purified by GPC (eluent: CHCl₃) to give 10 (1.02 g, 798 μmol, 88%) as a brown solid. ¹H NMR (500 MHz, CDCl₃): δ = 10.54 (s, 1 H), 8.02 (s, 2 H), 7.74 (s, 2 H), 7.69 (s, 2 H), 7.65 (s, 2 H), 7.52(s, 4 H), 7.46 (s, 2 H), 7.40 (d, J = 1.5 Hz, 4 H), 2.46–2.38 (sept, J = 6.7 Hz, 4 H), 1.39 (s, 36 H), 1.30 (d, J = 6.7 Hz, 12 H), 1.27 (d, J = 6.7 Hz, 12 H), 1.02 (s, 18 H), 0.21 (s, 12 H). ¹³C NMR (126 MHz, CDCl₃): δ = 151.49, 145.41, 143.25, 138.98, 133.80, 131.38, 130.65, 129.58, 128.15, 127.39, 126.67, 124.15, 123.06, 122.22, 121.68, 104.87, 93.73, 91.12, 88.74, 35.13, 31.65, 26.27, 24.73, 23.80, 16.86, –4.50. HRMS (ESI): m/z [10 – Cl^–]⁺ calcd for C₈₇H₁₁₃N₂Si₂ ⁺: 1241.8437; found: 1241.8408 (peak top).
• 19 Synthesis of 11 as a crude mixture Compound 10 (205 mg, 160 μmol) and TBAF (1.0 M in THF, 320 μL, 320 μmol) were dissolved in degassed THF (5.00 mL) under Ar. The solution was stirred for 15 min at 0 °C, then CH₂Cl₂ and saturated NH₄Cl aq. were added to the solution and the organic layer was separated and dried over Na₂SO₄, and then filtered. The solvent was removed by evaporation, and the residue was purified by GPC (eluent: CHCl₃) to give 11 (167 mg, 159 μmol, 99%) as a pale-yellow solid with a small amount of inseparable admixtures. ¹H NMR (500 MHz, CDCl₃): δ = 10.60 (s, 1 H), 7.98 (s, 2 H), 7.78 (s, 2 H), 7.71 (s, 2 H), 7.70(s, 2 H), 7.52 (s, 4 H), 7.47 (s, 2 H), 7.40 (s, 4 H), 3.14 (s, 2 H), 2.42–2.39 (sept, J = 6.7 Hz, 4 H), 1.39 (s, 36 H), 1.29 (d, J = 7.0 Hz, 12 H), 1.27(d, J = 7.0 Hz, 12 H). ¹³C NMR (126 MHz, CDCl₃): δ = 151.57, 145.40, 143.26, 138.76, 133.77, 131.57, 130.96, 129.56, 128.17, 127.29, 126.61, 123.24, 123.06, 122.33, 121.63, 90.93, 88.92, 82.89, 78.11, 35.12, 31.63, 29.30, 24.72, 23.82. The peaks of admixtures: 132.09, 132.01, 128.56, 128.65. HRMS (MALDI–TOF): m/z [11 – Cl^–]⁺ calcd for C₇₅H₈₅N₂ ⁺: 1013.6707; found: 1013.6689 (peak top).
• 20 Synthesis of 12 and 13 Compound 11 (54.1 mg, 51.0 μmol), CuCl (357 mg, 3.61 mmol), and TMEDA (8.53 mL, 3.61 mmol) were dissolved in CH₂Cl₂ (130 mL) under air. The solution was stirred for 20 h at 30 °C, then CH₂Cl₂ and saturated NH₄Cl aq. were added to the solution and the organic layer was separated and dried over MgSO₄, and then filtered. The solvent was removed by evaporation, and the residue was purified by GPC (eluent: CHCl₃) to give 12 (10.7 mg, 9.64 μmol, 19%) as a white solid and 13 (2.00 mg, 0.598 μmol, 1.7%) as a pale-yellow solid. Spectra of 12: ¹H NMR (500 MHz, CDCl₃): δ = 7.92 (s, 4 H), 7.74 (s, 4 H), 7.68 (s, 8 H), 7.50 (s, 8 H), 7.49 (s, 4 H), 7.43 (d, J = 1.7 Hz, 8 H), 7.19 (s, 4 H), 2.63–2.53 (sept, J = 6.8 Hz, 8 H), 1.41 (s, 72 H), 1.37–1.35 (d, J = 6.8 Hz, 24 H), 1.27–1.25 (d, J = 6.8 Hz, 24 H). ¹³C NMR (126 MHz, CDCl₃): δ = 181.34, 151.64, 146.23, 143.34, 138.98, 136.69, 134.57, 130.28, 130.23, 128.02, 125.63, 124.07, 123.34, 122.74, 122.37, 121.75, 90.17, 89.86, 81.82, 75.01, 35.22, 31.70, 24.82, 24.03. HRMS (MALDI–TOF): m/z [12 – Cl^–]⁺ calcd for C₁₅₀H₁₆₄ClCu₂N₄ ⁺: 2185.1427; found: 2185.1358 (peak top). Spectra of 13: ¹H NMR (500 MHz, CDCl₃): δ = 7.80 (s, 12 H), 7.75 (s, 6 H), 7.51 (s, 12 H), 7.49 (s, 6 H), 7.44 (s, 12 H), 7.17 (s, 6 H), 2.62–2.54 (sept, J = 6.7 Hz, 23 H), 1.41 (s, 72 H), 1.37–1.35 (d, J = 6.7 Hz, 36 H), 1.29–1.27 (d, J = 6.7 Hz, 36 H). HRMS (MALDI–TOF): m/z [13 – Cl^–]⁺ calcd for C₂₂₆H₂₆₀Cl₂Cu₃N₆ ⁺: 3295.6743; found: 3295.6762 (peak top).