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Synlett 2017; 28(14): 1775-1779
DOI: 10.1055/s-0036-1588824
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© Georg Thieme Verlag Stuttgart · New York

Thieme Chemistry Journals Awardees – Where Are They Now?
Synthesis of a Dinuclear Copper NHC Complex Bearing a Rigid π-Conjugated Cyclic Framework

Daiki Inamori
a   Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
,
Takuya Miwa
a   Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
,
Tetsuaki Fujihara
a   Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
,
Yasushi Tsuji
a   Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
,
Jun Terao*
b   Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, Tokyo 153-8902, Japan
› Author AffiliationsThis research was supported by the Funding Program for JSPS Research Fellow and a Grant-in-Aid for Scientific Research (B), and JSPS KAKENHI Grant Numbers JP16H00834 and JP16H00965 from MEXT, Japan. This research was also supported by The Uehara Memorial Foundation and Terumo Foundation for Life Sciences and Arts, and CREST, JST.
Further Information

Publication History

Received: 18 March 2017

Accepted after revision: 11 April 2017

Publication Date:
11 May 2017 (online)

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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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588824.
  • Supporting Information
 

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  • 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).