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

Daiki Inamori; Takuya Miwa; Tetsuaki Fujihara; Yasushi Tsuji; Jun Terao

doi:10.1055/s-0036-1588824

Synlett, Table of Contents

Synlett 2017; 28(14): 1775-1779
DOI: 10.1055/s-0036-1588824

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

Daiki Inamori

^aDepartment of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan

,

Takuya Miwa

^aDepartment of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan

,

Tetsuaki Fujihara

^aDepartment of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan

,

Yasushi Tsuji

^aDepartment of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan

,

Jun Terao*

^bDepartment of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, Tokyo 153-8902, Japan

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Abstract

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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

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References

References and Notes

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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).

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