Synlett, Inhaltsverzeichnis Synlett 2022; 33(18): 1868-1872DOI: 10.1055/a-1679-7161 cluster Development and Applications of Novel Ligands/Catalysts and Mechanistic Studies on Catalysis Synthesis of Novel Chiral Phenanthroline Ligands and a Copper Complex Jingjing Tang , Jian Li , Xueyan Yang∗ , Zhipeng Zhang ∗ Artikel empfehlen Abstract Artikel einzeln kaufen Alle Artikel dieser Rubrik Abstract A novel class of chiral multidentate ligands has been designed and synthesized from the important classic ligand 1,10-phenanthroline and amino acids. The ligands were proven to be able to coordinate with copper(2+) ion by the formation of a novel chiral copper complex, the structure of which was determined by single-crystal X-ray diffraction. Key words Key wordsphenanthroline - amino acids - ligands - asymmetric synthesis - copper complex Volltext Referenzen References and Notes 1a Summers LA. Adv. Heterocycl. Chem. 1978; 22: 1 1b Sammes PG, Yahioglu G. Chem. Soc. 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The combined organic layers were washed with brine, dried (Na2SO4), and concentrated. The residue was purified by column chromatography [silica gel, CH2Cl2–MeOH (80:1)] to give a yellow solid; yield: 1.361 g (58%); mp 160–161 °C. 1H NMR (400 MHz, CHCl3): δ = 10.42 (s, 2 H), 8.38 (d, J = 8.4 Hz, 2 H), 8.06 (dd, J = 8.0, 1.2 Hz, 2 H), 7.94 (d, J = 8.0 Hz, 2 H), 7.91 (d, J = 7.2 Hz, 2 H), 7.88 (s, 2 H), 7.71 (td, J = 7.6, 1.2 Hz, 2 H), 7.56 (t, J = 7.6 Hz, 2 H). 13C NMR (101 MHz, CDCl3): δ = 192.53, 156.30, 145.92, 143.30, 136.84, 135.72, 133.18, 130.88, 129.23, 128.59, 127.78, 126.75, 123.93. HRMS (ESI-TOF): m/z [M + H]+ calcd for C26H17N2O2: 389.1285; found: 389.1276. 9 Diamino Diester 8a; Typical Procedure A dried 50 mL Schlenk flask was charged with methyl l-phenylalaninate hydrochloride (397 mg, 1.84 mmol), intermediate 7a (300 mg, 0.77 mmol), and MgSO4 (222 mg, 1.84 mmol) under N2. CH2Cl2 (10 mL) was added, the mixture was cooled to 0 °C, and Et3N (255 μL, 1.84 mmol) was added. The mixture was stirred at 0 °C for 0.5 h; it was then allowed to warm to r.t. and stirred for 12 h. The mixture was then cooled again to 0 °C before NaBH(OAc)3 (1.632 g, 7.7 mmol) was added. The resulting mixture was stirred at 0 °C for 0.5 h, warmed slowly to r.t., and stirred overnight. The reaction was quenched with H2O, and the product was extracted with CH2Cl2 (×3). The organic layers were combined, dried (Na2SO4), and concentrated, and the residue was purified by column chromatography [silica gel, CH2Cl2–MeOH (80:1)] to give a yellow solid; yield: 386 mg (70%); mp 106–107 °C; [α]D 20 +45.6 (c = 0.25, CHCl3). 1H NMR (400 MHz, CDCl3): δ = 8.33 (d, J = 8.4 Hz, 2 H), 7.91 (s, 2 H), 7.85 (d, J = 8.0 Hz, 2 H), 7.65 (d, J = 7.6 Hz, 2 H), 7.51 (d, J = 5.6 Hz, 2 H), 7.44 (t, J = 6.4 Hz, 2 H), 7.34 (t, J = 7.2 Hz, 2 H), 7.11–7.05 (m, 6 H), 6.90–6.82 (m, 4 H), 4.06–3.82 (m, 4 H), 3.51–3.67 (m, 2 H), 3.08 (s, 6 H), 2.89 (s, 2 H), 2.41–2.59 (m, 2 H). 13C NMR (101 MHz, CDCl3): δ = 171.70, 158.72, 144.92, 140.88, 137.50, 136.26, 133.13, 132.74, 130.48, 129.58, 129.39, 129.21, 128.28, 127.89, 126.76, 126.73, 124.36, 61.73, 51.60, 49.60, 36.93. HRMS (ESI-TOF): m/z [M + H]+ calcd for C46H43N4O4: 715.3279; found: 715.3263. 10 Chiral Phenanthroline Ligand 9a; Typical ProcedureTo a solution of diester 8a (100 mg, 0.14 mmol) in MeOH (10 mL) and H2O (2 mL) was added NaOH (112 mg, 2.8 mmol) at r.t., and the mixture was heated to 60 °C with stirring for 12 h. Upon completion of the reaction, the pH of the solution was adjusted to 3–4 by addition of 1.0 M aq HCl. The solvent was then removed under reduced pressure and the crude product was dissolved in MeOH. The solution was filtered and concentrated, and the crude product was crystallized from MeOH to give a yellow solid; yield: 96 mg (91%); mp 200–201 °C; [α]D 20 –88.8 (c 0.25, MeOH). 1H NMR (400 MHz, DMSO-d 6): δ = 8.71 (d, J = 8.4 Hz, 2 H), 8.17 (s, 2 H), 8.08 (d, J = 8.4 Hz, 2 H), 7.72 (d, J = 7.2 Hz, 2 H), 7.67–7.61 (m, 2 H), 7.56–7.45 (m, 4 H), 7.09–7.00 (m, 6 H), 6.88–6.79 (m, 4 H), 4.18 (d, J = 13.2 Hz, 2 H), 4.09 (d, J = 12.8 Hz, 2 H), 3.45 (t, J = 7.0 Hz, 2 H), 2.94–2.76 (m, 2 H), 2.76–2.64 (m, 2 H). 13C NMR (101 MHz, DMSO-d 6): δ = 170.09, 157.68, 143.91, 140.81, 138.30, 136.16, 132.41, 131.46, 130.53, 129.29, 129.24, 128.92, 127.92, 127.67, 126.75, 126.43, 124.37, 60.60, 47.19, 34.97. HRMS (ESI-TOF): m/z [M + H]+ calcd for C44H39N4O4: 687.2966; found: 687.2962. 11 Copper Complex 10a To a solution of 9a (100 mg, 0.13 mmol) in MeOH (10 mL) was added NaH (112 mg, 60% dispersion in mineral oil, 2.8 mmol), and the mixture was stirred at r.t. for 0.5 h. A solution of CuCl2 in MeOH (1.0 mL) was added dropwise to the mixture, which was then heated to 40 °C and stirred for 5 h. After cooling to r.t., the mixture was filtered through a pad of Celite and concentrated under reduced pressure. The crude product was purified by crystallization from MeOH–Et2O to give a deep-blue solid; yield: 21 mg (40%); mp 210–211 °C. HRMS (ESI-TOF): m/z [M + H]+ calcd for C44H38ClCuN4O4: 784.1872; found: 784.1863. 12 CCDC 2106610 contains the supplementary crystallographic data for compound 10a. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures Zusatzmaterial Zusatzmaterial Supporting Information
