Palladium-Catalyzed Annulation of 2,2′-Dibromobiphenyls with Alkynes: Synthesis of Functionalized Phenanthrenes and Dibenzochrysenes

Jun Ma; Gaoqiang Li; Yan Qiao; Jingxuan Tu; Sha Liu; Feng Xu

doi:10.1055/s-0034-1378726

Synlett, Inhaltsverzeichnis

Synlett 2015; 26(14): 1991-1996
DOI: 10.1055/s-0034-1378726

letter

Palladium-Catalyzed Annulation of 2,2′-Dibromobiphenyls with Alkynes: Synthesis of Functionalized Phenanthrenes and Dibenzochrysenes

Jun Ma

Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China eMail: gqli@snnu.edu.cn eMail: fengxu@snnu.edu.cn

,

Gaoqiang Li*

Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China eMail: gqli@snnu.edu.cn eMail: fengxu@snnu.edu.cn

,

Yan Qiao

Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China eMail: gqli@snnu.edu.cn eMail: fengxu@snnu.edu.cn

,

Jingxuan Tu

Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China eMail: gqli@snnu.edu.cn eMail: fengxu@snnu.edu.cn

,

Sha Liu

Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China eMail: gqli@snnu.edu.cn eMail: fengxu@snnu.edu.cn

,

Feng Xu*

Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China eMail: gqli@snnu.edu.cn eMail: fengxu@snnu.edu.cn

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Abstract

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Abstract

A palladium-catalyzed annulation process of 2,2′-dibromobiphenyls with alkynes for the synthesis of functionalized phenanthrenes has been realized. The methodology provides an efficient approach to dibenzochrysene derivatives starting from simple reactants in two steps.

Key words

alkynes - annulations - domino reaction - fused-ring systems - palladium

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Referenzen

References and Notes

For reviews of PAHs in organic electronics, see:

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19 9,10-Disubustituted Phenanthrenes 3aa–3bd; General Procedure: A Schlenk flask was charged with 2,2′-dibromobiphenyls (0.3 mmol), alkyne (0.33 mmol), Pd(PPh₃)₂Cl₂ (11 mg, 5 mol%), Xantphos (10 mg, 5.5 mol%) and K₂CO₃ (124 mg, 0.9 mmol) under N₂. Mesitylene (5 mL) was added from a syringe, and the mixture was stirred at 150 °C until the reaction was complete (TLC). The mixture was cooled to r.t., and H₂O (10 mL) was added. The resulting mixture was extracted with EtOAc (3 × 15 mL). The organic layers were combined, dried over anhyd Na₂SO₄, and concentrated to give a residue that was purified by column chromatography (silica gel, PE–EtOAc). 9-(3-Methoxyphenyl)-10-phenylphenanthrene (3ac): white solid; yield: 63 mg (58%); mp189.8–191.1 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.81 (d, J = 8.3 Hz, 2 H), 7.60–7.68 (m, 3 H), 7.54–7.57 (m, 1 H), 7.46–7.51 (m, 2 H), 7.26–7.29 (m, 1 H), 7.18–7.25 (m, 3 H), 7.13–7.16 (m, 2 H), 6.70–6.79 (m, 3 H), 3.68 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 158.9, 140.9, 139.5, 137.0, 137.0, 131.9, 131.7, 131.0, 131.0, 130.0, 130.0, 128.5, 127.9, 127.7, 127.6, 126.6, 126.6, 126.5, 126.4, 123.8, 122.5, 122.5, 116.6, 112.4, 55.2. HRMS (ESI): m/z calcd for [C₂₇H₂₀ONa]⁺: 383.1412; found: 383.1418. 9-(2-Methoxyphenyl)-10-phenylphenanthrene (3ad): faint yellow solid; yield: 23 mg (21%); mp 198.9–191.1 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.71 (dd, J = 8.3, 4.0 Hz, 2 H), 7.53–7.58 (m, 2 H), 7.47–7.50 (m, 1 H), 7.36–7.41 (m, 3 H), 7.07–7.16 (m, 6 H), 6.93 (dd, J = 7.4, 1.7 Hz, 1 H), 6.68–6.77 (m, 2 H), 3.49 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 156.2, 138.8, 136.5, 133.0, 131.3, 131.0, 130.7, 129.7, 129.1, 128.9, 127.5, 127.5, 126.7, 126.4, 126.2, 125.6, 125.5, 125.4, 125.2, 125.2, 121.5, 121.5, 119.0, 109.3, 54.1. HRMS (ESI): m/z calcd for [C₂₇H₂₀ONa]⁺: 383.1412; found: 383.1407. 9-(4-Fluorophenyl)-10-phenylphenanthrene (3ae): white solid; yield: 55 mg (53%); mp 256.8–257.9 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.80 (d, J = 8.4 Hz, 2 H), 7.64–7.68 (m, 2 H), 7.47–7.56 (m, 4 H), 7.20–7.26 (m, 3 H), 7.08–7.14 (m, 4 H), 6.90–6.95 (m, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 162.8, 160.3, 139.5, 137.7, 136.1, 135.5, 132.6, 132.5, 131.8, 131.0, 130.1, 127.9, 127.7, 127.6, 126.7, 126.6, 126.6, 126.5, 122.6, 122.5, 114.7, 114.5. HRMS (ESI): m/z calcd for [C₂₆H₁₇FNa]⁺: 371.1212; found: 371.1225. 9-(4-Ethylphenyl)-10-phenylphenanthrene (3af): white solid; yield: 77 mg (72%); mp 163.3–164.5 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.80 (d, J = 8.3 Hz, 2 H), 7.54–7.67 (m, 4 H), 7.45–7.50 (m, 2 H), 7.18–7.26 (m, 3 H), 7.14–7.16 (m, 2 H), 7.05 (s, 4 H), 2.61 (q, J = 7.6 Hz, 2 H), 1.21 (t, J = 7.6 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 142.2, 141.6, 139.7, 137.3, 137.2, 136.7, 132.1, 132.0, 131.1, 130.9, 130.0, 129.0, 128.0, 127.8, 127.6, 127.2, 127.0, 126.6, 126.3, 126.3, 122.5, 122.4, 28.5, 15.4. HRMS (ESI): m/z calcd for [C₂₈H₂₂Na]⁺: 381.1620; found: 381.1629. 9,10-Bis(4-tert-butylphenyl)phenanthrene (3aj): white solid; yield: 80 mg (60%); mp 279.9–281.0 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.80 (d, J = 8.2 Hz, 2 H), 7.71 (dd, J = 8.2, 0.9 Hz, 2 H), 7.63–7.67 (m, 2 H), 7.48–7.51 (m, 2 H), 7.17–7.20 (m, 4 H), 7.01–7.03 (m, 4 H), 1.27 (s, 18 H). ¹³C NMR (101 MHz, CDCl₃): δ = 149.0, 137.6, 136.6, 132.0, 130.7, 129.9, 128.0, 126.5, 126.2, 124.1, 122.5, 34.4, 31.3. HRMS (ESI): m/z calcd for [C₃₄H₃₄Na]⁺: 465.2559; found: 465.2572. 9-Phenyl-10-(2-thienyl)phenanthrene (3am): yellow solid; yield: 64 mg (63%); mp 214.5–215.3 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.79 (d, J = 8.3 Hz, 2 H), 7.78–7.80 (m, 1 H), 7.65–7.70 (m, 2 H), 7.52–7.56 (m, 2 H), 7.46–7.50 (m, 1 H), 7.22–7.33 (m, 6 H), 6.92–6.95 (m, 1 H), 6.84–6.86 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 140.1, 139.9, 139.5, 132.5, 131.7, 130.7, 130.4, 129.9, 129.6, 129.2, 128.2, 127.6, 127.6, 126.9, 126.9, 126.8, 126.7, 126.6, 126.3, 126.0, 122.5, 122.4. HRMS (ESI): m/z calcd for [C₂₄H₁₆SNa]⁺: 359.0871; found: 359.0872. 4-(10-Phenylphenanthren-9-yl)pyridine (3ao): faint yellow solid; yield: 57 mg (57%); mp 235.8–236.8 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.75 (dd, J = 8.3, 4.9 Hz, 2 H), 8.42 (dd, J = 4.5, 1.4 Hz, 2 H), 7.60–7.65 (m, 2 H), 7.37–7.50 (m, 4 H), 7.16–7.22 (m, 3 H), 7.01–7.08 (m, 4 H). ¹³C NMR (101 MHz, CDCl₃): δ = 149.2, 148.2, 138.6, 137.3, 134.4, 131.5, 130.8, 130.5, 130.2, 128.1, 128.0, 127.9, 127.1, 127.1, 127.0, 127.0, 126.9, 126.8, 126.3, 122.8, 122.6. HRMS (ESI): m/z calcd for [C₂₅H₁₇NNa]⁺: 354.1259; found: 354.1265. 9-(p-Tolyl)-2,3,6,7-tetramethyl-10-phenylphenanthrene (3bb): faint yellow solid; yield: 60 mg (50%); mp 249.9–251.1 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.50 (s, 2 H), 7.11–7.24 (m, 7 H), 7.00 (s, 4 H), 2.52 (s, 6 H), 2.31 (s, 3 H), 2.30 (s, 6 H). ¹³C NMR (101 MHz, CDCl₃): δ = 140.3, 136.9, 135.9, 135.9, 135.5, 135.3, 135.3, 135.2, 131.2, 131.0, 130.3, 130.2, 128.2, 128.1, 128.1, 127.8, 127.7, 127.4, 126.1, 122.7, 29.7, 21.3, 20.4, 20.2, 20.2. HRMS (ESI): m/z calcd for [C₃₁H₂₈Na]⁺: 423.2089; found: 423.2089. 9-(3-Methoxyphenyl)-2,3,6,7-tetramethyl-10-phenylphenanthrene (3bc): faint yellow solid; yield: 42 mg (34%); mp 149.1–150.3 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.56 (s, 2 H), 7.37 (s, 1 H), 7.23–7.31 (m, 7 H), 6.72–6.82 (m, 3 H), 3.72 (s, 3 H), 2.58 (s, 6 H), 2.36 (d, J = 6.0 Hz, 6 H). ¹³C NMR (101 MHz, CDCl₃): δ = 158.8, 141.4, 140.1, 135.7, 135.7, 135.4, 135.4, 135.3, 131.1, 131.1, 130.1, 129.9, 128.4, 128.1, 128.1, 127.8, 127.8, 127.6, 127.4, 126.3, 123.9, 122.7, 116.6, 112.2, 55.2, 21.6, 20.5, 20.2, 15.4. HRMS (ESI): m/z calcd for [C₃₁H₂₈ONa]⁺: 439.2038; found: 439.2035. 9-(2-Methoxyphenyl)-2,3,6,7-tetramethyl-10-phenylphenanthrene (3bd): faint yellow solid; yield: 12 mg (10%); mp 203.5–204.8 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.50 (d, J = 5.4 Hz, 2 H), 7.12–7.21 (m, 8 H), 7.01 (dd, J = 7.4, 1.7 Hz, 1 H), 6.82–6.84 (m, 1 H), 6.75 (d, J = 8.2 Hz, 1 H), 3.56 (s, 3 H), 2.53 (s, 3 H), 2.52 (s, 3 H), 2.30 (s, 6 H). ¹³C NMR (101 MHz, CDCl₃): δ = 157.4, 140.4, 136.2, 135.3, 135.2, 135.1, 135.0, 132.6, 132.5, 130.9, 130.2, 130.1, 129.1, 128.3, 128.2, 128.1, 127.6, 127.3, 127.2, 127.1, 126.2, 122.7, 119.9, 110.3, 55.2, 20.5, 20.4, 20.2, 20.1. HRMS (ESI): m/z calcd for [C₃₁H₂₈ONa]⁺: 439.2038; found: 439.2036.
20 Dibenzochryenes 4aa and 4ab; General Procedure: A dried flask was charged with 9,10-disubstituted phenanthrene (0.4 mmol), CuCl₂ (270 mg, 2.0 mmol) and AlCl₃ (267 mg, 2.0 mmol) under argon, and CS₂ (5 mL) was added by a syringe. The mixture was stirred at r.t. until the reaction was complete. The mixture was diluted with CH₂Cl₂ and filtered through a plug of silica gel. The solvents were then removed under reduced pressure to provide a crude product, which was further purified by silica gel column chromatography (silica gel, PE–EtOAc). Palladium-Catalyzed Annulation of 2,2′-Dibromobiphenyls with Alkynes; Synthesis of Functionalized Phenanthrenes and Dibenzochrysenes: A palladium-catalyzed annulation process of 2,2′-dibromobiphenyls with alkynes for the synthesis of functionalized phenanthrenes was realized. The electron-deficient heteroaromatic-substituted acetylenes are capable of the annulation process. Thiophene-fused and pyridine-fused PAHs can also be synthesized easily. This methodology also provides a highly efficient and low-cost approach to dibenzochrysene derivatives starting from simple commercially available reactants in two steps.

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