Synthesis of Unsymmetrically Disubstituted Tetraphenylenes via Carbonyl-Directed C–H Functionalization

Abstract

A new strategy for the synthesis of unsymmetrically disubstituted tetraphenylenes from 2-acetylbiphenylene has been developed via ruthenium-catalyzed C–H functionalization. Four reactions, including alkenylation–cyclization, alkenylation, alkylation, and amidation, were achieved. The reactions provide easy access to a variety of unsymmetrically disubstituted tetraphenylene derivatives, which could accelerate research on the appliation of tetraphenylenes.

Key words

tetraphenylene - C–H activation - palladium - alkenation - alkylation - amidation

• References and Notes

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• 19 For the detailed conditions optimization, see Supporting Information.

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• 23 Ru(II)-Catalyzed C–H Functionalization of 1a with 2a A 25 mL Schlenk-type tube (with a Teflon high-pressure valve and side arm) was charged with compound 1a (34.6 mg, 0.10 mmol), 2a (35.6 mg, 0.20 mmol), Cu(OAc)₂·H₂O (5.0 mg, 0.025 mmol), [RuCl₂(p-cymene)]₂ (6.1 mg, 0.01 mmol), AgSbF₆ (13.7 mg, 0.04 mmol), and THF (1 mL). The reaction tube was evacuated and back-filled with N₂ (3×, ballon). After the reaction mixture was stirred at 120 °C for 12 h, it was allowed to cool down to room temperature. The reaction mixture was diluted with EtOAc (20 mL), and then filtered through a pad of Celite. The filtrate was washed with brine (10 mL), dried over Na₂SO₄, and concentrated in vacuo. The residue was purified by silica gel preparative TLC to give the corresponding product 3a; yellow solid, 80% yield; mp 161–162 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.52 (s, 1 H), 7.31–7.13 (m, 23 H), 6.19 (s, 1 H), 5.69 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 147.19, 141.85, 141.80, 141.66, 141.62, 141.55, 141.52, 141.46, 139.15, 138.06, 135.18, 134.48, 134.30, 130.61, 129.39, 129.12, 129.09, 129.06, 128.99, 128.22, 128.01, 127.40, 127.29, 127.26, 127.21, 126.95, 120.86, 120.80, 114.44. HRMS (ESI-TOF): m/z calcd for C₄₀H₂₆Na⁺: 529.1927 [M + Na]⁺; found: 529.1926.
• 24 Ru(II)-Catalyzed C–H Functionalization of 1a with 4a A 25 mL Schlenk-type tube (with a Teflon high-pressure valve and side arm) was charged with compound 1a (34.6 mg, 0.10 mmol), 4a (25.6 mg, 0.20 mmol), Cu(OAc)₂·H₂O (39.9 mg, 0.20 mmol), [RuCl₂(p-cymene)]₂ (6.1 mg, 0.01 mmol), AgSbF₆ (13.7 mg, 0.04 mmol), and t-BuOH (1 mL). The reaction tube was evacuated and back-filled with N₂ (3×, ballon). After the reaction mixture was stirred at 110 °C for 12 h, it was allowed to cool down to room temperature. The reaction mixture was diluted with EtOAc (20 mL), and then filtered through a pad of Celite. The filtrate was washed with brine (10 mL), dried over Na₂SO₄, and concentrated in vacuo. The residue was purified by silica gel preparative TLC to give the corresponding product 5a; white solid, 76% yield; mp 195–196 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.13 (d, J = 15.9 Hz, 1 H), 7.55 (s, 1 H), 7.42 (s, 1 H), 7.35–7.29 (m, 6 H), 7.21–7.14 (m, 6 H), 6.28 (d, J = 15.9 Hz, 1 H), 4.18 (t, J = 6.7 Hz, 2 H), 2.58 (s, 3 H), 1.70–1.16 (m, 2 H), 1.44–1.38 (m, 2 H), 0.94 (t, J = 7.4 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 200.38, 166.53, 145.43, 143.35, 142.85, 141.51, 141.28, 140.84, 140.78, 139.82, 139.78, 136.86, 133.84, 130.17, 129.36, 129.31, 129.26, 129.20, 129.16, 128.73, 128.63, 128.07, 128.02, 127.58, 127.54, 127.49, 127.46, 120.99, 64.38, 30.67, 29.14, 19.12, 13.69. HRMS (ESI-TOF): m/z calcd for C₃₃H₂₈O₃Na⁺: 495.1931 [M + Na]⁺; found: 495.1925.
• 25 Ru(II)-Catalyzed C–H Functionalization of 1a with 6a A 25 mL septum-capped vial equipped with a magnetic stir bar was charged with compound 1a (34.6 mg, 0.10 mmol), 6a (57.0 mg, 0.30 mmol), HCO₂Na (13.6 mg, 0.20 mmol), [RuCl₂(p-cymene)]₂ (6.1 mg, 0.01 mmol), and P(p-CF₃C₆H₄)₃ (23.3 mg, 0.05 mmol). The vial was closed and evacuated under vacuum during 10 min and placed under an argon atmosphere. Degassed dioxane (1 mL) was added, and the reaction vial was evacuated and back-filled with Ar (3×, ballon). After the reaction mixture was stirred at 100 °C for 12 h, it was allowed to cool down to room temperature. The reaction mixture was diluted with EtOAc (20 mL), and then filtered through a pad of Celite. The filtrate was washed with brine (10 mL), dried over Na₂SO₄, and concentrated in vacuo. The residue was purified by silica gel preparative TLC to give the corresponding product 7a; amorphous, 99% yield. ¹H NMR (400 MHz, CDCl₃): δ = 7.45 (s, 1 H), 7.33–7.27 (m, 6 H), 7.20–7.14 (m, 6 H), 7.12 (s, 1 H), 3.80 (q, J = 7.0 Hz, 6 H), 3.04–2.85 (m, 2 H), 2.54 (s, 3 H), 1.20 (t, J = 7.0 Hz, 9 H), 1.01–0.94 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 201.55, 144.82, 143.87, 141.62, 141.26, 141.19, 141.15, 140.59, 140.48, 139.02, 136.16, 131.53, 130.17, 129.32, 129.30, 129.22, 129.10, 128.87, 127.68, 127.58, 127.39, 127.32, 58.31, 29.75, 26.94, 18.28, 12.48. HRMS (ESI-TOF): m/z calcd for C₃₄H₃₆O₄SiNa⁺: 559.2275 [M + Na]⁺; found: 559.2270.
• 26 Ru(II)-Catalyzed C–H Functionalization of 1a with 8a A 25 mL Schlenk-type tube (with a Teflon high pressure valve and side arm) was charged with compound 1a (34.6 mg, 0.10 mmol), 8a (54.9 mg, 0.30 mmol), Cu(OAc)₂·H₂O (10.0 mg, 0.05 mmol), [RuCl₂(p-cymene)]₂ (6.1 mg, 0.01 mmol), AgSbF₆ (13.7 mg, 0.04 mmol), and CHCl₃ (1 mL). The reaction tube was evacuated and back-filled with N₂ (3×, ballon). After the reaction mixture was stirred at 100 °C for 24 h, it was allowed to cool down to room temperature. The reaction mixture was diluted with EtOAc (20 mL), and then filtered through a pad of Celite. The filtrate was washed with brine (10 mL), dried over Na₂SO₄, and concentrated in vacuo. The residue was purified by silica gel preparative TLC to give the corresponding product 9a; white solid, 70% yield; mp 244–245 °C. ¹H NMR (400 MHz, CDCl₃): δ = 11.35 (s, 1 H), 7.72 (d, J = 7.4 Hz, 2 H), 7.56 (s, 1 H), 7.52 (s, 1 H), 7.49 (t, J = 7.5 Hz, 1 H), 7.37–7.26 (m, 8 H), 7.20–7.12 (m, 4 H), 7.09–7.07 (m, 1 H), 6.99–6.97 (m, 1 H), 2.46 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 201.99, 148.46, 141.74, 140.99, 140.90, 140.73, 139.74, 139.58, 139.11, 138.67, 136.64, 132.88, 132.32, 129.32, 129.26, 129.24, 129.00, 128.83, 128.80, 128.26, 128.22, 127.90, 127.51, 127.48, 127.47, 127.28, 121.55, 119.98, 28.08. HRMS (ESI-TOF): m/z calcd for C₃₂H₂₃ NO₃SNa⁺: 524.1291 [M + Na]⁺; found: 524.1294.