Compound 2a

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InChIKey YZNBMLFEBACLBI-UHFFFAOYSA-N

Compound data: 1H NMR (CDCl3)

Compound data: 1H NMR (C6D6)

Compound data: 13C{1H} NMR (CDCl3)

Compound data: 13C{1H} NMR (C6D6)

Compound data: 1H-1H COSY

Compound data: HSQC

Compound data: HMBC

Compound data: Crystallographic data

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

A 500 mL Teflon-stoppered flask was charged with Pd₂(dba)₃ (0.26 g, 0.30 mmol), rac-BINAP (0.42 g, 0.70 mmol) and toluene (30 mL). After stirring for 5 min, 8-bromoquinoline (2.00 g, 10.1 mmol), 1c (2.50 g, 10.1 mmol), and an additional 20 mL of toluene were added, followed by sodium tert-butoxide (NaO^tBu; 1.4 g, 15.1 mmol). The reaction mixture was stirred and subject to reflux in an oil bath at 150 °C for 72 h. After cooling the flask, the volatiles were removed and the residue was taken up in dichloromethane. The suspension was then filtered over a silica plug and the solvent was removed to leave a brown solid. Isolated yield = 3.80 g (> 99 %). ¹H NMR (CDCl₃, 300 MHz, 25 °C): δ 10.53 (s, 1H, N₂-H), 9.29 (s, 1H, C₁-H), 8.98 (dd, 1H, J_HH = 4.2, 1.7 Hz, C₁₈-H), 8.68 (d, 1H, J_HH = 8.4 Hz, C₃-H), 8.21- 8.04 (m, 4H, C₆-H, C₁₃-H, C₂₀-H, C₂₆-H), 7.90 – 7.84 (m, 2H, C₁₁-H, C₂₅-H), 7.71 (ddd, 1H, J_HH = 8.0, 7.0 1.1 Hz, C₄-H), 7.55 (t, 1H, C₅-H), 7.47 (dd, 1H, J_HH = 8.2, 4.2 Hz, C₁₉-H), 7.32 (dd, 1H, J_HH = 8.2, 1.2 Hz, C₂₄-H), 1.55 ppm (s, 9H, ^tBu). ¹H NMR (C₆D₆, 500 MHz, 25 °C): δ 11.58 (s, 1H, N₂-H), 9.10 (s, 1H, C₁-H), 8.73 (dd, 1H, J_HH = 4.3, 1.6 Hz, C₁₈-H), 8.40 (d, 1H, J_HH = 8.3 Hz, C₃-H), 8.32 (s, 1H, C₁₃-H), 8.12-8.05 (m, 2H, C₁₁-H, C₂₆-H), 7.59 (dd, 1H, J_HH = 8.2, 1.6 Hz, C₂₀-H), 7.44 (d, 1H, J_HH = 7.9 Hz, C₆-H), 7.39 (m, 2H, C₄-H, C₂₅-H), 7.20 (t, 1H, J_HH = 7.4 Hz, C₅-H), 7.06 (d, 1H, J_HH = 8.2 Hz, C₂₄-H), 6.83 (dd, 1H, J_HH = 8.2, 4.1 Hz, C₁₉-H), 1.46 ppm (s, 9H, ^tBu). ¹³C{¹H} NMR (CDCl₃, 75 MHz, 25 °C): δ 150.6 (C₁), 150.5 (C₁₂), 148.1 (C₁₈), 140.2 (C_{21, 22 or 23}),), 139.5 (C_{10 or 23}),139.2 (C_{10 or 23}), 134.0 (C₂₀), 133.1 (C_{7 or 8}), 130.7 (C_{8 or 9}), 129.2 (C₄), 129.1 (C_{21, 22 or 23}), 128.9 (C₆), 128.3 (C₂₅), 127.3 (C_{2 or 7}), 127.3 (C₅), 124.3 (C_{2 or 7}), 122.3 (C₃), 121.7 (C₁₉), 117.5 (C₂₄), 110.6 (C₁₃), 109.2 (C₁₁), 108.9 (C₂₆), 35.7 (C₁₄), 31.7 ppm (C_15,16,17). ¹³C{¹H} NMR (C₆D₆, 125 MHz, 25 °C): δ 150.5 (C₁), 150.5 (C₁₂), 148.0 (C₁₈), 140.8 (C_{21, 22 or 23}),), 140.2 (C_{10 or 23}),140.0 (C_{10 or 23}), 135.9 (C₂₀), 134.6 (C_{7 or 8}), 133.3 (C_{8 or 9}), 130.5 (C₄), 129.5 (C_{21, 22 or 23}), 129.0 (C₆), 127.5 (C₂₅), 127.3 (C_{2 or 7}), 127.1 (C₅), 124.7 (C_{2 or 7}), 122.4 (C₃), 121.8 (C₁₉), 117.6 (C₂₄), 110.3 (C₁₃), 109.3 (C₁₁), 108.9 (C₂₆), 35.6 (C₁₄), 31.7 ppm (C_15,16,17). UV-Vis (CH₃CN): λ (ε) 306 (9 680), 388 nm (12 270 M^-1 cm^-1).