Rh-Catalyzed Sequential Hydroarylation/Hydrovinylation-Heterocyclization of β-(2-Aminophenyl)-α,β-ynones with Organoboron Derivatives: A New Approach to Functionalized Quinolines

Giorgio Abbiati; Antonio Arcadi; Fabio Marinelli; Elisabetta Rossi; Mirella Verdecchia

doi:10.1055/s-2006-956462

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Synlett 2006(19): 3218-3224
DOI: 10.1055/s-2006-956462

LETTER

Rh-Catalyzed Sequential Hydroarylation/Hydrovinylation-Heterocyclization of β-(2-Aminophenyl)-α,β-ynones with Organoboron Derivatives: A New Approach to Functionalized Quinolines

Giorgio Abbiati^a, Antonio Arcadi^b, Fabio Marinelli*^b, Elisabetta Rossi^a, Mirella Verdecchia^b
^a Ist. di Chimica Organica ‘Alessandro Marchesini’, Università di Milano, via Venezian 21, 20133 Milano, Italy
^b Dipartimento di Chimica, Ingegneria Chimica e Materiali, Università degli Studi dell’Aquila, via Vetoio - Coppito due, 67010 L’Aquila, Italy
Fax: +39(0862)433753; e-Mail: fmarinel@univaq.it;

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Received 27 July 2006
Publication Date:
23 November 2006 (online)

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Abstract

4-Aryl and 4-vinyl quinolines were prepared via a sequential procedure involving regioselective Rh(acac)(C₂H₂)/dppf-catalyzed hydroarylation/hydrovinylation of β-(2-aminophenyl)-α,β-ynones with arylboronic acids or potassium aryl and vinyl trifluoroborates, followed by nucleophilic attack of the amino group onto the carbonyl.

Key words

quinolines - hydroarylation - rhodium - alkynones - arylboronic acids

References and Notes

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23

Typical Procedure: To a mixture of 1c (0.106 g, 0.40 mmol), phenylboronic acid (0.244 g, 2 mmol), Rh(acac)(C₂H₄)₂ (0.0035 g, 0.014 mmol) and dppf (0.015 g, 0.027 mmol) in a screw-capped Pyrex tube were added dioxane (1 mL) and H₂O (0.1 mL). The tube was purged with N₂, closed and the mixture was stirred at 100 °C for 4.5 h. After cooling, the mixture was purified by column chromatography (silica gel; hexane-EtOAc, 97:3) to give 4g (0.106 g, 82% yield); mp 116-117 °C. IR (KBr): 1690, 1610, 1600 cm^-1. ¹H NMR (CDCl₃): δ = 8.29 (d, J = 8.5 Hz, 2 H), 8.26-8.22 (m, 1 H), 8.09 (d, J = 8.5 Hz, 2 H), 7.91 (d, J = 8.4 Hz, 2 H), 7.83 (s, 1 H, C3-H), 7.78-7.70 (m, 1 H), 7.54-7.45 (m, 6 H), 2.65 (s, 3 H). ¹³C NMR (CDCl₃): δ = 197.8, 155.4, 149.5, 148.8, 143.8, 138.2, 137.4, 130.2, 129.8, 129.5, 128.8, 128.6, 128.5, 127.7, 126.9, 126.0, 125.7, 119.2, 26.8. MS (EI): m/z (%) = 323 (100) [M⁺], 309 (8), 281 (20).

24

Characterization of other quinoline derivatives.
Compound 4a: oil. IR (neat): 1610, 1590, 1550 cm^-1. ¹H NMR (CDCl₃): δ = 8.22 (d, J = 8.3 Hz, 1 H), 7.95 (d, J = 7.9 Hz, 1 H), 7.76-7.68 (m, 1 H), 7.55-7.44 (m, 8 H), 7.14 (s, 1 H), 7.17-7.10 (m, 1 H), 2.45 (s, 3 H), 2.38 (s, 3 H). ¹³C NMR (CDCl₃): δ = 159.8, 148.4, 148.3, 138.3, 138.2, 137.8, 135.9, 131.7, 130.0, 129.8, 129.6, 129.4, 128.6, 128.3, 126.7, 126.3, 125.6, 125.1, 122.6, 21.2, 20.4. MS (EI): m/z (%) = 309 (100) [M⁺].
Compound 4b: oil. IR (neat): 1610, 1590, 1550 cm^-1. ¹H NMR (CDCl₃): δ = 8.22 (d, J = 8.4 Hz, 1 H), 7.89 (d, J = 8.3 Hz, 1 H), 7.76-7.68 (m, 1 H), 7.54-7.42 (m, 5 H), 7.24-7.09 (m, 3 H), 7.13 (s, 1 H), 2.44 (s, 3 H), 2.37 (s, 3 H). ¹³C NMR (CDCl₃): δ = 162.9 (d, J = 248.0 Hz, C-F), 159.9, 148.5, 147.2, 138.4, 137.7, 135.9, 134.2 (d, J = 3.2 Hz), 131.7, 131.4, 131.2, 130.1, 129.8, 129.5, 126.8, 126.5, 125.3, 122.7, 115.7 (d, J = 21.5 Hz), 21.2, 20.4. MS (EI): m/z (%) = 327 (100) [M⁺].
Compound 4c: oil. IR (neat): 1600, 1590, 1550 cm^-1.¹H NMR (CDCl₃): δ = 8.24 (d, J = 8.3 Hz, 1 H), 7.98 (d, J = 8.4 Hz, 1 H), 7.74-7.66 (m, 1 H), 7.48-7.42 (m, 5 H), 7.30 (d, J = 7.9 Hz, 2 H), 7.13 (s, 1 H), 7.17-7.09 (s, 1 H), 2.45 (s, 3 H), 2.43 (s, 3 H), 2.37 (s, 3 H). ¹³C NMR (CDCl₃): δ = 159.8, 148.4, 148.3, 138.2, 137.8, 135.8, 135.2, 131.6, 129.9, 129.8, 129.5, 129.3, 128.7, 126.7, 126.2, 125.6, 125.3, 122.6, 21.3, 21.2, 20.4. MS (EI): m/z (%) = 323 (100) [M⁺].
Compound 4d: oil. IR (neat): 1610, 1600, 1550 cm^-1. ¹H NMR (CDCl₃): δ = 8.20 (d, J = 8.5 Hz, 1 H), 8.14 (d, J = 8.8 Hz, 2 H), 7.85 (d, J = 8.3 Hz, 1 H), 7.74 (s, 1 H), 7.71-7.63 (m, 1 H), 7.53-7.50 (m, 5 H), 7.43-7.35 (m, 1 H), 7.01 (d, J = 8.8 Hz, 2 H), 3.83 (s, 3 H). ¹³C NMR (CDCl₃): δ = 160.8, 156.4, 148.9, 148.8, 138.5, 132.1, 129.9, 129.5, 129.4, 128.9, 128.5, 128.3, 125.9, 125.6, 125.5, 118.8, 114.2, 55.3. MS (EI): m/z (%) = 311 (100) [M⁺].
Compound 4e: mp 118-120 °C. IR (KBr): 1600, 1550 cm^-1. ¹H NMR (CDCl₃): δ = 8.21-8.10 (m, 1 H), 8.15 (d, J = 8.8 Hz, 2 H), 7.84 (d, J = 8.4 Hz, 1 H), 7.74 (s, 1 H), 7.72-7.65 (m, 1 H), 7.43 (d, J = 8.0 Hz, 2 H), 7.44-7.35 (m, 1 H), 7.32 (d, J = 8.0 Hz, 2 H), 7.01 (d, J = 8.8 Hz, 2 H), 3.84 (s, 1 H), 2.45 (s, 1 H). ¹³C NMR (CDCl₃): δ = 160.9, 156.5, 149.1, 148.9, 138.2, 135.7, 132.4, 129.9, 129.5, 129.34, 129.27, 128.9, 127.4, 125.8, 125.7, 118.8, 114.2, 55.4, 21.3. MS (EI): m/z (%) = 325 (100) [M⁺].
Compound 4f: mp 120-121 °C. IR (KBr): 1620, 1600, 1550 cm^-1. ¹H NMR (CDCl₃): δ = 8.17-8.10 (m, 4 H), 7.97 (s, 1 H), 7.79 (d, J = 16.1 Hz, 1 H), 7.72-7.59 (m, 3 H), 7.52-7.30 (m, 5 H), 7.04 (d, J = 8.8 Hz, 2 H), 3.86 (s, 3 H). ¹³C NMR (CDCl₃): δ = 160.7, 156.8, 148.8, 143.5, 136.8, 134.8, 132.5, 130.2, 129.4, 128.9, 128.7, 127.1, 125.9, 123.7, 123.3, 114.7, 114.2, 55.4. MS (EI): m/z (%) = 337 (100) [M⁺].
Compound 4h: mp 89-90 °C. IR (KBr): 1680, 1610, 1590 cm^-1. ¹H NMR (CDCl₃): δ = 8.25-8.23 (m, 1 H), 8.27 (d, J = 8.5 Hz, 2 H), 8.08 (d, J = 8.5 Hz, 2 H), 8.10-8.05 (m, 1 H), 7.87 (s, 1 H), 7.94-7.17 (m, 1 H), 7.60-7.50 (m, 3 H), 7.40-7.35 (m, 1 H), 2.65 (s, 3 H). ¹³C NMR (CDCl₃): δ = 197.8, 155.5, 148.5, 144.5, 143.4, 138.5, 137.4, 130.2, 129.9, 128.9, 127.7, 127.0, 126.5, 125.6, 125.1, 119.1, 26.7. MS (EI): m/z (%) = 329 (71) [M⁺], 314 (100), 286 (41).
Compound 4i: mp 112-113 °C. IR (KBr): 1600, 1560 cm^-1. ¹H NMR (CDCl₃): δ = 8.30 (d, J = 8.6 Hz, 1 H), 8.26-8.20 (m, 1 H), 8.01 (d, J = 8.4 Hz, 1 H), 7.96-7.90 (m, 2 H), 7.81-7.72 (m, 2 H), 7.67 (s, 1 H), 7.61-7.47 (m, 9 H). ¹³C NMR (CDCl₃): δ = 159.0, 148.7, 138.7, 138.1, 134.0, 131.3, 130.1, 129.6, 129.1, 128.6, 128.5, 128.4, 127.8, 126.6, 125.9, 125.7, 125.5, 125.4, 123.4. MS (EI): m/z (%) = 331 (100) [M⁺], 255 (40).
Compound 4j: mp 82-83 °C. IR (KBr): 1600, 1560 cm^-1. ¹H NMR (CDCl₃): δ = 8.49 (s, 1 H), 8.37 (d, J = 7.5 Hz, 1 H), 8.25 (d, J = 8.6 Hz, 1 H), 7.91 (d, J = 8.5 Hz, 1 H), 7.80 (s, 1 H), 7.80-7.60 (m, 3 H), 7.55-7.44 (m, 6 H). ¹³C NMR (CDCl₃): δ = 155.1, 149.7, 148.9, 140.4, 138.2, 130.8, 130.3, 129.8, 129.6, 129.3, 128.7, 128.6, 126.8, 125.9 (q, J = 3.6 Hz), 125.7, 124.4 (q, J = 3.7 Hz), 118.9, 29.7. MS (EI): m/z (%) = 349 (100) [M⁺].
Compound 4k: mp 75-77 °C. IR (KBr): 1600, 1570, 1550 cm^-1. ¹H NMR (CDCl₃): δ = 8.48-8.33 (m, 3 H), 8.19 (d, J = 8.4 Hz, 1 H), 8.06 (s, 1 H), 7.76-7.55 (m, 5 H), 7.01 (d, J = 3.3 Hz, 1 H), 6.63 (m, 1 H). ¹³C NMR (CDCl₃): δ = 155.2, 151.0, 149.2, 144.1, 140.2, 136.9, 130.7, 130.5, 129.8, 129.3, 127.2, 125.9 (q, J = 3.6 Hz), 125.2, 124.4 (q, J = 3.7 Hz), 123.7, 116.1, 112.4, 112.1. MS (EI): m/z (%) = 339 (100) [M⁺].
Compound 4l: mp 125-127 °C. IR (KBr): 1610, 1590, 1570 cm^-1. ¹H NMR (CDCl₃): δ = 7.96 (s, 1 H), 7.97-7.91 (m, 1 H), 7.56-7.49 (m, 5 H), 7.46-7.10 (m, 4 H), 7.01 (d, J = 8.2 Hz, 1 H), 3.85 (s, 3 H). ¹³C NMR (CDCl₃): δ = 159.6 (dd, J ₁ = 247.1 Hz, J ₂ = 12.0 Hz), 158.8 (dd, J ₁ = 259.9 Hz, J ₂ = 13.4 Hz), 157.3, 156.1, 146.8 (dd, J ₁ = 3.2 Hz, J ₂ = 5.4 Hz), 137.8, 131.8, 130.7, 129.4, 129.0, 128.8, 128.6, 125.4, 121.4, 111.3, 105.2-104.2 (two overlapping multiplets), 55.7. MS (EI): m/z (%) = 347 (100) [M⁺], 316 (51).
Compound 4m: mp 88-90 °C. IR (KBr): 1790, 1590, 1550 cm^-1. ¹H NMR (CDCl₃): δ = 8.15-8.06 (m, 3 H), 7.74-7.60 (m, 4 H), 7.52 (s, 1 H), 7.46-7.42 (m, 1 H), 6.81 (t, J = 2.6 Hz, 1 H), 3.05-2.95 (m, 1 H), 2.66 (s, 3 H), 2.60-2.25 (m, 2 H), 2.10-1.90 (m, 2 H), 1.45-1.35 (m, 2 H), 0.94 (s, 9 H). ¹³C NMR (CDCl₃): δ = 197.5, 158.4, 148.4, 147.0, 139.2, 137.6, 134.0, 133.0, 130.9, 130.1, 129.3, 128.8, 128.5, 128.3, 128.1, 126.0, 125.0, 118.3, 43.9, 32.2, 27.9, 27.5, 27.2, 26.7, 24.3. MS (EI): m/z (%) = 384 (100) [M⁺], 327 (40).
Compound 4n: mp 117-119 °C. IR (KBr): 1590, 1550, 1510 cm^-1. ¹H NMR (CDCl₃): δ = 8.13-8.06 (m, 2 H), 7.78 (d, J = 15.9 Hz, 1 H), 7.74 (s, 1 H), 7.70-7.56 (m, 3 H), 7.51-7.26 (m, 4 H), 7.30 (d, J = 15.9 Hz, 1 H), 6.81 (t, J = 2.6 Hz, 1 H), 3.05-2.92 (m, 1 H), 2.65-2.30 (m, 2 H), 2.20-2.00 (m, 2 H), 1.50-1.35 (m, 2 H), 0.94 (s, 9 H). ¹³C NMR (CDCl₃): δ = 158.9, 148.4, 142.7, 137.8, 136.9, 134.5, 130.4, 130.2, 129.1, 128.9, 128.6, 127.1, 125.7, 125.4, 123.9, 123.2, 114.2, 44.0, 32.3, 27.9, 27.7, 27.3, 23.3. MS (EI): m/z (%) = 368 (50) [M⁺], 353 (15), 311 (100).