Controlled and Efficient Synthesis of Quinoline Derivatives from Morita–Baylis–Hillman Adducts by Palladium-Catalyzed Heck Reaction and Cyclization

Kodirajan Selvakumar; Kandapalam Arun Prasath Lingam; Rama Varma Luxmi Varma; Veerappan Vijayabaskar

doi:10.1055/s-0034-1379938

Synlett, Table of Contents

Synlett 2015; 26(05): 646-650
DOI: 10.1055/s-0034-1379938

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Controlled and Efficient Synthesis of Quinoline Derivatives from Morita–Baylis–Hillman Adducts by Palladium-Catalyzed Heck Reaction and Cyclization

Kodirajan Selvakumar*

^aDepartment of Chemistry, Sethu Institute of Technology, Pulloor, Tamil Nadu 626 115, India

,

Kandapalam Arun Prasath Lingam

^bDepartment of Chemistry, Kamaraj Collage, Tuticorin, Tamil Nadu 628 003, India

,

Rama Varma Luxmi Varma

^cChemical Sciences and Technology Division, National Institute for Interdisciplinary Science and Technology, Thiruvananthapuram, Kerala 695 019, India Email: selvaramkumar@yahoo.co.in

,

Veerappan Vijayabaskar

^aDepartment of Chemistry, Sethu Institute of Technology, Pulloor, Tamil Nadu 626 115, India

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Abstract

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Abstract

An efficient synthesis of 2,3-disubstituted quinoline derivatives from easily accessible (het)aryl-substituted Morita–Baylis–Hillman (MBH) adducts was achieved by an approach involving a palladium-catalyzed Heck reaction and cyclization. This strategy converts the MBH adducts into α-benzyl β-keto ester derivatives that can cyclize into the corresponding quinolines in good yields.

Key words

quinolines - cyclizations - catalysis - palladium - Heck reactions - tandem reactions

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References

References and Notes

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11 1,4-Dihydroquinolines 3 and Quinolines 4; General Procedure A mixture of 2-iodoaniline (2a; 2.1 equiv), Pd (OAc)₂ (10 mol%), DABCO (0.6 equiv), and TBAB (2.1 equiv.) in MeCN (2 mL) was refluxed under argon. After 15 min, the MBH adduct 1 (100 mg) was added. When the reaction was complete (TLC), the mixture was allowed to cool to r.t. and filtered through a Celite pad. The resulting mixture of compounds 3 and 4 was subjected to aromatization with DBU and purified by column chromatography (silica gel) to give the quinoline 4. Methyl 2-(4-Chlorophenyl)-1,4-dihydroquinoline-3-carboxylate (3a) + Methyl 2-(4-Chlorophenyl)quinoline-3-carboxylate Yellow oil; yield: 110 mg (84%); IR (CH₂Cl₂): 3389, 3096, 1728, 1622, 1593, 1485, 1366, 755cm^–1; ¹H NMR (500.1 MHz, CDCl₃): δ = 3.50 (s, 3 H), 3.78 (s, 3 H), 3.91 (s, 2 H), 5.77 (br s, 1 H), 6.57 (m, 1 H), 6.94 (m, 1 H), 6.96 (m, 2 H), 7.08 (m, 2 H), 7.38 (m, 2 H), 7.45 (m, 2 H), 7.58 (m, 2 H), 7.62 (t, J = 7.0 Hz, 1 H), 7.83 (m, 1 H), 7.92 (d, J = 8 Hz, 1 H), 8.16 (d, J = 8.5 Hz, 1 H), 8.65 (s, 1 H); ¹³C NMR (125.7 MHz, CDCl): δ = 27.94, 50.87, 52.53, 95.58, 114.31, 121.38, 123.34, 124.61, 125.88, 127.08, 127.52, 128.30 (2 C), 128.43 (2 C), 128.59 (2 C), 129.09 (2 C), 129.31 (2 C), 129.53 (2 C), 130.01, 131.88, 134.81, 134.90, 136.62, 139.04, 139.58, 148.45, 156.89, 167.57, 168.00; FAB: m/z [M + 1]⁺ calcd for C₁₇H₁₂ClNO₂: 297.06; found: 298.31: m/z [M + 1]⁺ calcd for C₁₇H₁₄ClNO₂: 299.07; found: 300.28. Methyl 2-Pyridin-2-ylquinoline-3-carboxylate (4l) Pale-yellow solid; yield: 101 mg (74%); mp 109–110 °C; IR (KBr): 2932, 1718, 1625, 1598, 1488 cm^–1; ¹H NMR (300.1 MHz, CDCl₃): δ = 3.93 (s, 3 H), 6.49 (m, 1 H), 6.77 (m, 1 H), 7.14 (t, J = 8.0 Hz, 1 H), 7.23 (t, J = 7.5 Hz, 1 H), 7.50 (m, 1 H), 7.83 (m, 2 H), 8.13 (m, 1 H), 8.47 (s, 1 H); ¹³C NMR (125.7 MHz, CDCl₃): δ = 52.46, 120.09, 122.19, 122.45, 122.90, 124.52, 125.97, 126.99, 127.47, 127.84, 128.67, 130.31, 130.77, 135.61, 144.18, 166.47; FAB: m/z [M⁺] calcd for C₁₆H₁₂N₂O₂: 264.09; found: 264.45. Methyl 2-(2-Thienyl)quinoline-3-carboxylate (4n) Pale-yellow oil; yield: 71 mg (52%); IR (KBr): 2932, 1722, 1624, 1585, 1492 cm^–1. ¹H NMR (300.1 MHz, CDCl₃): δ = 3.92 (s, 3 H), 7.12 (m, 1 H), 7.26 (s, 1 H), 7.40 (m, 1 H), 7.48 (d, J = 8.5 Hz, 1 H), 7.57 (d, J = 7.5 Hz, 1 H), 7.78 (m, 1 H), 8.12 (m, 1 H), 8.45 (s, 1 H); ¹³C NMR (125.7 MHz, CDCl₃): δ = 52.08, 99.39, 99.89, 107.19, 110.43, 115.44, 116.74, 118.95, 126.88, 128.08, 139.39, 142.39, 147.42, 154.11, 166.48; FAB: m/z [M⁺] calcd for C₁₅H₁₁NO₂S: 269.05; found: 269.37.
12 Usually, short-lived H–Pd–I species undergo immediate reductive elimination with a base, but MBH adducts with electron-donating substituents can undergo coupling with H–Pd–I, presumably under the influence of the +I effect of the electron-donating group.
13 Ma G.-N, Jiang J.-J, Shi M, Wei Y. Chem. Commun. 2009; 5496

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