Synthesis of δ-Carbolines and the Alkaloid Quindoline through a Molybdenum-Catalyzed Cadogan Cyclization and their Photoluminescent Properties

Abstract

Cadogan reductive cyclization of substituted 2-aryl-3-nitropyridines to give δ-carbolines was performed under MoO₂Cl₂(DMF)₂ catalysis with triphenylphosphine as a ligand. A new approach for the synthesis of the alkaloid quindoline based on a Mo(VI)-catalyzed Cadogan reductive cyclization of 2-phenyl-3-nitro-5,6,7,8-tetrahydroquinoline followed by aromatization of the resulting 2,3,4,10-tetrahydro-1H-indolo[3,2-b]quinoline is proposed. Various о-nitroarylpyridines, obtained by reacting acylpyruvates and cyclic hydroxymethylene ketones with nitroacetophenone enamines, were used as starting compounds for the preparation of δ-carbolines. The synthesized δ-carbolines were found to act as phosphors; their photophysical properties were studied and a structure–property relationship was revealed.

Key words

quindoline - carbolines - Cadogan cyclization - nitro compounds - acylpyruvates - cyclic hydroxymethylene ketones

• References and Notes

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• 14 Ethyl 5H-Pyrido[3,2-b]indole-4-carboxylates 4a–j; General Procedure A solution of the appropriate ethyl 3-nitroisonicotinate 3a–f (1 mmol), PPh₃ (0.629 g, 2.4 mmol), and MoO₂Cl₂(DMF)₂ (0.017 g, 0.05 mmol) in p-cymene (10 mL) was refluxed with constant stirring under N₂. The solvent was removed under reduced pressure, and the residue was purified by column chromatography [silica gel, toluene then PE–EtOAc (1:1)], followed by crystallization from i-PrOH. Ethyl 2-Methyl-5H-pyrido[3,2-b]indole-4-carboxylate (4a) Light-yellow crystals; yield: 180 mg (71%); mp 130–131 °C (i-PrOH). IR (KBr): 3391, 2985, 1687, 1475, 1240, 1212, 1097, 730 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.48 (t, J = 7.1 Hz, 3 H), 2.80 (s, 3 H), 4.50 (q, J = 7.1 Hz, 2 H), 7.30 (ddd, J = 7.9, 6.8, 1.4 Hz, 1 H), 7.45–7.55 (m, 2 H), 7.69 (s, 1 H), 8.40 (d, J = 7.9 Hz, 1 H), 9.50 (br s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 14.3, 24.1, 61.7, 111.4, 118.4, 118.6, 120.6, 121.2, 121.5, 128.4, 130.5, 141.0, 144.0, 149.9, 166.4. Anal. Calcd for C₁₅H₁₄N₂O₂: C, 70.85; H, 5.55; N, 11.02. Found: C, 70.89; H, 5.57; N, 10.96.