Ni(acac)₂-Catalyzed Addition Reactions of Aryl- and Alkylboronic Acids to Tryptanthrins

Abstract

A Ni(acac)₂-catalyzed 1,2-addition reaction of tryptanthrins with aryl- or alkylboronic acids gave the corresponding indoloquinazolinone-type quaternary alcohols in 30–90% yield. Importantly, this reaction showed a good tolerance of functional groups and a remarkably broad substrate scope that included substrates bearing halogen atoms.

Key words

addition reactions - nickel catalysis - tryptanthrins - boronic acids - indoloquinazolinones

• References and Notes


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• 11 6-Aryl-6-hydroxyindolo[2,1-b]quinazolin-12(6H)-ones 3; Gen-eral Procedure The appropriate tryptanthrin 1 (0.2 mmol), arylboronic acids 2 (1 mmol), Ni(acac)₂ (0.01 mmol), K₂CO₃ (0.4 mmol), and CPME (2 mL) were added to a Schlenk tube. The mixture was stirred at the appropriate temperature for the time shown in Table 2 until the reaction was complete and then the solvent was evaporated under reduced pressure. The crude mixture was purified by flash column chromatography [eluent for TLC: CH₂Cl₂; eluent for silica gel column chromatography: PE–CH₂Cl₂ (1:3); CH₂Cl₂–EtOAc (25:1); R_f  = 0.2–0.4]. 6-Hydroxy-6-phenylindolo[2,1-b]quinazolin-12(6H)-one (3a) White solid; yield: 58.7 mg (90%); IR (KBr): 3338, 1655, 1466, 1358, 1186, 757, 699 cm^–1; ¹H NMR (500 MHz, DMSO): δ = 7.10 (s, 1 H), 7.29–7.43 (m, 7 H), 7.55 (m, 1 H), 7.62 (m, 1 H), 7.72 (m, 1 H), 7.84–7.87 (m, 1 H), 8.32 (d, J = 7.7 Hz, 1 H), 8.53 (d, J = 7.9 Hz, 1 H). ¹³C NMR (126 MHz, DMSO): δ = 78.98, 116.34, 121.44, 125.00, 125.63, 126.41, 127.02, 127.54, 127.65, 127.68, 128.17, 129.85, 134.75, 135.94, 138.56, 141.79, 147.08, 158.96, 161.68. HRMS (Micromass GCT-MS ESI): m/z calcd for C₂₁H₁₅N₂O₂ ⁺: 327.1128; found: 327.1124.
• 12 CCDC 1449571 (3a) and 1449572 (5a) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.