Highly Regioselective Synthesis of Indenocarbazolones via Palladium-Catalyzed Intramolecular ortho Arylation

Abstract

An efficient protocol for the synthesis of indenocarbazol­ones through palladium-catalyzed intramolecular arylation in good yield with high regioselectivity under ligand-free conditions is reported.

Key words

palladium catalysis - ortho arylation - indenocarbazol­ones - C-H activation

References and Notes

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See Supporting Information.

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Analytical Data
Compound 4a: CCDC deposition number 854724. Formula: C₂₁H₁₅N₁O₁. Unit cell parameters: a = 18.8910 (15), b = 14.7317 (11), c = 5.3252 (3), space group P2₁2₁2.
Compound 4ab: CCDC deposition number 854725. Formula: C₂₁H₁₅N₁O₁. Unit cell parameters: a = 15.9003 (8), b = 5.4237 (3), c = 17.1149 (8), space group Pna2₁.
Compound 4d: CCDC deposition number 854726. Formula: C₂₂H₁₇N₁O₂. Unit cell parameters: a = 8.3015 (8), b = 9.1172 (9), c = 10.6868 (10), α = 83.461 (2), β = 79.759 (2), γ = 81.777 (2), space group P1.
Compound 6b: CCDC deposition number 854727. Formula: C₂₉H₁₈Cl₃N₁O₂. Unit cell parameters: a = 9.0516 (13), b = 10.4572 (20), c = 13.2939 (17), α = 100.684 (14), β = 101.200(12), γ = 101.784 (15), space group P1.

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General Procedure
A mixture of compound 3a (0.10 g, 0.02 mmol), anhyd KOAc (0.04 g, 0.04 mmol), TBAB (0.06 g, 0.02 mmol), and Pd(OAc)₂ (0.003 g, 5 mol%) in DMF (3.0 mL) was taken in a Schlenk tube and heated at 140 ˚C for 3 h with continuous stirring. After completion of the reaction as monitored by TLC, the reaction mixture was cooled and poured into cold H₂O (10 mL). A solid precipitate was formed, extracted with CHCl₃ (3 × 20 mL), and washed with H₂O (3 × 20 mL) followed by brine (20 mL) and dried over anhyd Na₂SO₄. Evaporation of solvent, and the crude material was purified by column chromatography over silica gel (100-200 mesh), using 12% EtOAc in hexanes as eluent to give product 4a in 68% yield. Compounds 4b-g and 6b were obtained using same procedure.
5-Ethylindeno[1,2- b ]carbazol-11 (5 H )-one (4a) Yellow solid; mp 181-182 ˚C; yield 68%. IR (KBr): 2986, 1697, 1570, 1446, 1331, 1111, 931, 742 cm^-¹. ^¹H NMR (400 MHz, TMS, CDCl₃): δ = 8.39 (s, 1 H), 8.05 (d, 1 H, J = 7.6 Hz), 7.66 (d, 1 H, J = 7.2 Hz), 7.59 (d, 1 H, J = 7.2 Hz), 7.50-7.46 (ddd, 2H, J ₁ = 1.2 Hz, J ₂ = 7.6 Hz, J ₃ = 15.2 Hz), 7.42 (s, 1 H), 7.33-7.27 (m, 3 H), 4.41 (q, 2 H, J = 7.2 Hz), 1.51 (t, 3 H, J = 7.2 Hz). ^¹³C NMR (100 MHz, TMS, CDCl₃): δ = 193.2, 144.6, 144.1, 142.6, 140.7, 136.3, 134.1, 128.8, 126.4, 126.2, 123.8, 123.1, 120.6, 120.5, 119.9, 118.0, 109.1, 100.7, 37.9, 14.0. LC-MS (positive mode): m/z = 298 [M + H]⁺. Anal. Calcd (%) for C₂₁H₁₅NO: C, 84.82; H, 5.08; N, 4.71. Found: C, 84.65; H, 5.12; N, 4.68.