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Synlett 2007(14): 2222-2226  
DOI: 10.1055/s-2007-985590
LETTER
© Georg Thieme Verlag Stuttgart · New York

Novel Reaction of Indoles and Pyrrole with Pyrillium Catalyzed by Ceric Ammonium Nitrate (CAN)

Shun-Yi Wang, Shun-Jun Ji*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry and Chemical Engineering, Suzhou (Soochow) University, Renai Road, Suzhou Industrial Park, Suzhou 215123, P. R. of China
Fax: +86(512)65880307; e-Mail: chemjsj@suda.edu.cn;
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Publication History

Received 6 May 2007
Publication Date:
14 August 2007 (online)

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Abstract

The reaction of xanthene derivatives with indoles and pyrrole catalyzed by CAN in methanol through SN1 reaction of ­pyrillium with a nucleophilic reagent afforded the corresponding ­indole- and pyrrole-substituted xanthene derivatives in high yields, respectively.

Key words

CAN - indole - pyrrole - xanthen - pyrillium

    References and Notes

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Compound 1a with 3.0 equiv morpholine proceeded smoothly under sonic waves to give the 3′ after 3 h under neat conditions.

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General Procedure for the Reaction of Indoles with 1-Oxo-13c-alkyloxy-1,13c-dihydro-dibenzo[ a , kl ]-xanthene
A mixture of 1-oxo-13c-methoxy-1,13c-dihydro-dibenzo[a,kl]-xanthene (1a, 0.157 g, 0.5 mmol), indole 2a (0.059 g, 0.5 mmol), CAN (0.014 g, 5 mol%), and anhyd MeOH (2 mL) was irradiated with ultrasound in an open vessel at r.t. until the indole was completely consumed (3 h, monitored by TLC). Then the reaction mixture was washed with cold H2O (3 × 15 mL) and cold EtOH (3 × 0.5 mL), respectively. The crude mixture was purified by flash chromatography to afford the pure product 4a (0.190 g, yield: 95%).

1-Oxo-13c-3-indoly-1,13c-dihydro-dibenzo[ a , kl ]-xanthene ( 4a)
Kelly needles (chartreuse, acicular crystals) mp 192-194 °C. IR (KBr): ν = 3465, 3056, 1697 (C=O), 1458, 1227, 1026, 810, 740 cm-1. 1H NMR (400 MHz, CDCl3): δ = 6.43 (d, 1 H, J = 9.6 Hz), 6.84-6.88 (m, 2 H), 6.97-7.21 (m, 4 H), 7.78-7.81 (m, 7 H), 7.35-7.40 (m, 3 H), 7.65 (d, 1 H, J = 8.0 Hz), 7.75 (d, 1 H, J = 8.8 Hz), 7.89 (d, 1 H, J = 8.0 Hz), 8.08 (br, s, 1 H, NH). 13C NMR (100 MHz, DMSO-d 6): δ = 50.1, 111.8, 112.8, 115.8, 117.3, 117.4, 117.9, 118.8, 120.8, 122.2, 123.2, 123.6, 124.4, 124.5, 125.5, 127.4, 127.7, 128.0, 129.0, 130.6, 130.9, 132.3, 132.4, 135.3, 138.3, 147.6, 148.6, 201.0. HRMS: m/z calcd for C28H17NO2: 399.1259; found: 399.1240 [M+].

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Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC No. 268046 for compound 4e. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [e-mail: linstead@ccdc.cam.ac.uk or deposit@ccdc.cam.ac.uk; fax: +44 (1223)336033]. Crystal data for 4e·C3H6O: C29H19NO2·C3H6O, Mr = 471.53, triclinic, space group P-1, a = 9.7116(16) Å, b = 10.9061(18) Å, c = 11.572(2) Å, α = 95.996(5)°, β = 101.305(5)°, γ = 96.887(5)°, V = 1182.8(4) Å3, Z = 2, Dcalc = 1.324 g cm-3, (MoKα) = 0.085 mm-1; 11701 reflections collected, 4286 unique reflections, R = 0.0196.

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General Experimental Procedure
A mixture of indole 2a (0.059 g, 0.5 mmol), 7 (0.099 g, 0.5 mmol), CAN (0.014 g, 0.025 mmol), and anhyd MeOH (2 mL) was stirred in flask at r.t. until 2a was completely consumed (1 h, checked by TLC). After standing 0.5 h, the reaction mixture was washed with cold H2O (3 × 15 mL). The crude mixture was purified by flash chromatography to afford the pure product 3a (0.134 g, yield: 90%).
3-(9 H -Xanthen-9-yl)-1 H -indole ( 8a)
Mp 143-145 °C (lit. [13a] 145 °C). IR (KBr): ν = 3429 (NH), 3051, 2920, 2850, 1254, 749 cm-1. 1H NMR (400 MHz, CDCl3): δ = 5.55 (s, 1 H, CH), 6.90-7.36 (m, 13 H), 8.02 (br, s, 1 H, NH). 13C NMR (100 MHz, CDCl3): δ = 59.8, 111.2, 116.3, 119.6, 119.6, 120.3, 122.1, 122.8, 123.1, 124.4, 125.8, 127.7, 129.4, 136.7, 151.3. HRMS: m/z calcd for C21H15NO: 297.1154; found: 297.1157 [M+].