Microwave-Accelerated Samarium Triiodide Catalyzed Conjugate Addition of Indoles with Electron-Deficient Olefins

Zhuang-Ping Zhan; Kai Lang

doi:10.1055/s-2005-869849

LETTER

Microwave-Accelerated Samarium Triiodide Catalyzed Conjugate Addition of Indoles with Electron-Deficient Olefins

Zhuang-Ping Zhan*, Kai Lang
Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China
Fax: +86(592)2185780; e-Mail: zpzhan@xmu.edu.cn;

Abstract

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Abstract

A fast, efficient, environmentally benign, solvent-free procedure under microwave irradiation, using silica gel supported reagents, for the samarium triiodide catalyzed conjugated addition of indoles with electron-deficient olefins has been developed.

Key words

microwave irradiation - samarium triiodide - indoles - α,β-unsaturated compounds - Michael reaction

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References

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11

Typical Experimental Procedure.
To a solution of SmI₃ (0.1 mmol) in MeCN (1 mL) was added indole (1 mmol) or 2-methylindole (1 mmol) or 2-phenylindole (1 mmol), electron-deficient olefin (1 mmol) and silica gel (0.25 g). Then the mixture was mixed thoroughly and dried under reduced pressure. The contents were taken in a 5-mL conical flask and was placed in a microwave oven (cooking type, Galanz WP 700P 21-6) and irradiated for 2 min or 15 min at 680 W. After completion of the reaction indicated by TLC, the reaction mixture was allowed to cool, diluted with CH₂Cl₂ and passed through a short silica gel column using CH₂Cl₂ as eluent. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography to afford the corresponding 3-alkylated indole.
Procedure for the Reactions with Methyl Vinyl Ketone. To a solution of SmI₃ (0.1 mmol) in MeCN (1 mL) was added indole (1 mmol) or 2-methylindole (1 mmol) or 2-phenylindole (1 mmol), and silica gel (0.25 g). Then the mixture was mixed thoroughly and dried under reduced pressure, followed by the addition of methyl vinyl ketone (1 mmol) in CH₂Cl₂ (0.5 mL) while stirring. The following work up was the same to typical experimental procedure. All new compounds were fully characterized by ¹H NMR, ¹³C NMR, MS, IR and elemental analysis.
3-(1-Benzyl-1 H -indol-3-yl)-1,3-diphenylpropan-1-one (e): Yield: 332 mg (80%). IR (film): ν_max = 3034, 1680, 1598, 1493 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 3.72 (dd, J = 7, 16.5 Hz, 1 H), 3.81 (dd, J = 7, 16.5 Hz, 1 H), 5.09 (t, J = 7 Hz, 1 H), 5.26 (s, 2 H), 6.90-7.07 (m, 4 H), 7.10-7.21 (m, 3 H), 7.23-7.30 (m, 5 H), 7.33-7.47 (m, 5 H), 7.50-7.55 (m, 1 H), 7.88-7.93 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 38.3, 45.3, 49.9, 109.7, 118.4, 119.1, 119.8, 121.9, 125.6, 126.3, 126.6, 127.3, 127.5, 127.8, 128.1, 128.4, 128.5, 128.7, 132.9, 137.0, 137.2, 137.6, 144.3, 198.6. ESI-MS: m/z (%) = 416 (88)[M + H⁺], 438 (100) [M + Na⁺]. Anal. Calcd for C₃₀H₂₅NO: C, 86.72; H, 6.06; N, 3.37. Found: C, 86.84; H, 6.05; N, 3.43.
3-[1-(4-methoxyphenyl)-2-nitroethyl]-1 H -indole (m): Yield: 278 mg (94%). IR (film): ν_max = 3412, 3058, 1610, 1548, 1509, 1373 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 3.79 (s, 3 H), 4.91 (dd, J = 7.5, 12.5 Hz, 1 H), 5.06 (dd, J = 7.5, 12.5 Hz, 1 H), 5.15 (t, J = 7.5 Hz, 1 H), 6.86 (d, J = 8.5 Hz, 2 H), 7.03 (s, 1 H), 7.09 (t, J = 7.5 Hz, 1 H), 7.21 (t, J = 7.5 Hz, 1 H), 7.26 (d, J = 8.5 Hz, 2 H), 7.36 (d, J = 7.5 Hz, 1 H), 7.45 (d, J = 7.5 Hz, 1 H), 8.10 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 40.9, 55.2, 79.7, 111.3, 114.3, 114.8, 119.0, 119.9, 121.4, 122.7, 126.1, 128.8, 131.2, 136.5, 158.9. ESI-MS: m/z (%) = 297 (15) [M + H⁺], 319 (100) [M + Na⁺]. Anal. Calcd for C₁₇H₁₆N₂O₃: C, 68.91; H, 5.44; N, 9.45. Found: C, 68.80; H, 5.32; N, 9.46.
1-Benzyl-3-[1-(4-methoxyphenyl)-2-nitroethyl]-1 H -indole (n): Yield: 367 mg (95%). IR (film): ν_max = 3027, 1606, 1548, 1501, 1373 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 3.53 (s, 3 H), 4.66 (dd, J = 7, 11 Hz, 1 H), 4.79 (dd, J = 7, 11 Hz, 1 H), 4.93 (t, J = 7 Hz, 1 H), 5.00 (s, 2 H), 6.64-6.71 (m, 2 H), 6.76-6.80 (m, 1 H), 6.86-6.93 (m, 3 H), 6.96-7.02 (m, 1 H), 7.04-7.16 (m, 6 H), 7.26-7.34 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 40.6, 49.6, 54.8, 79.5, 109.8, 113.6, 114.0, 119.0, 119.4, 122.2, 125.4, 126.4, 126.6, 127.4, 128.5, 128.6, 131.2, 136.7, 137.1, 158.6. ESI-MS: m/z (%) = 387 (100) [M + H⁺], 409 (91) [M + Na⁺]. Anal. Calcd for C₂₄H₂₂N₂O₃: C, 74.59; H, 5.74; N, 7.25. Found: C, 74.46; H, 5.73; N, 7.13.

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