Diastereoselective Tandem Michael Additions of Indoles to 3-Nitrocoumarin Derivatives and Methyl Vinyl Ketone

Meng-Chun Ye; Yao-Yu Yang; Yong Tang; Xiu-Li Sun; Zhi Ma; Wei-Min Qin

doi:10.1055/s-2006-932472

LETTER

Diastereoselective Tandem Michael Additions of Indoles to 3-Nitrocoumarin Derivatives and Methyl Vinyl Ketone

Meng-Chun Ye^a, Yao-Yu Yang^b, Yong Tang*^a, Xiu-Li Sun^a, Zhi Ma^a, Wei-Min Qin^b
^a State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. of China
^b College of Chemistry and Chemical Engineering, Donghua University, 1882 West Yan’an Road, Shanghai 200051, P. R. of China
Fax: +86(21)54925078; e-Mail: tangy@mail.sioc.ac.cn;

Abstract

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Abstract

Tandem Michael additions of indole derivatives to 3-nitrocoumarins 2, followed by MVK, in one pot, has been developed for the synthesis of multi-functionalized 3,4-dihydrocoumarins bearing a quaternary stereocenter. The reaction proceeds with high diastereoselectivities in good to excellent yields.

Key words

α,β-unsaturated nitroesters - tandem Michael additions - one-pot reactions - 3,4-dihydrocoumarins

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Referenzen

References and Notes

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Typical Procedure: To a stirred solution of Mg(OTf)₂ (0.01 mmol) and 3-nitrocoumarin 2 (0.50 mmol) in i-PrOH (3 mL) at 20 °C in air was added indole derivative 1 (0.51 mmol). After the reaction was complete (ca. 3-12 h, monitored by TLC), MVK (124 µL, 1.50 mmol) and Ph₃P (26.2 mg, 0.10 mmol) were added in turn, then DME (3 mL) was added in ca. five minutes. The resulting mixture was stirred for the required time (TLC), concentrated, and purified by flash chromatography on silica gel (PE-EtOAc, 2:1) to give the product 4.
Selected spectral data:
4a: IR (neat): 3418, 1773, 1710, 1554, 1458, 1356, 1226, 1169, 747 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 8.43 (br s, 1 H), 7.40-7.33 (m, 3 H), 7.25-7.20 (m, 2 H), 7.14-7.07 (m, 4 H), 4.98 (s, 1 H), 2.86-2.73 (m, 2 H), 2.66-2.44 (m, 2 H), 2.09 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 205.75, 161.25, 149.76, 135.81, 129.64, 128.56, 126.70, 125.60, 124.70, 122.83, 122.60, 120.41, 117.88, 116.78, 111.72, 107.69, 92.98, 43.96, 38.12, 29.87, 28.42. LRMS-EI: m/z (%) = 378 (M⁺), 274 (100). Anal. Calcd for C₂₁H₁₈N₂O₅: C, 66.66; H, 4.79; N, 7.40. Found: C, 66.67; H, 4.84; N, 7.40.
4b: IR (neat): 3052, 2926, 1774, 1718, 1554, 1487, 1456, 1338, 1226, 1166, 742 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.38-7.32 (m, 3 H), 7.28-7.20 (m, 2 H), 7.13-7.07 (m, 3 H), 6.97 (s, 1 H), 4.97 (s, 1 H), 3.78 (s, 3 H), 2.80-2.71 (m, 2 H), 2.60-2.44 (m, 2 H), 2.08 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 205.62, 161.22, 149.75, 136.66, 129.56, 128.99, 128.52, 127.41, 125.54, 122.90, 122.37, 120.00, 117.89, 116.75, 109.78, 105.91, 93.04, 43.81, 38.11, 33.07, 29.83, 28.40. LRMS-ESI: m/z = 393 (M + H⁺). HRMS: m/z calcd for C₂₂H₂₀N₂O₅Na (M + Na⁺): 415.1270; found: 415.1267.
4c: IR (neat): 3418, 1770, 1716, 1587, 1556, 1509, 1455, 1360, 1264, 1237, 1169, 1091, 735 cm^-1. ¹H NMR (300 MHz, DMSO-d ₆): δ = 11.27 (s, 1 H), 7.41-7.30 (m, 3 H), 7.05-6.94 (m, 3 H), 6.73-6.61 (m, 2 H), 5.44 (s, 1 H), 3.52 (s, 3 H), 3.00-2.49 (m, 4 H), 2.05 (s, 3 H). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 206.94, 161.87, 150.40, 137.42, 136.24, 130.01, 129.87, 125.64, 121.95, 121.13, 119.26, 119.20, 116.90, 111.76, 103.26, 92.88, 44.23, 38.33, 30.34, 28.41, 12.27. LRMS-ESI: m/z = 393 (M + H⁺). HRMS: m/z calcd for C₂₂H₂₀N₂O₅Na (M + Na⁺): 415.1270; found: 415.1265.
4d: IR (neat): 3421, 1767, 1716, 1554, 1509, 1361, 1264, 1092, 736 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 8.50 (br s, 1 H), 7.34-7.30 (m, 1 H), 7.20-7.05 (m, 4 H), 6.98 (d, J = 8.4 Hz, 1 H), 6.87 (d, J = 1.8 Hz, 1 H), 6.53 (d, J = 8.1 Hz, 1 H), 5.86 (br s, 1 H), 3.88 (br s, 3 H), 2.94-2.48 (m, 4 H), 2.08 (s, 3 H). ¹³C NMR (75 MHz, acetone-d ₆): δ = 205.15, 161.57, 154.03, 149.97, 137.47, 128.96, 128.48, 125.23, 124.71, 123.42, 122.72, 117.42, 116.20, 107.21, 105.25, 99.92, 94.32, 54.42, 42.54, 37.47, 28.85, 27.69. LRMS-ESI: m/z = 409 (M + H⁺). HRMS: m/z calcd for C₂₂H₂₀N₂O₅Na (M + Na⁺): 431.1219; found: 431.1217.
Spectral data for compound 3: ¹H NMR (300 MHz, CDCl₃): δ = 8.27 (br s, 1 H), 7.46-7.04 (m, 9 H), 5.84 (d, J = 9.3 Hz, 1 H), 5.40 (d, J = 9.3 Hz, 1 H).