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Synlett 2009(18): 2997-2999  
DOI: 10.1055/s-0029-1218004
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Total Synthesis of Horsfiline: A Palladium-Catalyzed Domino Heck-Cyanation Strategy

Stéphanie Jaeglia, Jean-Pierre Vorsb, Luc Neuville*a, Jieping Zhu*a
a Institut de Chimie des Substances Naturelles, CNRS, 91198 Gif-sur-Yvette Cedex, France
Fax: +33(1)69077247; e-Mail: zhu@icsn.cnrs-gif.fr; e-Mail: neuville@icsn.cnrs-gif.fr;
b Bayer CropScience SA, 14-20 Rue Pierre Baizet, 69009 Lyon, France
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Publikationsverlauf

Received 20 July 2009
Publikationsdatum:
08. Oktober 2009 (online)

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Abstract

A total synthesis of horsfiline has been accomplished featuring a key intramolecular palladium-catalyzed domino Heck-cyanation sequence for the formation of the 3,3′-disubstituted oxindole.

Key words

domino reaction - palladium - Heck - cyanation - oxindole - horsfiline

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18

Experimental Procedure: To a degassed solution of iodoanilide 14 (1.90 g, 3.29 mmol, 1.0 equiv) in DMF (16 mL) were added K4Fe(CN)6˙3H2O (306.0 mg, 0.72 mmol, 0.22 equiv), Na2CO3 (350.0 mg, 3.30 mmol, 1.0 equiv) and Pd(OAc)2 (22.0 mg, 0.1 mmol, 0.03 equiv). After being stirred at 120 ˚C under an argon atmosphere for 3 h, the reaction mixture was quenched with H2O and extracted with EtOAc. The combined organic layers were washed with brine, dried (Na2SO4) and concentrated. The residue was purified by flash chromatography (SiO2, heptane-EtOAc, 95:5 → 90:10) to give the corresponding oxindole 15 (0.94 g, 60%) as a light orange solid. Compound 15: ¹H NMR (500 MHz, CDCl3): δ = 7.06 (d, J = 2.6 Hz, 1 H), 7.02 (d, J = 8.6 Hz, 1 H), 6.88 (dd, J = 8.6, 2.6 Hz, 1 H), 5.17 (d, J = 11.0 Hz, 1 H), 5.11 (d, J = 11.0 Hz, 1 H), 3.92 (d, J = 9.7 Hz, 1 H), 3.80 (s, 3 H), 3.73 (d, J = 9.7 Hz, 1 H), 3.62-3.51 (m, 2 H), 3.02 (d, J = 16.7 Hz, 1 H), 2.79 (d, J = 16.7 Hz, 1 H), 0.92 (t, J = 8.2 Hz, 2 H), 0.84 (s, 9 H), 0.00 (s, 3 H), -0.01 (s, 3 H), -0.03 (s, 9 H). ¹³C NMR (75 MHz, CDCl3): δ = 175.4, 156.4, 135.4, 129.1, 116.2, 114.3, 111.2, 110.6, 69.9, 66.5, 66.1, 55.8, 51.9, 25.7, 21.7, 18.1, 17.7, -1.4, -5.6, -5.7. HRMS (ES+): m/z [M + Na]+ calcd for C24H40N2O4Si2Na: 499.2424; found: 499.2415.