Efficient Iron-Catalyzed Tsuji-Trost Coupling Reaction of Aromatic Allylic Amides through a sp^³-Carbon-Nitrogen Breaking

Abstract

The catalytic activation of sp^³-carbon-nitrogen of allylic amides is generally difficult because of the inefficient leaving-group ability of the amide group. In this article, we have discovered for the first time that FeCl₃-catalyzed Tsuji-Trost coupling reaction of aromatic allylic amides with active methylene compounds, cyclohexanone, and allytrimethylsilane work efficiently under mild conditions.

Key words

iron catalysis - Lewis acid - Brønsted acid - Tsuji-Trost reaction

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8

General Procedure for Tsuji-Trost Coupling Reaction of Allylic Amides with Activated Methylene Compound or Cyclohexanone
A catalytic amount of FeCl₃ (10 mol%) was added to the mixture of allylic amide (0.5 mmol) and activated methylene compound or cyclohexanone (0.75 mmol) in MeNO₂ (2 mL). After vigorous stirring at r.t. for the times showed in the Tables and Schemes, the reaction mixtures were poured into an extraction funnel containing brine, diluted with distilled H₂O and EtOAc. The aqueous phase was extracted with EtOAc. The combined organic phases were dried with Na₂SO₄, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography to furnish the desired products. All the products are known compounds and confirmed by GC-MS, NMR, and IR (see spectra).