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Synlett 2010(8): 1251-1254  
DOI: 10.1055/s-0029-1219809
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Efficient Iron-Catalyzed Tsuji-Trost Coupling Reaction of Aromatic Allylic Amides through a sp³-Carbon-Nitrogen Breaking

Zhen-Yu Jianga, Cai-Hua Zhanga, Feng-Lei Gua, Ke-Fang Yanga, Guo-Qiao Lai*a, Li-Wen Xu*a,b, Chun-Gu Xiab
a Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, 310012, P. R. of China
Fax: +86(571)28865135; e-Mail: liwenxu@hznu.edu.cn;
b State Key Laboratory of Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, P. R. of China
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Publication History

Received 11 January 2010
Publication Date:
07 April 2010 (online)

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Abstract

The catalytic activation of sp³-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).