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Synlett 2003(10): 1431-1434
DOI: 10.1055/s-2003-40859
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Rhodium- and Iridium-Catalyzed Allylation of Electron-Rich Arenes with Allyl Tosylate

Naofumi Tsukada*, Yasushige Yagura, Tetsuo Sato, Yoshio Inoue
Department of Biomolecular Engineering, Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
Fax: +81(22)2175873; e-Mail: tsukada@aporg.che.tohoku.ac.jp;
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Publication History

Received 20 March 2003
Publication Date:
24 July 2003 (online)

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Abstract

The allylation of electron-rich arenes with allyl tosylate proceeded at 0 °C in the presence of [Rh(nbd)(CH3CN)2]PF6. Various oxygenated arenes were allylated with high para-selectivity in almost all cases. Especially in the reaction of anisoles, the tendency was remarkable.

Key words

allylations - arenes - catalysis - iridium - rhodium

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11

Reactions with cotyl tosylate and 1-methyl-2-propenyl tosylate should provide some information about the mechanism. However, we were not able to prepare 1-methyl-2-propenyl tosylate because of its instability.

14

Typical Procedure: To a suspension of an arene (5.0 mmol) and [Rh(nbd)(CH3CN)2]PF6 (0.025 mmol) in dry toluene (1 mL), allyl tosylate (0.5 mmol) was added at 0 °C under an N2 atmosphere. After stirring for 15 h or 24 h, the mixture was filtered thorough a plug of silica, followed by washing with diethyl ether (ca. 30 mL). The solvent was removed under reduced pressure to give an oil that was further purified by flash column chromatography to yield an allylated product. The products obtained were identified by comparison of their 1H NMR spectral data with those of commercial or reported samples.