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Synthesis 2010(21): 3609-3614  
DOI: 10.1055/s-0030-1258208
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Claisen Rearrangement through Enolization of 2-Allyloxyindolin-3-ones: Construction of Adjacent Carbon Stereocenters in 3-Hydroxyindolin-2-ones

Kazuhiro Higuchi, Keita Saito, Tetsuya Hirayama, Yoshiaki Watanabe, Emiko Kobayashi, Tomomi Kawasaki*
Meiji Pharmaceutical University, 2-522-1 Noshio Kiyose, Tokyo 204-8588, Japan
Fax: +81(42)4958764; e-Mail: kawasaki@my-pharm.ac.jp;
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Publication History

Received 8 June 2010
Publication Date:
13 August 2010 (online)

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Abstract

The Claisen rearrangement of 3-oxy-2-allyloxyindoles through base-induced enolization of 2-allyloxyindolin-3-ones was investigated. This rearrangement reaction proceeded smoothly at low temperature and showed intriguing diastereoselectivity that did not depend on the initial olefin geometry.

Key words

diastereoselectivity - heterocycles - indoles - rearrangement - solvent effects

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15

When NaOMe was used as a base, the reaction resulted in 56% yield and 79% de.

18

The ratio (1.4-1.9:1) of anti/syn-9 decreased when the aprotic solvent(toluene) was used for the Claisen rearrangement of 5b and 5d.