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Reverse Aromatic Cope Rearrangement of 2-Allyl-3-alkylideneindolines Driven by Olefination of 2-Allylindolin-3-ones:  Synthesis of α-Allyl-3-indole Acetate Derivatives

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Meiji Pharmaceutical University, 2-522-1, Noshio, Kiyose, Tokyo 204-8688, Japan, and Kissei Pharmaceutical Co., Ltd., Discovery Research, R & D, 4365-1, Kashiwabara, Hotaka, Minamiazumi, Nagano 399-8304, Japan
Cite this: J. Org. Chem. 2001, 66, 4, 1200–1204
Publication Date (Web):January 30, 2001
https://doi.org/10.1021/jo0014921
Copyright © 2001 American Chemical Society
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    Abstract

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    The reverse aromatic Cope rearrangement of 2-allyl-3-alkylideneindolines obtained by Horner−Wadsworth−Emmons olefination of 2-allylindolin-3-ones was performed. When 2-allylindolin-3-ones were treated with phosphonium ylides in refluxing toluene, domino Wittig reaction and reverse aromatic Cope rearrangement took place to give α-allyl-3-indole acetate derivatives in good yields. The aromatization as a new driving force in the Cope rearrangement is preferable to the conjugation with the carbonyl and cyano groups and also to the alkyl substitution pattern, which are well-known driving forces.

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     To whom correspondences should be addressed. Tel.:  +81-424-95-8764. Fax:  +81-424-95-8763.

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     Meiji Pharmaceutical University.

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     Kissei Pharmaceutical Co., Ltd.

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    The force field parameters for computations of the reverse aromatic Cope rearrangement 7a−9a to 11a−13a (Table 2), the full Experimental Section, and 1H NMR spectra for compounds Z-7a, E-7a, E,Z-mixtures of 8a, 9a,b, and 17, 10a, 11a−e, 12a,b, 12e,f, 15, a mixture of 13b and 15, and 13a,b. This material is available free of charge via the Internet at http://pubs.acs.org.

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