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Kostik EI, Abiko A, Oku A. Chichibabin indolizine synthesis revisited: synthesis of indolizinones by solvolysis of 4-alkoxycarbonyl-3-oxotetrahydroquinolizinium ylides. J Org Chem. 2001;66(8):2618-23doi: 10.1021/jo0011639.
Kostik, E. I., Abiko, A., & Oku, A. (2001). Chichibabin indolizine synthesis revisited: synthesis of indolizinones by solvolysis of 4-alkoxycarbonyl-3-oxotetrahydroquinolizinium ylides. The Journal of organic chemistry, 66(8), 2618-23. https://doi.org/10.1021/jo0011639
Kostik, E I, et al. "Chichibabin indolizine synthesis revisited: synthesis of indolizinones by solvolysis of 4-alkoxycarbonyl-3-oxotetrahydroquinolizinium ylides." The Journal of organic chemistry vol. 66,8 (2001): 2618-23. doi: https://doi.org/10.1021/jo0011639
Kostik EI, Abiko A, Oku A. Chichibabin indolizine synthesis revisited: synthesis of indolizinones by solvolysis of 4-alkoxycarbonyl-3-oxotetrahydroquinolizinium ylides. J Org Chem. 2001 Apr 20;66(8):2618-23. doi: 10.1021/jo0011639. PMID: 11304179.
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J Org Chem. 2001 Apr 20;66(8):2618-23. doi: 10.1021/jo0011639.

Chichibabin indolizine synthesis revisited: synthesis of indolizinones by solvolysis of 4-alkoxycarbonyl-3-oxotetrahydroquinolizinium ylides.

The Journal of organic chemistry

E I Kostik, A Abiko, A Oku

Affiliations

  1. Venture Laboratory, and Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto, 606-8585 Japan.

PMID: 11304179 DOI: 10.1021/jo0011639

Abstract

Solvolysis of 4-alkoxycarbonyl-(or 4-acyl)-3-oxo-1,2,3,4-tetrahydroquinolizinium ylides (1-4) was studied and three types of reactions were found to proceed competitively. Thus, alcoholysis afforded the Chichibabin rearrangement products, 2,3-dihydro-2-indolizinones (5-8), solvolysis in trifluoroethanol or in aqueous methanol caused ring opening (and subsequent ester cleavage) to 2-alkoxycarbonylethylpyridinium-1-acetates 10, 15, and 16, and hydrolysis resulted in ring opening to 1-alkoxycarbonylmethylpyridinium-2-propionates 11 or 13 (and subsequently to 12 or 14). Characteristically, all the types of reactions proceeded significantly faster with t-butoxycarbonyl substituted ylides than with smaller alkoxycarbonyl substituted ones. The general mechanism for the solvolysis, involving a ketene intermediate, is proposed based on kinetic measurements.

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