Butenolide annelation using a manganese(III) oxidation. A synthesis of chromolaenin (Laevigatin)

A procedure was developed for the annelation of a butenolide to an aromatic ketone that highlighted a manganese(III) oxidation of an aromatic ketone. The merit of this procedure was illustrated in a synthesis of Chromolaenin (Laevigatin) ( 1 ) from 4,7-dimethyl-1-tetralone ( 2c ). Oxidation of tetra...

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Bibliographic Details
Published inCanadian journal of chemistry Vol. 77; no. 8; pp. 1336 - 1339
Main Authors Demir, Ayhan S, Gercek, Zuhal, Duygu, Nese, Igdir, A Cigdem, Reis, Omer
Format Journal Article
LanguageEnglish
Published Ottawa, Canada NRC Research Press 01.08.1999
Canadian Science Publishing NRC Research Press
Subjects
Chemistry
Chromolaenin
Ketones
Manganese
Metals
Oxidation
VOCs
Volatile organic compounds
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Summary:A procedure was developed for the annelation of a butenolide to an aromatic ketone that highlighted a manganese(III) oxidation of an aromatic ketone. The merit of this procedure was illustrated in a synthesis of Chromolaenin (Laevigatin) ( 1 ) from 4,7-dimethyl-1-tetralone ( 2c ). Oxidation of tetralone and indanone with manganese(III) acetate in the presence of chloro- or bromopropionic acid or their Mn(II) salts furnished a -haloesters 3a - d . An Arbuzov reaction of haloesters with triethylphosphite and an intramolecular Horner-Watsworth-Emmons cyclization of the resulting phosphonate gave butenolide 5a , b in 77-79% yield. This methodology was also applied to 4,7-dimethyl-1-tetralone ( 2c ), and the corresponding butenolide 6 is synthesized in 85% yield, which was then converted to Chromolaenin ( 1 ) using DIBAL-H.Key words: chromolaenin (Laevigatin), manganese(III) acetate oxidation, aromatic ketones, butenolide annelation, lactone, Horner-Watsworth-Emmons cyclization, Arbuzov reaction.
ISSN:0008-4042
1480-3291
DOI:10.1139/v99-136