2-Azabarrelenone and 3-Methoxy-2-azabarrelene

✍ Scribed by Prof. Dr. Rudolf Gompper; Dipl.-Chem. Axel Schmidt

• Book ID: 101551365
• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: English
• Weight: 220 KB
• Volume: 19
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.198004631

✦ Synopsis

Dedicated to Professor Rolf Huisgen on the occasion of his 60th birthday

Barrelene is to be classed among the antibicycloaromatic compounds"'. In the case of the anions of the barrelenone and other bicyclo[2.2.2]octenones the antibicycloaromaticity or antihomoaromaticity has its effect on the polarity of the enol systems and hence on the course of methylation in accordance with the allopolarization (0-US.

C-methylation). Besides (1) and methylenebarrelene~2"1, 2azabarrelenone ( 2) is a further interesting species for the study of homoallylic interactions. Moreover, (2) can be used as starting material for the synthesis of the hitherto unknown 2-azabarrelenes (cf. 131). According to STO-3G calculations, 2-azabarrelene (3) and barrelene have similar stabilitie~~~]; 2methoxycarbonyl-2-azabicyclo[2.2.2]octa-5,7-diene already decomposes at room temperaturecs1. C,N-Substituted derivatives of (2) have been prepared by reaction of N-substituted a-pyridones with dehydrobenzene['"l or acetylenedicarboxylates[6b1. For the synthesis of (2) and C-unsubstituted derivatives of (2) we have used the 2-aza-3-oxobicyclo[2.2.2]octa-7-ene-5,6-dicarboxylic acids 0 R / ? 0 ,-.