Conformational Effect on the Bridgehead Reaction of Bicyclo[3.3.1]nonan-2-ones. A Facile Bridgehead Deuteration of a Bicyclo[3.3.1]nonan-2-one Derivative with the Cyclohexanone Ring Locked in the Boat Conformation

Autor:	Masaaki Suzuki, Yoshimasa Hirata, Yoshinori Kyotani, Shunichi Manabe, Kiyoyuki Yamada
Rok vydání:	1979
Předmět:	chemistry.chemical_classification chemistry.chemical_compound Ketone 13c nmr spectroscopy chemistry Deuterium Bicyclic molecule Stereochemistry Cyclohexane conformation Cyclohexanone General Chemistry Ring (chemistry) Derivative (chemistry)
Zdroj:	Bulletin of the Chemical Society of Japan. 52:186-190
ISSN:	1348-0634 0009-2673
DOI:	10.1246/bcsj.52.186
Popis:	Five bicyclo[3.3.1]nonan-2-ones, two known (1, 3) and three new ones (2, 4, 5) were prepared. The hydrogen-deuterium exchange reaction at the bridgehead position of the bicyclo[3.3.1]nonan-2-one system was examined under mild basic conditions (2 M NaOMe-MeOD, 33 °C, 22 h) using these five bicyclo[3.3.1]nonan-2-ones. Virtually no deuteration took place at the bridgehead in each case of the bicyclic ketones (1, 2, 3, 4), whereas one deuterium was incorporated into the bridgehead of the ketone (5). 13C NMR spectroscopy was employed for the unambiguous determination of the site(s) of deuteration in all cases studied. The enhanced bridgehead acidity of (5) could be explained in terms of the locked boat conformation of the cyclohexanone ring contained in (5).
Databáze:	OpenAIRE
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