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Bicyclo[3.3.1]nonanes as synthetic intermediates XIII. : Novel transannular hydride shifts enforced by relief of the steric constraint in the bicyclo[3.3.1]nonane system bearing endo-substituents at position 7

✍ Scribed by Takefumi Momose; Toshiyuki Itooka; Takafumi Nishi; Mari Uchimoto; Keiko Ohnishi; Osamu Muraoka


Publisher
Elsevier Science
Year
1987
Tongue
French
Weight
697 KB
Volume
43
Category
Article
ISSN
0040-4020

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✦ Synopsis


The Huang-Minlon reduction of 7a-hydroxymethylbicyclo[3.3.11nonan-3-one (1) gave 7B-methylbicyclo[3.3.llnonan-36-01 (21, a product formed as a result of the transannular 1,6-hydride shift enforced by relief of the steric constraint in the system. Another example of the intramolecular hydride transfer on the same basis was observed in the deketalization of 9,9-disubstituted 7,7-ethylenedioxybicyclo[3.3.1]nonan-30-01 (13 and 18) resulting in the formation of 7S-(2-hydroxyethoxy)bicyclo[3.3.1]nonan-3-one (15 and 20).