alpha -Nitroketones. 3. Stereochemistry of the nitration of 1-acetoxycyclohexenes: synthesis of 2-nitrocyclohexanones.

The nitration of enol acetates of substituted cyclohexanones in Ac2O at 15 Deg with concd. HNO3 is a kinetically controlled process which can lead to cis-trans-substituted 2-nitrocyclohexanones in very good yields. The stereochem. of the reaction is controlled by the transition-state geometry which...

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Journal Title: Journal of Organic Chemistry Vol. 46; no. 15; pp. 3082 - 3087
Authors: Walter W. Zajac, Hadi Oezbal
Format: Article
Published: 1981
Application Date: Dep. Chem.,Villanova Univ.,Villanova,PA,USA.
Subjects:
Summary: The nitration of enol acetates of substituted cyclohexanones in Ac2O at 15 Deg with concd. HNO3 is a kinetically controlled process which can lead to cis-trans-substituted 2-nitrocyclohexanones in very good yields. The stereochem. of the reaction is controlled by the transition-state geometry which resembles the enol acetate. The following 2-nitrocyclohexanones were prepd. from the corresponding cyclohexanones via the enol acetates: 4-Me, 4-Et, 4-iso-Pr, 4-tert-Bu, 3-Me, 3-tert-Bu, 5-Me, 5-tert-Bu, 3,3,5-tri-Me, 3,5,5-tri-Me, 3,3,5,5-tetra-Me, and 2-Me-4-tert-Bu.
ISSN: 0022-3263