V. N. Krutii, S. A. Chelmakova, A. S. Gurovets
May 1, 1975
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Journal
Russian Chemical Bulletin
Abstract
1. The insertion into cycloheptanone of a methyl in either the 3 or 4 position, and also of two methyls in the 3 and 6 positions, does not affect the rate of hydrogen transfer from 2-propanol to the cycloheptanones in the presence of the triphenylphosphine complexes of Rh and Ru. 2. The presence of geminal dimethyl groupings in the 3 and 6 positions lowers the reduction rate of the cycloheptanones, which is explained by a shielding of the carbonyl by the axial methyls. 3. Conformational analysis revealed that in principle the cycloheptanone homologs differ from the homologs with smaller rings: transition of the axial substituent to the equatorial can occur without the complete inversion of the seven-membered ring. Both stereoisomers of 3, 6-dimethylcycloheptanone can exist in the equatorial form. This is in good agreement with the experimental data on the reduction rates.