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.
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.
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.
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Krutii, V.N., Chelmakova, S.A., Gurovets, A.S. et al. Conformation effects in reduction of methyl-substituted cyclopentanones with 2-propanol in presence of RhCl(PPh3)3 or RuCl2(PPh3)3 . Russ Chem Bull 24, 1019–1022 (1975). https://doi.org/10.1007/BF00922956
- Reduction Rate
- Equatorial Form
- Hydrogen Transfer