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2-Methylcyclohexanone is converted into by LDA in THF at followed by , and into by in at room temperature followed by (major products in each case). The ketone (all of its stereoisomers together) is reduced by to give a mixture of alcohols . Identify , and the total number of stereoisomers (enantiomers counted separately) of the alcohol that are possible.
- A. = 2,2-dimethylcyclohexanone; = 2,6-dimethylcyclohexanone; has stereoisomers
- B. = 2,6-dimethylcyclohexanone; = 2,2-dimethylcyclohexanone; has stereoisomers
- C. = 2,6-dimethylcyclohexanone; = 2,2-dimethylcyclohexanone; has stereoisomers
- D. = 2,6-dimethylcyclohexanone; = 2,2-dimethylcyclohexanone; has stereoisomers
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Answer: (C) = 2,6-dimethylcyclohexanone; = 2,2-dimethylcyclohexanone; has stereoisomers
LDA is bulky and strong and, at , removes the more accessible proton of the less substituted -carbon (kinetic enolate); methylation therefore gives = 2,6-dimethylcyclohexanone. / is reversible and gives the more substituted, more stable (thermodynamic) enolate, so methylation at that carbon gives = 2,2-dimethylcyclohexanone. is 2,6-dimethylcyclohexan-1-ol, which has three stereocentres (, , ) in a ring with a symmetric substitution pattern. For cis-2,6-dimethyl the may be cis or trans to both methyls: 2 meso compounds. For trans-2,6-dimethyl (chiral) the is necessarily cis to one methyl and trans to the other, and the two choices are the same by the relation, giving one enantiomeric pair: 2 isomers. Total . Answer: (C).
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