4- rerr-Butylcyclohexanone

Similar stereoselectivity was noticed in reductions of ketones by alkali metals in liquid ammonia and alcohols. 4-rerr-Butylcyclohexanone gave almost exclusively the more stable equatorial alcohol, norcamphor 68-91% of the less stable e cfo-norborneol, and camphor a mixture of bomeol and isoborneol [860],... 

With 4-rerr-butylcyclohexanone, sulfoxonium ylides (78, 80,81, 82) give (Z)-oxiranes, whereas mainly (E)-oxirane is formed from 77. The A -p-toluyl-sulfonimidoyl-stabilized carbanions 83 are similarly regio- and stereoselective. 

Write the structures of the two products obtained by reaction of 4-rerr-butylcyclohexanone with sodium acetylide. Predict which one is obtained in the larger amount. 

Hydroxymethyhtion of ketones. A ketone can be converted into the a-hydroxy-methyl derivative in two. steps acylation with ethyl formate, followed by aluminum hydride reduction. The sequence is illustrated for the conversion of 4-rerr-butylcyclo-hcxanone(l) inlo 2-hydroxymelhyl-4-ferf-butylcyclohexanone(3). 

Dimethyl sulfide added at 0° under argon to a stirred soln. of N-dilorosuccinimide in toluene, cooled to -25°, a soln. of 4-rerr-butylcyclohexanol in toluene added dropwise, stirring continued 2 hrs. at -25°, then a soln. of triethylamine in toluene added dropwise, the cooling bath removed, and the product isolated after 5 min. 4-tert-butylcyclohexanone. Y ca. 100%. F. e. s. E. J. Corey and C. U. Kim, Am. Soc. 94, 7586 (1972) J. Org. Chem. 38, 1233 (1973). 

Two cyanohydrins of 4-rerr-butyl-butylcyclohexanone exist. Which is the kinetic product Which is the thermodynamic product ... 

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