Ketones norbornyl

Me3SiOCH3, Me3SiOTf, CH2CI2, -78°, 86% yield. The use of TMSOFs to catalyze this transformation has also been demonstrated. A norbornyl ketone was not ketalized under these conditions. 

Nitrogen compounds, reduction, 103-104 N-(exo-2-Norbornyl)acetamide, ketone amidation, 130 Nucleophilic species ... 

Besides the obvious D3 twisted bicyclo[2.2.2]octane framework, another characteristic of pentacyclic [m.n.o] triblattanes is the presence of a strained bicyclo [2.2.0] hexane moiety whose facile reductive cleavage of the central single bond correlates this class of triblattanes to the corresponding tetracyclic [m.n] triblattanes. Figure 21 illustrates the configurational correlation between these two classes of triblattanes the key liaison compound is the (+) <, 0-unsaturated ketone 172, whose absolute configuration had been related to that of the levorotatory carboxylic acid (-)-151 via (+)-methyl 3-(enrfo-2-norbornyl) propionate (179) (146). 

Reaction of several bicyclo[2,2,l]heptenes with phenyl(trichloromethyl)mer-cury reveals the fact that born-2-ene (281) (the synthesis of which has just appeared in Organic Syntheses ) is completely unreactive to this substance, because steric hindrance prevents the cxo-attack required by torsional strain. The labelled bornyl-isobornyl Grignard mixture (282) undergoes cis-exo eliminative transfer to phenyl isopropyl ketone, although to a lesser extent than in the norbornyl system, this probably being a reflection of the fact that the gem-dimethyl group reduces the energy difference between exo- and e/ido-transfer. ... 

Fig. 4. Correlation of acetolysis rates of arenesulfonates and carbonyl frequencies of the corresponding ketones.The numbers represent the following 1-10, cyclohexyl through cyclopentadecyl, respectively 11, 2-propyl 12, 2-butyl 13, 3-methyl-2-butyl 14, 3,3-dimethyl-2-butyl 15, 7-norbornyl 16, enifo-8-bicyclo[3.2.1]octyl 17, 2-adamantyl 18, a-nopinyl 19, jS-nopinyl 20, l,4-a-5,8-j5-dimethanperhydro-9-anthracyl. Reprinted by permission of the American Chemical Society.

In attempting to determine the effect of electron-withdrawing substituents on the solvolysis of 2-norbornyl derivatives, Gassman et found that the endo-ketal (144) solvolyzed with MeO-4 participation to produce (148) through methoxy group migration. The other products, (146) and (147), were also thought to arise from MeO-4 participation, since ketonic... 

A soln. of norbornene in acetaldehyde containing 0.02 mole of azodiisobutyronitrile heated- 40 hrs. at 80° in an autoclave exo-norbornyl methyl ketone. Y 80%.—Other free-radical sources of peroxidic nature give much lower yields. H. Stockmann, J. Org. Ghem. 29, 245 (1964). 

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