Tricyclo decane-2-carboxylic

To a stirred solution of [4-(2-pyrimidinyl)piperazino]ethylamine (2.0 g, 0.01 mol) in 50 ml of methylene chloride, adamantane-l-carboxylic acid chloride (3.6 g, 0.018 mol) and triethylamine (2.9 g, 0.015 mol) were added. Stirring was continued at room temperature overnight. The methylene chloride solution was washed with water, dried over anhydrous sodium sulfate and evaporated under reduced pressure. The remaining residue was subjected to preparative HPLC. The residue was dissolved in ethyl acetate (10 ml) and subjected to flash chromatography using a 9 inch column of silica gel and ethyl acetate as the eluent. The N-[2-[4-(2-pyrimidinyl)-l-piperazinyl]ethyl]tricyclo[3.3.1.1(3,7)] decane-l-carboxamide was separated. 

Treatment of the dimer of chloro entfo-5-[(Z)-prop-l-enyl]tricyclo[2.2.1.0 ]hept-e r/o-3-yl palladium with carbon monoxide in methanol afforded methyl 5-methyl-6-oxotet-racyclo[5.3.0.0 °.0 ]decane-4-carboxylate in 54% yield, which results from intramolecular acylpalladium addition to the double bond followed by carbonylation. An analogous reaction was involved when (exo-5-acetoxytricyclo[2.2.1.0 ]hept-ent/o-3-yl)chlorodipyridinepal-ladium was reacted successively with bis[( )-2-chlorovinyl]mercury and carbon monoxide in methanol. 

Cyclobutane formation, occasionally in fairly low yield due to ring-opening reactions, also occurred by photochemical [2 - - 2] cycloaddition of vinylcyclopropane derivatives to an a, -unsaturated ketone moiety, " a cyclobuta-1,3-diene, a 1,4-benzoquinone, 2-acylthiophenes, and on irradiation of e t/o,enr/o-2,4-bis[( )-2-(methoxycarbonyl)vinyl]bi-cyclo[1.1.0]butane. A formal [2-1-2] cycloaddition also occurred on reaction of tricyclo[3.1.0.0 ]hex-3-ene with methyl 6-oxo-5-phenyl-l,3,4-oxadiazine-2-carboxylate to give methyl 9-oxo-10-phenyl-8-oxapentacyclo[4.4.0.0 ". 0 .0 °]decane-7-carboxylate, albeit in very low yield, after nitrogen extrusion. ... 

The present strategy was successfully applied to the preparation of adamantane-dicarboxylic acid, which is an interesting monomer in polymer chemistry, through a stepwise procedure (Eq. (6.24)), although the dicarboxylic acid is difficult to obtain by conventional methods. Similarly, 1,3-dimethyladamantaneand mdo-tricyclo[5.2.1.0] decane were carboxylated to the respective mono- and dicarboxylic acids. 

Similarly, reductions of different racemic 2-oxabicyclo[3.2.0]heptan-6-ones [139], 2-oxabicyclo[2.2.1]heptane-7-carboxylates [140], norbomenone [102], and bicyclo[2.2.2]octan-2-one [141] have been performed the ee values, however, were moderate. For the reduction [141] of a 4-twistanone (tricyclo[4.4.0.0 ]decan-4-one), the alternative use of Rhodotorula rubra has been suggested. Kinetic resolution of racemic 5,6-epoxy-bicyclo[2.2.1]heptane-2-one using whole cells of genetically engineered S. cerevisiae allowed the synthesis of (+)-5,6-epoxy-bicyclo[2.2.1] heptane-2-ol [142]. 

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