Tricyclo decane, preparation

Wiseman and coworkers have succeeded in preparing tricyclo[5.3.0.0 ]decane (393), a CioHig hydrocarbon which unlike adamantane is chiral. Their elegantly simple approach entails Diels-Alder addition of cyclobutene to l,4-dihalocyclohexa-l,3-dienes, catalytic hydrogenation of the adduct, reaction with aluminium triiodide, and ultimately di- -butyltin dihydride reduction. 

Twistane derivatives (tricyclo [4.4.0.03>8 ] decanes) may be prepared in one step from the readily available ds-decal in-2,7-dione (Eq. (26)) 85, 86. ... 

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. 

Figure 11. Molecules that are chiral in the excited state only, (a) (lS,3R,7R,9S)-tricyclo-[7.3.0.03 7]dodecane-5,11 -dione in the electronic ground state, (RS), and in locally excited n ->Jt states, (.RS ) and (RS).5S (b) 3-(1nJt )-(lS,6R)-bicyclo[4.4.0.]decane-3,8-dione prepared by thermal decomposition of enantiopure 1,2-dioxetanes. 56...

An additional example is a two-step approach to the preparation of 1,5-cyclo-decadiene. By a photochemical cycloaddition of a substituted cyclobutene and 2-cyclohexenone, a strained tricyclo[4.4.0.02,5]decane system is generated. Thermolysis of the tricycle gave 1,5-cyclodecadiene [52]. 

Polyisocyanates bicyclo[2.2.1]heptane-2,5(6)-diisocyanate, (VII), and tricyclo [5.2.1.0. ]-decane-3(4),8(9)-diisocyanate were used by Haseyama [4] to prepare high-transparency polythiourethane, (VIII), lens materials. 

Camphorsultam. 10,10-Dimethyl-3-thia-4-aza-tricyclo[5.2.1.0 ]decane 3,3-dioxide (camphorsultam, 2, Scheme II) was prepared according to the literature (76), using camphorsulfonic acid as a starting compound. 

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. 

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