Decalin derivatives reactivity

In 2001, Marko et al. reported a neutral variant of their Cu Cl(phen)-DBADH2-base system 91). A catalytic amount of base was used, i.e., 5mol% potassium er -butoxide, which was advantageous for pH-sensitive substrates and products. The order of addition of the different reactants turned out to be crucial for the reactivity. The best catalytic procedure was obtained when the base was added to the [Cu Cl(Phen)]2 complex in the presence of the alcohol, followed by the addition of DEAD. A number of sensitive and/or sterically hindered alcohols were oxidized at 80°C using this optimized protocol and the results are shown in Table IX 91). (lS,2S,5i )-Neomenthol was converted to menthone without any epimerization to isomenthone. A rather hindered decaline derivative could be smoothly oxidized as well as... 

Thiazoles have a low reactivity in cycloaddition reactions due to their high aromatic character. However, it has been possible to achieve intramolecular Diels-Alder reactions in some cases. The reaction of the acetylenic thiazole (66) in decalin at 350 °C affords, after loss of acetonitrile, the thiophene derivative (67) in 75% yield (Equation (16)). The reaction is also applicable to other thiazoles although with some limitations <88T3327>. 

As good examples for the analytical approach for dicyclic terpanes we chose camphane and decalin. Camphane derives from its ketone precursor (i.e. camphor) and decalin is the fully hydrogenated naphthalene. The two bicyclic compounds exhibit large differences in their physical properties and also in their chemical reactivity. The camphane belongs to the bridged bicyclics whereas the decalin is a fused dicycloalkane. Hence in decalin we have cis, trans isomers. In the cis the two hydrogens point in the same direction, whilst in the trans they point in different directions. 

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