Cis-decalin

The Birch reductions of C C double bonds with alkali metals in liquid ammonia or amines obey other rules than do the catalytic hydrogenations (D. Caine, 1976). In these reactions regio- and stereoselectivities are mainly determined by the stabilities of the intermediate carbanions. If one reduces, for example, the a, -unsaturated decalone below with lithium, a dianion is formed, whereof three different conformations (A), (B), and (C) are conceivable. Conformation (A) is the most stable, because repulsion disfavors the cis-decalin system (B) and in (C) the conjugation of the dianion is interrupted. Thus, protonation yields the trans-decalone system (G. Stork, 1964B). 

Property Tetralin cis Decalin Mixed isomers trans... 

Examine the structures of trans and cis-decalin. What is the conformation of the two cyclohexane rings in each isomer Obtain the energy of each decalin isomer. Which is more stable and why ... 

This dry ozonation procedure is a general method for hydrox-ylation of tertiary carbon atoms in saturated compounds (Table 1). The substitution reaction occurs with predominant retention of configuration. Thus cis-decalin gives the cis-l-decalol, whereas cis- and frans-l,4-dimethylcyclohexane afford cis- and trans-1,4-dimethylcyclohexanol, respectively. The amount of epimeric alcohol formed in these ozonation reactions is usually less than 1%. The tertiary alcohols may be further oxidized to diols by repeating the ozonation however, the yields in these reactions are poorer. For instance, 1-adamantanol is oxidized to 1,3-adamantane-diol in 43% yield. Secondary alcohols are converted to the corresponding ketone. This method has been employed for the hydroxylation of tertiary positions in saturated acetates and bromides. 

Parameters Toluene cis-Decalin frans-Decalin Cyclohexane... 

Furthermore, while no significant difference in the product distribution, with the exception of the trans-decalin/cis-decalin ratio, is observed for the tested proton-form zeolites, dissimilarity between Pt/H-Y on one hand and both Pt/H-Beta zeolites on the other hand is found (Figure 6). More ROP and CP, accompanied by less Iso, are formed on Pt/H-Y than on Pt/H-Beta zeolites. This implies that the consecutive ring opening and cracking are faster over Y-zeolite than over Beta-zeolites resulting in lower concentration of isomers and higher concentrations of ROP and CP. 

Mechanisms of the formation of the decal ins in the recovered solvent were based on their isotopic contents. The cis-Decalin-die had a greater protium content than the recovered Tetralin-di2-This suggested that hydrogen transfer from the coal to the tetralin is involved in the formation of cis-Decalin. 

The isotopic composition of the Decal ins in the spent solvents is indicative of the mechanisms of their formation. A total of 6 hydrogen atoms are added to the Tetralin to form Decal in. In E10, during the course of the experiment, the average protium concentration in the Tetralin increased from 2.3 to 21.3 atom % 1H. The protium content of 34 atom % 1H in the cis-Decalin was greater than the protium content in the Tetralin. Likewise in El9, the protium content in the Tetralin increased from 1.0 to 12.3 atom% H, while the cis contained 18.8 atom % 1H. This increase of pro-... 

Tetralin. Therefore, either trans-Decalin was formed on the surface of the coal with deuterium from the solvent or gas, or it was formed by isomerization from cis-Decalin with accompanying isotopic exchange with a deuterium source. Because the protium content of the cis-Decalins is much greater than the trans-Decalins, cis-trans isomerization is not very important. 

An investigation of the isotopic composition of the Decal ins, which were formed as minor products in the donor solvent experiments, showed that cis-Decalin was formed preferentially. Its formation and its increased protiurn incorporation may have resulted from increased contact with the coal surface. Trans-Decal in contained less protiurn than the Tetralin, which suggests that most of the trans-Decalin was formed with deuterium from the Tetralin-di2 and deuterium gas. 

Because the cis-decalin molecule extends its two methine carbon-hydrogen bonds on the same side in contrast to frans-decalin, the carbon-hydrogen bond dissociation of adsorbed decalin would be advantageous to the cis-isomer on the catalyst surface (Figure 13.17). A possible reaction path by octalin to naphthalene in dehydrogeno-aromatization of decalin will be favored to the cis-isomer, since its alkyl intermediate provides the second hydrogen atom from the methine group to the surface active site easily. 

Starting from quinic acid, a highly substituted, cis-afi unsaturated nitrile oxide has been synthesized and used in a 1,3-dipolar cycloaddition, to afford a precursor of the cis -decalin system of branimycin (468). 

Once regioselective and stereoselective controls have been exerted, the cis-decalins must be isomerised to rrans-decalins, the configuration present in the target molecules. Since frans-decalins are thermodynamically more stable than the corresponding cis-decalins, it is possible to isomerise the latter through enolisation, a process that can be favored by the presence of a carbonyl group near to the centre to be inverted. 

On the other hand, twistane is a chiral molecule and the disconnection of either one of the two identical strategic bonds, 11 and 12, in each one of two possible enantiomers leads to one of the two possible conformationally enantiomeric cis-decalins (Aj and A2), the resolution of which is indeed not possible since they... 

Synthesis of twistane from cis-decalins. Strategic bond... 

When we look at the structures of trans- and cis-decalin, it is apparent that a further plane of symmetry, through the ring fusion, is present in both structures. This means that each isomer is superimposable on its mirror image consequently, there are only two configurational isomers of decalin, one trans and one cis. 

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