This section is from the book "Research In Physiopathology As Basis Of Guided Chemotherapy With Special Application To Cancer", by Emanuel Revici. Also available from amazon: Research In Physiopathology
Figure 257 shows the template formation in cortisone, which extends from C11 to C21. Each one of these six carbons will attract a carbon from the radical in front of it. The energetic character of each of the six carbons of the template will determine the electrophilic or nucleophilic character of the carbon so attracted. This attraction is easily induced when acetic radicals, with an electrophilic and a nucleophilic carbon, form these groups. Furthermore, the value of the carbons of the template also will determine which polar radical will be bound to the respective carbon kept in front of it. In general, the carbon kept in front of a carbon of the template will have an opposite electrical sign. The polar group bound to the carbon kept in place will be opposite in sign to the polar group bound to the carbon of the template. When the first polar group takes a position parallel to that of the polar group of the template, both will have the same electrical sign.
It can be seen that C21 within the template has an OH, the group being electrophilic. This will cause the carbon kept in front to preferably bind an oxygen, realizing a nucleophilic center. C20 of the template, which corresponds to a carbonyl, represents a nucleophilic center. With an oxygen bound through a double bond, it has strong reactivity. The positivity of C20 also is highly enhanced through its bond to the two strongly negative carbons, C20 and C17, each being bound respectively to a hydroxyl. With this high positivity, C20 will induce a strong reactivity in the carbon kept in front of it. This will be strong enough to bind a radical energetically opposite to oxygen and stronger than the hydroxyl; that is, an amino group.
The special position of the OH bound to C17 as related to the template will induce the carbon kept in front of it to bind another hydroxyl. The same applies to carbon 13. This is the result of the relatively strong molecular reactivity of these two carbons, due to the twin formation which they realize. The methyl bound to C13 will determine the steric position of the hydroxyl bound to the respective carbon kept in front of this carbon.
The effect of carbon 12 is different. It is highly influenced by the twin formation and has an opposite energetic character to carbons 13 and 17, consequently, it will favor the binding of the carbon kept in front of it to an oxygen which is the same which binds the carbon in front of C21. Posi tionally, the carbon in front of C12 also will be nearest to the C kept in front of C21, which also was induced to bind an oxygen as seen above. This will make it possible for a similar oxygen to be bound by the two carbons kept in front of C12and C21, thus closing an hexagonic cycle. The radical bound to carbon 11 will cause the carbon in front of it to bind an opposite radical. In the cases in which C11 has an oxygen bound to it, as in cortisone, the carbon kept in front of it will bind a hydroxyl. The presence of an hydroxyl bound to C11, as in hydrocortisone, will cause a carboxyl to be bound to the respective carbon kept in front of it. It is thus seen that the synthesis induced by the template formation of cortisone will result in a molecule of glucosamine, while for hydrocortisone, the synthesized molecule will correspond to glucosamine acid.
Fig. 257. Hypothetical view of the template formation between carbon 11 and carbon 21 of the corticoid molecule. The groups kept in front of the different carbons of the formation serve to synthesize new substances. In the example presented above, the template of the cortisone molecule would lead to the appearance of a glucosamine molecule.