Trigger tautomer

In line with the mechanistic results from above and from the oxidation of stable enols (Sect. 3.1), the following mechanism was postulated (Scheme 8). Considering the multistep nature of the mechanism it is obvious that several, sometimes conflicting requirements have to be accomodated in the reaction system to maximize yields. For example, the redox potential of the oxidant has to be low in order to avoid dir rt oxidation of the carbonyl compound, but should still allow oxidation of the enol tautomer. In this case the chosen oxidant may turn out to be too weak for fast oxidation of the a-carbonyl radical intermediate, and as a consequence only radical reactions will be triggered. 

This addition does not correct the issues with tautomers, but it does allow an easy way to detect tautomers in the database. Note also that alerting the user is the responsibility of the client program and is not performed in this trigger function or in any of the other constraints in the registration schema. 

There is some overhead in the use of indexes, constraints, triggers, etc. as discussed here. The overhead is incurred when rows are inserted or updated in the table. However, the value of this approach is that the data in the table are well validated and can be searched more reliably and efficiently. Direct lookups of canonical or stereo SMILES is simple and quick because of the index on these columns. Using the fingerprint column speeds up substructure search. Tautomers can be readily selected using the column of simple graphs. 

Although the experimental determination of K is possible, see Chapters 2 and 5 in [1], the theoretical calculations raise important questions. If Eq. 6.4 is applied for a real solution, the standard chemical potential is hypothetical, and does not correspond to any real physical state. Thus, if one wants to calculate K theoretically as exp(-( g - fi )/RT), no direct modeling of the individual values is possible. When a continuum solvent approach is applied, the customary way to calculate K is setting the in-solution determined AGt t equal to —RT In K. This assumption triggers a very important question. Through the calculations of the individual Gs, it is assumed that the solute-solute interactions, including the interactions of the tautomeric forms should not be taken into consideration. Thus, for these very dilute solution models, only one tautomer is considered as a solute. Then the derived for the solutes in the modeled dilute solutions is... 

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