A Highly Efficient Solvent-Free Asymmetric Direct Aldol Reaction Organocatalyzed by Recoverable (s)-Binam-L-Prolinamides. ESI-MS Evidence of the Enamine-Iminium Formation

Recoverable (Sa)-binam-l-prolinamide in combination with benzoic acid is used as catalysts in the direct aldol reaction between cycloalkyl, alkyl, and α-functionalized ketones and aldehydes under solvent-free reaction conditions. Three different methods are assayed: simple conventional magnetic stirring, magnetic stirring after previous dissolution in THF and evaporation, and ball mill technique. These procedures allow one to reduce not only the amount of required ketone to 2 equiv but also the reaction time to give the aldol products with regio-, diastereo-, and enantioselectivities comparable to those in organic or aqueous solvents. Generally anti-isomers are mainly obtained with enantioselectivities up to 97%. The reaction can be carried out under these conditions also using aldehydes as nucleophiles, yielding after in situ reduction of the aldol products the corresponding chiral 1,3-diols with moderate to high enantioselectivities mainly as anti-isomers. The aldol reaction has been studied by the use of positive ESI-MS technique, providing the evidence of the formation of the corresponding enamine−iminium intermediates.

Diversity for Texts Builds in Language L(MT): Indexes Based in Theory of Information

If one has a distribution of words (SLUNs or CLUNS) in a text written in language L(MT), and is adjusted one of the mathematical expressions of distribution that exists in the mathematical literature, some parameter of the elected expression it can be considered as a measure of the diversity. But because the adjustment is not always perfect as usual measure; it is preferable to select an index that doesn't postulate a regularity of distribution expressible for a simple formula. The problem can be approachable statistically, without having special interest for the organization of the text. It can serve as index any monotonous function that has a minimum value when all their elements belong to the same class, that is to say, all the individuals belong to oneself symbol, and a maximum value when each element belongs to a different class, that is to say, each individual is of a different symbol. It should also gather certain conditions like they are: to be not very sensitive to the extension of the text and being invariant to certain number of operations of selection in the text. These operations can be theoretically random. The expressions that offer more advantages are those coming from the theory of the information of Shannon-Weaver. Based on them, the authors develop a theoretical study for indexes of diversity to be applied in texts built in modeling language L(MT), although anything impedes that they can be applied to texts written in natural languages.