Aliphatic cyclic tertiary amines constitute a major class of naturally occurring and synthetic drugs directed at central biogenic amine receptors. Microsomal metabolism of these amines is known to be associated with low levels of covalent binding and/or suicide inactivation of the pertinent metabolizing P-450 isozymes; two of the more notorious examples are phencyclidine (1-(1phenylcyclohexyl)p...

Quantum-chemical calculations were performed for all possible isomers of neutral aniline and its redox forms, and intramolecular proton-transfer (prototropy) accompanied by π-electron delocalization was analyzed. One-electron oxidation (PhNH(2) - e → [PhNH(2)](+•)) has no important effect on tautomeric preferences. The enamine tautomer is preferred for oxidized aniline similarly as for the neut...

The discovery of new strategies that emulate nature!s capacity to rapidly construct architectural complexity continues to be a central focus for research and development in the chemical sciences. Recently, our laboratory disclosed the concept of organocascade catalysis, a new chemical paradigm that combines two modes of catalyst activation (iminium and enamine catalysis) into one mechanism, the...

General and operative domino Claisen-Schmidt/Henry (CS/H) reaction has been revealed to obtain highly substituted chiral decalines in good yields with excellent ees and des by using push-pull enamine catalysis.

Through the studies on structure-activity relationships o f 5-acyl-3-(l-aminoalkylidene)4-hydroxy-2 H-pyran-2,6(3 H)-dione derivatives in photosystem II (PS II) inhibition, overall lipophilicity o f the molecule was found to be a major determinant for the activity. In the sub­ stituted N-benzyl derivatives, not only the lipophilicity but also the electronic and steric char­ acters o f the subst...

Asymmetric enamine base activation of carbonyl compounds is a well-known and widely used strategy for providing functionalization organic in an efficient way. The use solely substances, which most cases are commercially available primary or secondary amines that easy to obtain, avoids the hazardous substances metal traces, making this type catalysis highly convenient methodology from sustainabl...

SOMO catalysis has lately obtained large interest as a new and powerful version of enantioselective organocatalysis which includes radical steps initiated by a one-electron oxidation. The intermediate enamine radical cation has been postulated, but has not been observed directly so far. This communication now reports the direct detection of this key intermediate.

Aldehydes can be α-alkylated with allenamides by the combined action of an organocatalyst and a gold complex. The reaction requires the simultaneous generation of an enamine and a gold-activated allenamide. Importantly, by using a chiral amine as organocatalyst it is possible to obtain aldehyde products featuring all-carbon quaternary stereocenter at their α-position, with moderate to good leve...

Cationic rhodium(I) complexes containing the flexible hemilabile phosphine ligand (3-ethoxypropyl)diphenylphosphine efficiently catalyzed the anti-Markovnikov oxidative amination of styrene in tetrahydrofurane at 80 degrees C to produce (E)-1-styrylpiperidine with turnover frequencies up to 75 h(-1) with excellent enamine selectivity (96%).