a method is described by which it is possible to determine the high barrier to ring inversion and hindered rotation by neat racemization of optically active compounds when the racemization is caused by ring inversion or hindered rotation. the method is based preparation of sufficiently pure enantiomers, mainly by chromatography on swollen microcrystalline triacetylcellulose (tac). by this techn...

A method is described by which it is possible to determine the high barrier to ring inversion and hindered rotation by neat racemization of optically active compounds when the racemization is caused by ring inversion or hindered rotation. The method is based preparation of sufficiently pure enantiomers, mainly by chromatography on swollen microcrystalline triacetylcellulose (TAC). By this t...

Human dipeptidyl-peptidase III (h.DPP III) is a zinc-exopeptidase that hydrolyses dipeptides from the N-terminus of its substrates. Its mechanism of action was assumed to be similar to that of thermolysin, but was never thoroughly investigated. This study presents the first insight into the reaction mechanism of h.DPP III, determined on the model and real (hydrated enzyme with Leu-enkephalin bo...

DFT-GGA method of Perdew-Burke-Ernzerhof (PBE) is used with aug-cc-PVTZ, 6-311++G**, and Def2-TZVP large basis sets to study the hydrogen bond interactions between oxygen lone pair as a donor electron with hydrogen atom connected to the aniline’s nitrogen as an electron acceptor (H2O···HNH-Ph), and nitrogen lone pair with hydrogen of water molecule (Ph-H2N···HOH...

ab initio calculations were employed to investigate nitrogen inversion as a configuration change that can supply an infinitely useful switchable control mechanism for some complex systems. in this paper, design of a new artificial molecular nanohinge is discussed based on nitrogen inversion in which reciprocating motion of substituent in effect of inversion phenomenon, led to an open–close moti...

mndo semi-empirical scf mo calculations are used to study the pyramidal nitrogen atom inversion and configurational equilibria in the title compounds.

Equatorial/axial conversion in piperidine and phosphorinane with different substituents wereinvestigated with great details. Three possible routes, i.e. heteroatom inversion and two ring inversiontype were considered. Ring conversion can occur via two pathways one starts with ring flatteningfrom the heteroatom site (nitrogen in piperidine and phosphorous in phosphorinane) and the otherinitiates...

The intrinsic conformational and structural properties of the tropinone azabicycle have been investigated in a supersonic jet expansion using rotational spectroscopy. The spectrum revealed the presence of equatorial and axial conformers originated by the inversion of the N-methyl group, with the tropane motif adopting a distorted chair configuration. The determination of substitution and effect...

equatorial/axial conversion in piperidine and phosphorinane with different substituents wereinvestigated with great details. three possible routes, i.e. heteroatom inversion and two ring inversiontype were considered. ring conversion can occur via two pathways one starts with ring flatteningfrom the heteroatom site (nitrogen in piperidine and phosphorous in phosphorinane) and the otherinitiates...

A bowl-shaped nitrogen-doped nanographene composed of a pyrrolo[3,2-b]pyrrole core substituted with six arene rings circularly bonded one another undergoes bowl-to-bowl inversion low barrier. This resembles that an umbrella flipped by the strong wind. The transition state is not planar, but possesses rather twisted, S-shaped conformation Ci symmetry. bowl-inversion mechanism follows quadruple-w...