A Theoretical Investigation of Enantioselectivity: Michael Reaction of Secondary Enamines with Enones

A theoretical study of the enantioselective Michael-type addition of chiral secondary enamines to enones has been achieved. In a first step, the structures of various free enamines have been investigated at the ab initio and MNDO levels. The results clearly show that upon substitution of the prototype vinylamine, the N-center is pyramidalized. The study of enamines with chiral N-substituents such as (S)-Ph(Me)CH or (S)-cyclohexyl(Me)CH reveals a very complex pattern, where up to 8 local energy minimums are characterized whose examination shows that no prediction can be. done regarding the final enantioselectivity of their reaction with enones. These sets of conformers can be regarded as nearly energetically degenerate, at least for the three or four ones of lowest energy. The study of the compact complexes formed between the latter optimal conformers and acrylaldehyde shows that: (i)syn complexation with respect to the N lone pair is the only one which remains possible for steric reason, (ii) small geometrical rearrangements take place as the complexation proceeds, (iii) no clear-cut correspondence exists between the relative sequence of the low-energy conformers of the free enamines and the sequence of the low-energy complexes, (iv) the examination of the relative gradients of the complexation energies provides an index for predicting the relative facilities of the enantiometric pathways, in good agreement with the experimental facts. Our study emphasizes the great complexity of systems of realistic size and brings about critical conclusions regarding classical ad hoc models.     

N-H..S hydrogen bonds

Infrared spectra of some compounds containing weak and medium-strong NH..S hydrogen bonds have been investigated. Spectroscopic and structural data have been correlated and compared with those obtained for NH..O and NH..N systems. At the same strength, the N..S distance is 0.51 and 0.36 Å longer than the corresponding N..O and N..N distances, respectively.     

Example of diffusion in a disordered Lorentz gas

We prove a diffusion law for a disordered Lorentz gas obtained by modification of a model of Gates, Gerst, Kac in Ref. 1, even though the motion is not a Markovian one in the technical sense of the word.     

Polarisation remanente dans les varietes de basse temperature de (NH4) 3AlF6 ET (NH4) 3FeF6

Dielectric and thermocurrent measurements have been carried out on (NH₄) ₃AlF₆ and (NH₄) ₃FeF₆ ceramic samples. A maximum of permittivity is observed close to the transition temperature (T_{T(NH4) 3AlF6} = 217K; T_T(NH43FeF6 = 264K. In the low-temperature phase a polarization current of about 10^-9A is obtained and can be reversed when the sign of the polarization field is changed, a property which could correspond to a ferroelectric behavior. However, no pyroelectric current is detected when the temperature decreases from T_T. Another hypothesis, based on a field-induced polarization, has been considered : the depolarization current could be due to charge displacements from potential minima favored by rising temperature. In any way, the low-temperature phase is characterized by a remanent polarization.     

Fluoration de telomeres polyhalogenes par le fluorure de potassium: synthese d'olefines perfluorees

Action of potassium fluoride on chlorofluorinated telomers of general formula Cl-(CFCl-CF₂)_n-CCl₃ leads to a mixture of perfluorinated cis isomers of internal olefins with the more substitued isomer being preponderant. The influence of temperature and solvant has also been studied. Only reactions carried out in tetramethylene sulfone or preferably in dimethylsulfoxide lead to perfluorinated alkenes. We suggest a mechanism with elimination followed by fluorination.     

Phosphoranes bicycliques a liaison PH : Bases de Lewis potentielles

By reaction of Borane Dimethyl Sulfide on the bicyclophosphorane $\text{1}$ the adduct $\text{2}$ is obtained with 56 % yield; by-products $\text{3}$ and $\text{4}$ are characterized .     

Anionic polymerization of 2-vinylpyridine initiated by symmetrical organomagnesium compounds in tetrahydrofuran

Anionic polymerization of 2-vinylpyridine has been studied, initiated either by dialkyl and diaryl magnesium or by living oligomers in tetrahydrofuran solution at 20°C. Spectrophotometric observations indicate the existence of stable active species with different structures. Kinetic data for propagation and viscosimetric measurements on two-ended polymers agree with a cyclic structure of living polymers and lead us to the conclusion of the existence of reactive negative “tripleions.”     

Isomerisation de l'ion moleculaire de derives substitues polycycliques du benzodioxinne-1,4

Three fragmentations (loss of phenyl, hydrogen and a RCO radical) of benzocyclobutene derivatives of differently substituted 1,4-benzodioxin were studied. In some cases these molecules, deuteriated in a specific position, revealed the existence of several isomers of the molecular ion.