A total synthesis of tarchonanthuslactone exploiting N-pyrrole carbinols as efficient stereocontrolling elements

[reaction: see text] A short stereoselective total synthesis of the polyketide natural product, tarchonanthuslactone, has been achieved. The key sequence involves the first reported catalytic enantioselective reduction of an N-acyl pyrrole and subsequent use of this stereocenter in a diastereoselective reductive cascade. This proceeded with unprecedentedly high stereocontrol and offered an elegant method of generating the desired syn stereochemistry present in the final target in one step.     

Computer simulation studies of anisotropic systems. The influence of external fields on the nematic—isotropic transition

The results of Monte Carlo simulations are reported for a model nematogen in the presence of an intense magnetic field. The predictions of a molecular field theory for the system are found to be in reasonable accord with the simulations. It would appear therefore that the critical field for a real nematogen may be unobservably high.     

Field-induced alignment of a smectic-A phase: a time-resolved x-ray diffraction investigation

The field-induced alignment of a smectic-A phase is, in principle, a complicated process involving the director rotation via the interaction with the field and the layer rotation via the molecular interactions. Time-resolved nuclear magnetic resonance spectroscopy has revealed this complexity in the case of the director alignment, but provides no direct information on the motion of the layers. Here we describe a time-resolved x-ray diffraction experiment using synchrotron radiation to solve the challenging problem of capturing the diffraction pattern on a time scale which is fast in comparison with that for the alignment of the smectic layers. We have investigated the alignment of the smectic-A phase of 4-octyl-4(')-cyanobiphenyl by a magnetic field. The experiment consists of creating a monodomain sample of the smectic-A phase by slow cooling from the nematic phase in a magnetic field with a flux density of 7 T. The sample is then turned quickly through an angle phi(0) about an axis parallel to the x-ray beam direction but orthogonal to the field. A sequence of two-dimensional small angle x-ray diffraction patterns are then collected at short time intervals. Experiments were carried out for different values of phi(0), and at different temperatures. The results show that the alignment behavior changes fundamentally when phi(0) exceeds 45 degrees, and that there is a sharp change in the alignment process when the temperature is less than 3 degrees C below the smectic-A-nematic transition. The results of the x-ray experiments are in broad agreement with the NMR results, but reveal major phenomena concerning the maintenance of the integrity of the smectic-A layer structure during the alignment process.     

Biaxial nematics: computer simulation studies of a generic rod-disc dimer model

One possible route to the elusive biaxial nematic phase is through rod-disc dimers in which the rod and disc mesogenic units are linked via a flexible spacer. We have developed a continuous generic model of such rod-disc dimers in which neighbouring like groups tend to align parallel to each other while unlike groups tend to be orthogonal. A torsional potential controls the relative orientations of the groups within a single dimer; depending on the strength of the torsional potential, the groups may be orthogonal or parallel in the conformational ground state. Monte Carlo simulations show that a rigid rod-disc dimer is most likely to form a biaxial nematic phase if the anisotropies of the two groups are the same. Introduction of flexibility is found to have little effect on the qualitative behaviour of the dimer as the relative anisotropy of the two mesogenic groups is changed. However, when the torsional potential strongly favours the alignment of the rod and disc within a single molecule with their symmetry axes parallel there is a dramatic change. The system then exhibits a strong hysteresis in the molecular shape and biaxiality and the biaxial nematic-isotropic transition becomes strongly first order, in marked contrast to the second-order character usually found for this transition. This first-order transition is observed to occur for a range of relative anisotropies of the two groups rather than at a single point.     

Electric-field driven director oscillations in a nematic liquid crystal: a NMR investigation

We have investigated the oscillatory behavior of the nematic director for 4-pentyl-4'-cyanobiphenyl (5CB) when it is subjected to a static magnetic field and a sinusoidal electric field. In these experiments the two fields were inclined at about 50 degrees and the frequency of the electric field was varied from several hertz to approximately 1000 Hz. The director orientation was measured using time-resolved deuterium NMR spectroscopy since this has the advantage of being able to determine the state of director alignment in the sample. In fact, for all of the frequencies studied the director is found to remain uniformly aligned. Since the diamagnetic and dielectric anisotropies are both positive the director oscillates in the plane formed by the two fields. These oscillations were observed to continue for many cycles, indicating that the coherence in the director orientation was not lost during this motion. The maximum and minimum angles made by the director with the magnetic field were determined, as a function of frequency, from the NMR spectrum averaged over many thousand cycles of the oscillations. At low frequencies (several hertz) these limiting angles are essentially independent of frequency but as the frequency increases the two angles approach each other and become equal at high frequencies, typically 1000 Hz. Our results are well explained by a hydrodynamic theory in which the sinusoidal time dependence of the electric field is included in the torque-balance equation. This analysis also shows that, for a range of frequencies between the high and low limits, these NMR experiments can give dynamic as well as static information concerning the nematic phase.     

Asymmetric dimeric liquid crystals The preparation and properties of the α-(4-cyanobiphenyl-4'-oxy)-ω-(4-n-alkylanilinebenzylidene-4'-oxy)hexanes

Abstract

The first eleven members of the homologous series of α-(4-cyanobiphenyl-4'-oxy)-ω-(4-n-alkylanilinebenzylidene-4'-oxy)hexanes have been synthesized. The compounds are all enantiotropic nematogens and, with the exception of the heptyl, octyl and nonyl homologues, exhibit smectic phases. The thermal stability of the smectic A phase initially increases with the length of the terminal alkyl chain, passes through a maximum and then falls dramatically before disappearing. The smectic A phase subsequently reappears with the decyl homologue which has the highest smectic A-nematic transition temperature of the series. In order to understand this unusual behavior we have determined the entropies of transition for the compounds and we have measured the layer spacing of the smectic A phase for three of them.     

Pretransitional behaviour in nematic liquid crystals

A simple (four sites on the water molecule) potential for Cl^-/H₂O has been generated from six gradient calculations. The potential is in reasonable agreement with the extensive SCF calculations of Dacre.