New chiral cyclooctatriene-based polycyclic architectures

The synthesis and properties of new chiral polycyclic architectures that display both helicity and a saddle-type shape are described. The enantiomers have been separated, and their absolute configuration was determined by VCD and ECD. The unprecedented molecular architecture is based on a cyclooctatriene core surrounded by an association of benzo[c]fluorene and ortho-phenylene units.     

Enantioselective alkylidenecyclopropanation of norbornenes with terminal alkynes catalyzed by palladium–phosphinous acid complexes

Pd(II)-coordinated phosphinous acids catalyzed the formal enantioselective [2+1] cycloaddition of norbornene derivatives with terminal alkynes. The absolute configuration of (+)-3aa was assigned using VCD.     

Breaking Symmetry Relaxes Structural and Magnetic Restraints,Suppressing QTM in Enantiopure Butterfly Fe2Dy2 SMMs**

The {Fe₂Dy₂} butterfly systems can show single molecule magnet (SMM) behaviour, the nature of which depends on details of the electronic structure, as previously demonstrated for the [Fe₂Dy₂(μ₃-OH)₂(Me-teaH)₂(O₂CPh)₆] compound, where the [N,N-bis-(2-hydroxyethyl)-amino]-2-propanol (Me-teaH₃) ligand is usually used in its racemic form. Here, we describe the consequences for the SMM properties by using enantiopure versions of this ligand and present the first homochiral 3d/4 f SMM, which could only be obtained for the S enantiomer of the ligand for [Fe₂Dy₂(μ₃-OH)₂(Me-teaH)₂(O₂CPh)₆] since the R enantiomer underwent significant racemisation. To investigate this further, we prepared the [Fe₂Dy₂(μ₃-OH)₂(Me-teaH)₂(O₂CPh)₄(NO₃)₂] version, which could be obtained as the RS-, R- and S-compounds. Remarkably, the enantiopure versions show enhanced slow relaxation of magnetisation. The use of the enantiomerically pure ligand suppresses QTM, leading to the conclusion that use of enantiopure ligands is a “gamechanger” by breaking the cluster symmetry and altering the intimate details of the coordination cluster's molecular structure.     

Experimental study of the near-field impact of an oyster table on the flow

Oyster farming structures are artificial obstacles which disturb tidal flow and wave propagation. These effects can induce modifications of erosion and sedimentation patterns, turbidity changes, local silting up and can be threatening for the shellfish farming itself. The understanding of the impact of these structures in terms of hydrodynamics and sediment dynamics in the far-field, i.e. at the scale of a bay, is a very challenging task.In order to investigate the far-field impact, it is very important to understand in the first place all the changes which occur at a smaller scale, i.e. at the scale of a single table for a farm consisting of oyster tables made of metallic wire structures on which porous bags of oysters are laid. This work is carried out through the idealized representation of the in-situ flow in a free surface flume tank. The flow characteristics around the overall structure are determined from velocity measurements obtained by laser velocimetry. The results highlight an asymmetric development of the boundary layers which suggest the existence of preferential areas for silting up and suspended matter fragmentation under the table.     

The absolute configuration of an inherently chiral phosphonatocavitand and its use toward the enantioselective recognition of l-adrenaline

An inherently chiral ABii diphosphonato cavitand (±)-4 bearing a single quinoxaline bridging moiety was synthesized and resolved by chiral HPLC. Its chiroptical properties were investigated and VCD experiments allowed the determination of its absolute configuration. Distinguishable diastereomeric complexes in solution with l-adrenaline were observed by ¹H and ³¹P NMR together with a noticeable enantio-discrimination at 253 K (dr ～2:1) in favor of the dextrorotatory cavitand (+)-4.     

Stereoselective Syntheses,Structures, and Properties of Extremely Distorted Chiral Nanographenes Embedding Hextuple Helicenes

We report a molecular design and concept using π-system elongation and steric effects from helicenes surrounding a triphenylene core toward stable chiral polycyclic aromatic hydrocarbons (PAHs) with a maximal π-distortion to tackle their aromaticity, supramolecular and molecular properties. The selective syntheses, and the structural, conformational and chiroptical properties of two diastereomeric large multi-helicenes of formula C₉₀H₄₈ having a triphenylene core and embedding three [5]helicene units on their inner edges and three [7]helicene units at their periphery are reported based on diastereoselective and, when applicable, enantiospecific Yamamoto-type cyclotrimerizations of racemic or enantiopure 9,10-dibromo[7]helicene. Both molecules have an extremely distorted triphenylene core, and one of them exhibits the largest torsion angle recorded so far for a benzene ring (twist=36.9°).     

Chromatographic resolution, solution and crystal phase conformations, and absolute configuration of tert-butyl(dimethylamino)phenylphosphine-borane complex

The enantiomers of tert-butyl(dimethylamino)phenylphosphine-borane complex 2 have been separated by HPLC using cellulose tris-p-methylbenzoate as chiral stationary phase. The borane protection could be removed without racemization and the P-configuration of the free aminophosphine 1 has shown to be stable in solution. Infrared (IR) and vibrational circular dichroism (VCD) spectra have been measured in CD2Cl2 solution for both enantiomers. B3LYP/6-31+G(d) DFT calculations allowed a prediction that complex (S)-2 exists as three conformers in equilibrium and computed population-weighted IR and VCD spectra. Predicted and experimental IR and VCD spectra compared very well and indicate that enantiomer (+)-2 has the S absolute configuration. This assignment has been confirmed by an X-ray diffraction study on a single crystal of (+)-2. The crystal structure of enantiomerically pure 2 appears to be very close to the most stable computed conformer which proved to be predominant in solution.     

Enantiospecific Syntheses of Congested Atropisomers through Chiral Bis(aryne) Synthetic Equivalents

The synthetic equivalents of the enantiopure binaphthyl bis(aryne) atropisomers derived from BINOL (1,1′-bi-2,2′-naphtol) featuring a stereogenic axis vicinal to the two reactive triple bonds can be generated for the first time in solution in an enantiospecific manner. Using a two-step sequence based on the bidirectional [4+2] cycloaddition of furan derivatives followed by an aromatizative deoxygenation reaction, several 9,9’-bianthracenyl-based atropisomers could be prepared enantiospecifically in high enantiomeric purity. Alternatively, bidirectional reactions with anthracene, 2-bromostyrene, and perylene as the arynophiles afforded very congested bis(benzotriptycene), bis(tetraphene) and bis(anthra[1,2,3,4-ghi]perylene) nanocarbon atropisomers in equally high enantiomeric purity. In complement, cross reactions with two different arynophiles revealed possible. The unusual atropisomer prototypes described in this study open the way to enantiopure nanographene atropisomers designed for functions.