Laurent Vial

Grignard cross-coupling catalyzed by chiral phosphino–quincorine and phosphino–quincoridine derivatives

Abstract New β-aminoalkylphosphines with a stereogenic nitrogen center have been synthesized from quincorine and quincoridine. Nickel catalysts were studied for their enantioselectivity in the asymmetric Kumada–Corriu reaction. The (2 S ,4 S ,5 R )-2-diphenylphosphinomethyl-5-ethyl-quinuclidine–nickel complex led to e.e. of 85% for the cross-coupling of 1-phenylethylmagnesium chloride with vinyl bromide.

Enantioselective Recognition of a Chiral Quaternary Ammonium Ion by C3 Symmetric Cyclic Hexapeptides

C3 Symmetric cyclic hexapeptides containing alternating L-proline and 3-aminobenzoic acid derivatives as subunits possess different affinities towards the two enantiomers of the N,N,N-trimethyl-1-phenylethyl ammonium cation.

On-Demand Cyclophanes: Substituent-Directed Self-Assembling, Folding, and Binding

A family of p-cyclophanes based on bis- or tetrafunctionalized 1,4-bisthiophenol units linked by disulfide bridges was obtained by self-assembly on a gram scale and without any chromatographic purification. The nature of the functionalities borne by these so-called dyn[4]arenes plays a crucial role on their structural features as well as their molecular recognition abilities. Tuning these functions on demand yields tailored receptors for cations, anions, or zwitterions in organic or aqueous media.

Diastereoselective Synthesis of a Dyn[3]arene with Distinct Binding Behaviors toward Linear Biogenic Polyamines

The extension of the family of dyn[ n]arenes toward a three-membered macrocycle is reported. Through a templated approach, a single diastereoisomer of a dyn[3]arene that bears six carboxyl groups could be isolated by precipitation in 59-63% yield and excellent purity (≥95%). A combination of experimental and computational experiments in water at physiological pH revealed that the macrocycle could bind parent biogenic polyamines with a unique diversity of surface-binding modes. Whereas no binding event could be accurately measured with 1,3-diaminopropane, spermidine formed a classical stoichiometric complex with the dyn[3]arene in the millimolar concentration range. On the other hand, the data obtained for spermine could only be attributed to a more complex binding event with the formation of a 2:1 complex at high [host]/[guest] ratios and redistribution toward a 1:1 complex upon further addition of guest.

Novel heteroleptic cis-(C⁁N)2Pd(II) chelates for the preparation of enantiopure planar chiral cyclopalladated 2-[tricarbonyl(η6-phenyl)chromium]pyridine

In the presence of large amounts of [Me4N]Cl, the reaction of ortho-chloromercurated 2-[(eta6-phenyl)tricarbonylchromium]pyridine with mu-chloro cyclopalladated aromatic compounds yields a series of new heteroleptic heterodinuclear cis-(C--N)2Pd(II) complexes, which are valuable precursors of planar chiral cyclopalladated (eta6-arene)Cr(CO)3 complexes.