William Smadja

Acyclic diastereofacial selection in radical addition.

Abstract 1,2-asymmetric induction with up to 83 % of diastereoisomeric excess has been observed during intermolecular addition of silicon centered radical to carbon-carbon double bond of chiral non-racemic α,β- unsaturated esters derived from glyceraldehyde acetonide. The stereoselectivity observed should be mainly due to some electronic effects.

Phénylation d'alcools allyliques acycliques : II. Regioselectivite du transfert d'hydrogene

PdCl2, HNaCO3-catalysed phenylation of deuterium-labelled allylic butenols, a Heck type reaction, proceeds by a highly regioselective 1,2-hydrogen shift via a Wacker type intermediate. No decomplexed enol was formed during this reaction.

RuCl3–NaOH as a reaǵent for chirality transfer. Synthesis of chiral β-deuteriated ketones by asymmetric induction

Chiral β-deuteriated acyclic ketones have been quantitatively obtained by a 37% stereospecific isomerisation of the corresponding allylic alcohols.

Chirality transfer. A stereospecific palladium salt catalyzed phenylation of chiral butenols.

Abstract (R)-(|) and (S)-(+)-3-phenyl butanones have been obtained by a 20% stereospecific palladium catalyzed β-phenylation of the corresponding chiral butenols, the catalyst acting preferentially, through an alkoxide complex, by one face of the alcohol double bond, e.g. the si face of (R)-(|)3-butene-2-ol(I).

Analysis of natural abundance deuterium NMR spectra of enantiomers in chiral liquid crystals via 2D auto-correlation experiments

Natural abundance deuterium auto-correlation 2D NMR experiments of enantiomers orientated in a chiral polypeptide liquid crystalline solvent (PBLG) are used as a novel analytical tool for the study of chiral solutes.

Visualisation of axial chirality using 2H-{1H} NMR in poly(γ-benzyl L-glutamate),a chiral liquid crystal solvent

Disubstituted, racemic, axially chiral compounds with true and isotopic chiralities have been discriminated through the differential ordering effect of enantiomers when dissolved in a chiral liquid crystal solvent made of organic solutions of poly(γ-benzyl L-glutamate).

RuCl3, NaOH-catalyzed isomerization of allylic alcohols to saturated ketones: Part II Regiochemistry

Abstract The RuCl 3 , NaOH-catalyzed isomerization of allylic alcohols to saturated ketones is shown to occur by an intramolecular 1,3-hydrogen shift. The rate-determining step does not involve cleavage of an allylic carbon-hydrogen bond.

Deuterium isotope effects in 13C NMR spectroscopy: Stereochemical assignment of monodeuteriated allylic alcohols.☆

Abstract Vicinal deuterium isotope effects on 13C NMR chemical shifts, 3ΔC (Φ) are given for ten monodeuteriated allylic alcohols. The relationship found for nine of them: 3ΔC(0°) ≅ 5/3 x 3ΔC(180°) allows the stereochemical assignement of their deuterium labeling. This assignment is in agreement with that from the Karplus-type relationship of vicinal coupling constants, 3JC-D(Φ).