Palladium-catalysed asylletric allylic alkylation using phosphine-amide derived from chiral trans-2-aminocyclohexanol.

International audienceA novel phosphine-amide derived from resolved trans-2-aminocyclohexanol has been synthesized and studied in palladium-catalyzed asymmetric allylic alkylation of racemic (E)-1,3-diphenyl-2-propenyl acetate with various nucleophiles

Myrtenal and Myrtanal as Auxiliaries in the Synthesis of Some C,P-Stereogenic Hydroxyphosphine Oxides and Hydroxyphosphine-Boranes Possessing up to Four Contiguous Centers of Chirality

1,4- and 1,2-additons of secondary phosphine oxides to (1R)-myrtenal and (1S)-myrtanal were evaluated as potential routes to P,C-stereogenic phosphine oxides bearing additional hydroxyl or aldehyde functions. 1,4-Additions of racemic secondary phosphine oxides to (1R)-myrtenal were found to offer moderate to good stereoselectivity which shows some promise for utility in kinetic resolution processes, especially at lower conversions. In case of 1,2-additions making the process doubly asymmetric by using an enantiomerically pure secondary phosphine oxide as substrate turned out to be practical. The stereochemical course of the addition reactions under study is presented. The P-resolved 1,2-addition products were demonstrated to undergo facile reduction by BH3 at room temperature leading to the formation of the corresponding α-hydroxyphosphine-boranes with clean inversion of configuration at the P-centre. All P,C-stereogenic phosphine oxides and boranes that were isolated in the form of a single diastereoisomer were assigned their absolute configurations by means of X-ray crystallography and/or 2D NMR spectral techniques

Michael-Type Addition of Secondary Phosphine Oxides to (1,4-Cyclohexadien-3-yl)phosphine Oxides

Base-induced reaction between (1,4-cyclohexadien-3-yl)­phosphine oxides and secondary phosphine oxides gives 3,4-bis­(phosphinoyl)­cyclohexenes and 2,3-bis­(phosphinoyl)­cyclohexenes through an in situ isomerization of one of the cyclohexadienyl double bonds and a subsequent Michael-type addition of the secondary phosphine oxide

D-Glucosamine based-phosphine for Suzuki-Miyaura cross-coupling reactions in the supported aqueous phase catalysis system

International audienceA d-glucosamine-based phosphine/Pd(OAc)2 complex has been applied to the Suzuki-Miyaura coupling reaction of aryl bromides with arylboronic acids using the supported aqueous phase catalysis, SAPC, concept. The recyclability of the catalyst was investigated and revealed a very high activity during the 4 runs

Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (<i>R</i>,<i>R</i>)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State

The resolution of racemic 1-phenylphosphin-2-en-4-one 1-oxide (2), was achieved through the fractional crystallization of its diastereomeric complexes with (4R,5R)-(−)-2,2-dimethyl -α,α,α′,α′-tetraphenyl-dioxolan-4,5-dimethanol (R,R-TADDOL) followed by the liberation of the individual enantiomers of 2 by flash chromatography on silica gel columns. The resolution process furnished the two enantiomers of 2 of 99.1 and 99.9% e.e. at isolated yields of 62 and 59% (counted for the single enantiomer), respectively. The absolute configurations of the two enantiomers were established by means of X-ray crystallography of their diastereomerically pure complexes, i.e., (R)-2•R,R)-TADDOL and (S)-2•(R,R)-TADDOL. The structural analysis revealed that in the (R)-2•(R,R)-TADDOL complex, the P-phenyl substituent occupied a pseudoequatorial position, whereas in (S)-2•(R,R)-TADDOL, it appeared in both the pseudoequatorial and the pseudoaxial positions in four symmetrically independent molecules. Concurrent conformational changes of the TADDOL molecules were best described by the observed changes of a pseudo-torsional CO...OC angle that could be considered as a possible measure of TADDOL conformation in its receptor–ligand complexes. The structural analysis of the (R,R)-TADDOL molecule revealed that efficiency of this compound for use as an effective resolving factor comes from its ability to flexibly fit its structure to both enantiomers of a ligand molecule, producing a rare case of resolution for both pure enantiomers with one chiral separating agent. The resolved (R)-2 was used to assign the absolute configuration of a recently described (−)-1-phenylphosphin-2-en-4-one 1-sulfide by chemical correlation. In addition, an attempted stereoretentive reduction of (R)-2 by PhSiH3 at 60 °C revealed an unexpectedly low barrier for P-inversion in 1-phenylphosphin-2-en-4-one

New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis

A simple, highly efficient synthesis of a series of novel chiral non-racemic rigid tetracyclic phosphorus ligands, applicable in important chemical asymmetric transformations, was performed. In a tandem cross-coupling/C-H bond activation reaction, a well-recognised and readily available ligand (R,R)-NORPHOS was used as the starting material. The palladium complexes of new ligands were obtained and characterised on the example of a crystalline dichloropalladium complex of [(1R,2R,9S,10S,11R,12R)-4-phenyltetracyclo[8.2.1.02,9.03,8]trideca-3,5,7-triene-11,12-diyl]bis(diphenylphosphane). A notably high activity and stereoselectivity of the palladium catalysts based on the new ligands were confirmed in a model asymmetric allylic substitution reaction. Herein, we discuss the geometry of the palladium complexes formed and its impact on the efficiency of the catalysts. A comparison of their geometric features with other bis(phosphane) ligand complexes found in the Cambridge Structural Database and built density functional theory (DFT) commutated models is also presented and rationalised

A General Phenomenon of Spontaneous Amplification of Optical Purity under Achiral Chromatographic Conditions

This work explores the behavior of chiral compound mixtures enriched in one of the enantiomers whilst a typical chromatography on the achiral stationary phase is employed. The influence of several factors, such as the eluent composition, ratio of the compound to the stationary phase, and the initial enatiomeric purity of the compound used on the distribution of the enantiomers in the collected chromatographic fraction, was studied. The obtained results indicate that the phenomenon of Self Disproportionation of Enantiomer (SDE) occurred in all cases, and some of the collected fractions got higher optical purities than the initial one. Thus, achiral column chromatography could be applied in some cases as the simplest approach for chiral purification. Based on the experimental results and DFT calculations, an alternative concept explaining the SDE phenomenon was proposed. Due to its generality and simplicity, SDE may also be responsible for the formation of the first chiral non-racemic compounds on the early Earth