Let's resolve this: A planar chiral benzimidazole ferroceneboronic acid catalyst demonstrates low to moderate asymmetric induction in the kinetic resolution of racemic α-substituted benzylamines by direct amide formation with achiral carboxylic acids (see scheme).

The synthesis of phosphorus molecules presenting a chiral center on the P‐atom, also known as P‐stereogenic compounds, has long attracted curiosity scientific community. Indeed, these chemical compounds feature many peculiar properties, allowing their use in various fields applications, ranging from medicine to enantioselective catalysis. However, synthesis, and more particularly introduction retention information center, remains very challenging task. That is why this review article focuses...

A new family of H-adamantylphosphinates as universal precursors P-stereogenic ligands was obtained in one step from commercial chlorophosphines. Both enantiomers these air- and moisture-stable intermediates can easily be separated by semipreparative chiral HPLC on a gram scale individually undergo stereoselective transformations to afford each enantiomer set compounds such secondary phosphine oxides boron-protected monophosphines.

Spaltwerkzeug: Eine planar-chirale Benzimidazolferrocen-Boronsäure katalysiert die kinetische Racematspaltung α-substituierter Benzylamine durch direkte Amidbildung mit achiralen Carbonsäuren mäßiger asymmetrischer Induktion (siehe Schema).

Abstract A frustrated Lewis pair (FLP) system was obtained by confinement of the base partner, a Verkade's superbase, in molecular cavity. Whereas model superbase lacking cavity displayed no catalytic activity Morita–Baylis–Hillman (MBH) reactions, when associated to titanium (IV) chloride, encaged turns out be an efficient catalyst under same conditions. The crucial role endohedral functionalized cage on performance further demonstrated fact that superbases with bulky substituents were much...

Abstract Access to hydroxy‐functionalized P‐chiral phosphine–boranes has become an important field in the synthesis of P‐stereogenic compounds used as ligands asymmetric catalysis. A family optically pure α and β‐hydroxyalkyl tertiary been prepared by using a three‐step procedure from readily accessible enantiopure adamantylphosphinate, obtained semi‐preparative HPLC on multigram scale. Firstly, two‐step one‐pot transformation affords hydroxyalkyl phosphine oxides good yields...

N,N'-Diisopropylferrocenecarboxamide is utilized for an asymmetric, directed metalation approach to several planar chiral bifunctional ferrocene derivatives. Directed using n-butyllithium-(−)-sparteine on N,N'-diisopropylferrocenecarboxamide can be achieved give high yields of the corresponding boronic acid; however, it was found that a sequence involving asymmetric metalation−bromination, followed by lithium−halogen exchange, more convenient access same derivatives since this allowed...

The synthesis of functionalized tertiary phosphine-boranes has been developed via a chemodivergent approach from readily accessible (hydroxymethyl) under mild conditions. O-Alkylation or decarbonylative P-alkylation product could be exclusively obtained. reaction was found to proceed in moderate very good yields and high enantiospecificity (es >95%) using variety alkyl halides as electrophiles. configurational stability the sodium phosphido-borane intermediate also investigated allowed...

Covalent cages with a well‐defined cavity located close to reactive center are of increasing interest because their outstanding ability mimic the catalytic properties enzymatic systems. The size and shape such synthetic nanosized reactors strongly affect behavior trapped reaction partners, which can adopt specific conformations orientations. In particular, use molecular confined functions modifies outcome transformations that carried out therein. This review article describes covalent...

We report on the synthesis of C3-symmetric enantiopure cage molecules 1, which exhibit remarkable to exclusive enantioselective recognition properties toward chiral ammonium neurotransmitters. Strong changes in substrate selectivity are also observed when different stereoisomers 1 used. Furthermore, protonation/deprotonation induces a reversible modification conformation switches from an imploded inflated form, leading ejection and reuptake guest initially encaged inside cavity.

Proazaphosphatranes ‐Verkade's superbases‐ proved to be efficient organocatalysts for the Strecker reaction between protected imines and trimethylsilyl cyanide (TMSCN). Excellent quantitative yields were reached and, compared other systems, only low catalyst loading short times required proceed efficiently. A remarkable initial turnover frequency (TOF), close 10 5 h –1 , was achieved, associated with an excellent selectivity since no side reactions observed. mechanism proposed key role...

Accessing each enantiomer of a chiral molecule starting from racemic mixture remains daunting challenge in chemistry. Indeed, until now, only few solutions exist to separate enantiomers an equimolar precursor. In this study, we establish new strategy prepare simultaneously and physically both enantioenriched substrate. This process combines two enantiomeric catalytic systems, working parallel, separation by achiral membrane with selective permeability. unprecedented system was successfully...

2-Ferrocenyl- and 2-phenyl-N-n-butylbenzimidazoles were synthesized to evaluate the influence of benzimidazole functional group upon their directed lithiation. The regiochemistry lithiation was studied, as well effect stabilization lithiated species by diamine coordination using tetramethyl- ethylenediamine (-)-sparteine. lithiations followed reaction with a variety electrophiles give disubstituted 2-ferrocenyl- compounds. This study showed that despite simple n-butyl function on...

Abstract A frustrated Lewis pair (FLP) system was obtained by confinement of the base partner, a Verkade's superbase, in molecular cavity. Whereas model superbase lacking cavity displayed no catalytic activity Morita–Baylis–Hillman (MBH) reactions, when associated to titanium (IV) chloride, encaged turns out be an efficient catalyst under same conditions. The crucial role endohedral functionalized cage on performance further demonstrated fact that superbases with bulky substituents were much...

A new, more environmentally benign route to hydroxyethylsulfonylstyrene has been developed, starting from 4-bromobenzenethiol, involving a solventless thioether formation, water-based perborate oxidation, and Suzuki−Miyaura cross coupling with vinylborate reagent.

In this paper we describe the synthesis of functionalised mesoporous organosilicas containing a mannitol derivative in framework. For purpose, bis-silylated precursor 3,4-Di-O-[3-(triethoxysilylpropyl)carbamate]-1,2:5,6-di-O-isopropylidene-D-mannitol was prepared by coupling 1,2:5,6-di-O-isopropylidene-D-mannitol with 3-(triethoxysilylpropyl)isocyanate. The framework-functionalised materials were obtained one step "direct synthesis" method which consists co-hydrolysis and polycondensation...

Abstract We present recent advances in the understanding of reduction optically pure hydroxyalkylphosphinates and phosphine oxides, which represent key intermediates for preparation P-stereogenic ligands. Their leads to P-chiral phosphinites phosphines, respectively, occurs stereospecifically with inversion configuration using BH 3 ·THF, plays three roles: activating, reducing protecting agent. The formation by-products as hydroxyalkyl secondary phosphine–boranes has also been studied.

From achiral imidazolinium salts, chiral transition metal complexes containing an N-heterocyclic carbene (NHC) ligand were prepared (metal = palladium, copper, silver, gold, rhodium). Axial chirality in these results from the formation of metal-carbene bond leading to restriction rotation dissymmetric N-aryl substituents about C-N bond. When exhibited a sufficient configurational stability, resolution by high-performance liquid chromatography (HPLC) on preparative scale enabled isolation...