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Ru(BINAP)(PPh3)HCl cleanly reacts with LiCH2TMS to give Ru(BINAP)(PPh3) (1) that has been fully characterized, including by X‐ray diffraction (BINAP and TMS stand for (2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl‐free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C−H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh3 ligand with alkenes and dienes, thus behaving like a "masked" 16‐e Ru(0) species. Electron‐poor alkenes coordinate more readily than electron‐rich ones, which testifies for the nucleophilic character of the Ru(0)‐BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C−H and N−H bonds, and even of cleaving an inert N−Et bond. The combination of high reactivity and stability originates from the P,arene‐chelation by the BINAP ligand, i.e., the coordinated π‐arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions. [ABSTRACT FROM AUTHOR]

Ru(BINAP)(PPh3)HCl cleanly reacts with LiCH2TMS to give Ru(BINAP)(PPh3) (1) that has been fully characterized, including by X‐ray diffraction (BINAP and TMS stand for (2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl‐free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C−H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh3 ligand with alkenes and dienes, thus behaving like a "masked" 16‐e Ru(0) species. Electron‐poor alkenes coordinate more readily than electron‐rich ones, which testifies for the nucleophilic character of the Ru(0)‐BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C−H and N−H bonds, and even of cleaving an inert N−Et bond. The combination of high reactivity and stability originates from the P,arene‐chelation by the BINAP ligand, i.e., the coordinated π‐arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions. [ABSTRACT FROM AUTHOR]

Ru(BINAP)(PPh3)HCl cleanly reacts with LiCH2TMS to give Ru(BINAP)(PPh3) (1) that has been fully characterized, including by X‐ray diffraction (BINAP and TMS stand for (2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl‐free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C−H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh3 ligand with alkenes and dienes, thus behaving like a "masked" 16‐e Ru(0) species. Electron‐poor alkenes coordinate more readily than electron‐rich ones, which testifies for the nucleophilic character of the Ru(0)‐BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C−H and N−H bonds, and even of cleaving an inert N−Et bond. The combination of high reactivity and stability originates from the P,arene‐chelation by the BINAP ligand, i.e., the coordinated π‐arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions. [ABSTRACT FROM AUTHOR]

Ru(BINAP)(PPh3)HCl cleanly reacts with LiCH2TMS to give Ru(BINAP)(PPh3) (1) that has been fully characterized, including by X‐ray diffraction (BINAP and TMS stand for (2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl‐free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C−H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh3 ligand with alkenes and dienes, thus behaving like a "masked" 16‐e Ru(0) species. Electron‐poor alkenes coordinate more readily than electron‐rich ones, which testifies for the nucleophilic character of the Ru(0)‐BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C−H and N−H bonds, and even of cleaving an inert N−Et bond. The combination of high reactivity and stability originates from the P,arene‐chelation by the BINAP ligand, i.e., the coordinated π‐arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions. [ABSTRACT FROM AUTHOR]

Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title heteroleptic cuprous complex, [2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl‐κ2P,P′](2‐phenylpyridine‐κN)copper(I) hexafluoridophosphate, rac‐[Cu(C44H32P2)(C11H9N)]PF6, conventionally abbreviated rac‐[Cu(BINAP)(2‐PhPy)]PF6 (I), where BINAP and 2‐PhPy represent 2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl and 2‐phenylpyridine, respectively, is described. In this complex, the asymmetric unit consists of a hexafluoridophosphate anion and a heteroleptic cuprous complex cation, in which the cuprous centre in a CuP2N coordination triangle is coordinated by two P atoms from the BINAP ligand and by one N atom from the 2‐PhPy ligand. Time‐dependent density functional theory (TD–DFT) calculations show that the UV–Vis absorption of I should be attributed to ligand‐to‐ligand charge transfer (LLCT) characteristic excited states. It was also found that the paper‐based film of this complex exhibited obvious luminescence light‐up sensing for pyridine. [ABSTRACT FROM AUTHOR]

Herein, we disclosed the contra‐thermodynamic E→Z isomerization of alkenyl silanes, according to the in situ formation of a chromophoric species, in the presence of rac‐BINAP as the catalyst. The reaction carried out in DMSO or CH3CN under irradiation at 405 nm allowed the interconversion of the E‐isomers into the Z‐congeners in good to excellent yields and outstanding Z/E selectivities, on 18 examples. Finally, the mechanism of this E→Z isomerization was studied to get insight into the reaction mechanism. [ABSTRACT FROM AUTHOR]

A series of novel 'drug-like' small molecules based on 1 H -benzo[ d ]imidazole derivatives bearing furan-2-yl, 4-piperidine and 5-aryl/aminoaryl substitutions were designed and synthesised. The key intermediate tert -butyl-4-(5-bromo-2-(furan-2-yl)-1 H -benzo[ d ]imidazol-1-yl)piperidine-1-carboxylate (5) was synthesised via sequential reaction starting from 4-bromo-1-fluoro-2-nitrobenzene (1). The 5-aryl-substituted molecular library was generated via Suzuki–Miyura coupling of tert -butyl-4-(5-bromo-2-(furan-2-yl)-1 H -benzo[ d ]imidazol-1-yl)piperidine-1-carboxylate (5) with various boronic acids while Buchwald coupling of 5 with various anilines generated the second molecular library of tert -butyl-4-(2-(furan-2-yl)-5-(arylamino)-1 H -benzo[ d ]imidazol-1-yl)piperidine-1-carboxylates. The structures of all the newly synthesised compounds were confirmed by spectral analysis. The optimised procedure gives easy access to two new molecular libraries of 1 H -benzo[ d ]imidazoles with operational simplicity and good yield. A series of novel 'drug-like' small molecules based on 1 H -benzo[ d ]imidazole derivatives bearing furan-2-yl, 4-piperidine and 5-aryl/aminoaryl substitutions were designed and synthesised. The optimised procedure gave easy access to two novel molecular libraries of 1 H -benzo[ d ]imidazoles with operational simplicity and good yield. [ABSTRACT FROM AUTHOR]

[Display omitted] • Synthesis of novel solid molecular catalysts (SMC) bearing a BINAP ligand moiety for metal coordination. • High catalytic activity for Ru loaded BINAP-SMC in hydrogen release from formic acid reaching TOFs of up to 134 000 h−1 at 160 °C and TONs of up to 921 000. • Stable catalytic activity for formic acid concentrations from 10 wt% to 50 wt% FA. • Ru single sites confirmed by EXAFS, HAADF-STEM and XPS measurements with minor formation of nanoparticles under reaction conditions. • Ru agglomerates proposed as stable catalyst species under continuous operation conditions with slow oxidation of the phosphine moieties and reduction of the aromatic backbone as deactivation mechanisms of the catalyst. In this work, a Suzuki cross-coupling procedure towards highly porous BINAP-based polymeric Ru-catalyst materials with tunable specific surface areas (SSAs) were synthesized and their stability towards reducing conditions was investigated. After the removal of Pd impurities by an oxidative treatment with H 2 O 2 /HCl, P=O reduction and metal loading, the resulting catalysts were employed for the base-free ruthenium-catalyzed decomposition of aqueous formic acid to CO 2 and H 2 with TOFs of up to 134 000 h−1 and TONs up to 920 000. [ABSTRACT FROM AUTHOR]

Ru(BINAP)(PPh 3 )HCl cleanly reacts with LiCH 2 TMS to give Ru(BINAP)(PPh 3 ) (1) that has been fully characterized, including by X-ray diffraction (BINAP and TMS stand for (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl-free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C-H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh 3 ligand with alkenes and dienes, thus behaving like a "masked" 16-e Ru(0) species. Electron-poor alkenes coordinate more readily than electron-rich ones, which testifies for the nucleophilic character of the Ru(0)-BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C-H and N-H bonds, and even of cleaving an inert N-Et bond. The combination of high reactivity and stability originates from the P,arene-chelation by the BINAP ligand, i.e., the coordinated π-arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions., (© 2024 The Authors. Published by Wiley-VCH GmbH.)

In the title compound (systematic name: bis{1,2-bis[12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3(8),4,6,9,16,18(23),19,21-decaen-13-yl]ethane}dichloridoiron(II) dichloromethane disolvate), [FeCl2(C42H28O4P2)2]·2CH2Cl2, the FeII ion lies on a crystallographic twofold rotation axis and is coordinated by four P atoms from two (R,R)-1,2-bis(binaphthylphosphonito)ethane (BPE) ligands and two Cl ligands in a distorted cis-FeCl2P4 octahedral coordination geometry. In the crystal, weak C—H...O and C—H...π interactions link the molecules into layers lying parallel to (001). A weak intramolecular C—H...O hydrogen bond is also observed. The asymmetric unit contains one CH2Cl2 solvent molecule, which is disordered over two sets of site with refined occupancies in the ratio 0.700 (6):0.300 (6).

Asymmetric catalysis is the preferred method for the synthesis of pure chiral molecules in the fine chemical industry. Cellulose has long been sought as a support in enantioselective catalysis. Dialdehyde cellulose (DAC) is produced by the selective oxidation of cellulose and is used to bind 5,5′-diamino Binap by forming a Schiff base. Here, we report the synthesis of modified cellulose-supported Rh as a novel biomass-supported catalyst and the characterization of its morphology, composition, and thermal stability. DAC-BINAP-Rh was a very effective catalyst in the asymmetric hydrogenation of enamides and could be easily recycled. This work provides a novel supported catalyst that broadens the applications of cellulose in asymmetric catalysis.

In the title compound (systematic name: bis­{1,2-bis[12,14-dioxa-13-phospha­penta­cyclo­[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3(8),4,6,9,16,18(23),19,21-deca­en-13-yl]ethane}­dichlorido­iron(II) di­chloro­methane disolvate), [FeCl2(C42H28O4P2)2]·2CH2Cl2, the FeII ion lies on a crystallographic twofold rotation axis and is coordinated by four P atoms from two (R,R)-1,2-bis­(bi­naphthyl­phospho­n­ito)ethane (BPE) ligands and two Cl ligands in a distorted cis-FeCl2P4 octa­hedral coordination geometry. In the crystal, weak C—H...O and C—H...π inter­actions link the mol­ecules into layers lying parallel to (001). A weak intra­molecular C—H...O hydrogen bond is also observed. The asymmetric unit contains one CH2Cl2 solvent mol­ecule, which is disordered over two sets of site with refined occupancies in the ratio 0.700 (6):0.300 (6). [ABSTRACT FROM AUTHOR]

Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The heteroleptic cuprous complex solvate rac‐(acetonitrile‐κN)(3‐aminopyridine‐κN)[2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl‐κ2P,P′]copper(I) hexafluoridophosphate dichloromethane monosolvate, [Cu(C5H6N2)(C2H3N)(C44H32P2)]PF6·CH2Cl2, conventionally abbreviated as [Cu(3‐PyNH2)(CH3CN)(BINAP)]PF6·CH2Cl2, (I), where BINAP and 3‐PyNH2 represent 2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl and 3‐aminopyridine, respectively, is described. In this complex solvate, the asymmetric unit consists of a cocrystallized dichloromethane molecule, a hexafluoridophosphate anion and a complete racemic heteroleptic cuprous complex cation in which the cuprous centre, in a tetrahedral CuP2N2 coordination, is coordinated by two P atoms from the BINAP ligand, one N atom from the 3‐PyNH2 ligand and another N atom from a coordinated acetonitrile molecule. The UV–Vis absorption and photoluminescence properties of this heteroleptic cuprous complex have been studied on polycrystalline powder samples, which had been verified by powder X‐ray diffraction before recording the spectra. Time‐dependent density functional theory (TD‐DFT) calculations and a wavefunction analysis reveal that the orange–yellow phosphorescence emission should originate from intra‐ligand (BINAP) charge transfer mixed with a little of the metal‐to‐ligand charge transfer 3(IL+ML)CT excited state. [ABSTRACT FROM AUTHOR]

Bis(azido)palladium(II) Complexes Bearing an (R or S)-(BINAP) Ligand: Synthesis, Structures, and Catalytic Application to Suzuki-Miyaura C-C Coupling Reactions However, the utility of neutral (BINAP)Pd-catalyzed C-C coupling reactions as compared with that of ionic (BINAP)Pd complexes has not been reported. In this context, we examined the applicability of the (BINAP)Pd-pseudohalogen complexes prepared in this study for catalyzing Suzuki-Miyaura C-C coupling reactions. We also reported the first example of Pd(II) pseudo-halogen complexes containing chiral BINAP ligands, a potential precursor for new types of heterocyclic tetrazole compounds, which can be useful in other palladium-catalyzed organic transformation. [Extracted from the article]

The need of long-term treatment for chronic HBV, emergence of drug-resistant viruses and inefficiency of currently approved therapies to eliminate covalently closed circular DNA (cccDNA), mandates identification of potent and selective inhibitors of HBV replication with novel mechanisms of action. Entecavir, a carbocyclic guanosine nucleoside analog, is the most potent inhibitor of HBV replication on the market. Moreover, the naturally occurring carbocyclic nucleosides aristeromycin are known for their wide range of antiviral activities. In this research, we have utilized BINAP directed rhodium catalyzed reductive carbocyclization of 1,6-enynes (8a–b) through asymmetric hydrogenation which is an approach, not yet explored in carbocyclic sugar synthesis. Interestingly, we obtained exclusive anti-(9a) and Z-anti(9b) carbocyclic sugars. The new aristeromycin analogs (10a–b) with scaffold combination of entecavir and aristeromycin were then synthesized using the Mitsunobu reaction followed by deprotection. [ABSTRACT FROM AUTHOR]

Abstract: A Pd/(R)‐BINAP‐catalyzed enantioselective benzylic sulfonation of diarylmethyl carbonates with sodium sulfinates proceeds to deliver the corresponding chiral diarylmethyl sulfones in good yields with high enantioselectivity. The reaction occurs in a dynamic kinetic asymmetric transformation (DYKAT) manner and thus provides convergent access to optically active benzylic sulfones from racemic secondary benzylic carbonates. Additionally, the addition of H2O is found to be critical for high enantioselectivity. [ABSTRACT FROM AUTHOR]

Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title heteroleptic cuprous complex, [2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl-κ 2 P,P'](2-phenylpyridine-κN)copper(I) hexafluoridophosphate, rac-[Cu(C 44 H 32 P 2 )(C 11 H 9 N)]PF 6 , conventionally abbreviated rac-[Cu(BINAP)(2-PhPy)]PF 6 (I), where BINAP and 2-PhPy represent 2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl and 2-phenylpyridine, respectively, is described. In this complex, the asymmetric unit consists of a hexafluoridophosphate anion and a heteroleptic cuprous complex cation, in which the cuprous centre in a CuP 2 N coordination triangle is coordinated by two P atoms from the BINAP ligand and by one N atom from the 2-PhPy ligand. Time-dependent density functional theory (TD-DFT) calculations show that the UV-Vis absorption of I should be attributed to ligand-to-ligand charge transfer (LLCT) characteristic excited states. It was also found that the paper-based film of this complex exhibited obvious luminescence light-up sensing for pyridine.

The self-assembly of [Au 2 (μ-(±)binap)X 2 ], which have weakly coordinated anions X − = trifluoroacetate, triflate or nitrate, with bis(amidopyridyl) ligands (NN) has given three different macrocyclic complexes of general formula [Au 4 (μ-(±)binap) 2 (μ-NN) 2 ]X 4 , an open complex [Au 2 (μ-(±)binap)(κ 1 -NN) 2 ]X 2 , and a polymer [{Au 2 (μ-(±)binap)(μ-NN)} n ]X 2 n . Macrocycles with both homochiral ( RR / SS ) and heterochiral ( RS / SR ) combinations of the two binap ligands in the cations [Au 4 (μ-binap) 2 (μ-NN) 2 ] 4+ have been structurally characterized. The polymeric complex has the syndiotactic (heterochiral) architecture. The donor ability of the anion X − is shown to affect both the degree of self-assembly in solution, through competition with the bis(amidopyridyl) ligand for coordination to gold(I), and the conformation of the bis(amidopyridyl) ligand in the products, through hydrogen bonding effects. In solution, there is a rapid equilibrium between cyclic and open chain oligomers, as determined by ESI-MS and NMR studies. [ABSTRACT FROM AUTHOR]

A fluorescence-active modified BINOL with heteroaromatic fused rings containing two different heteroatoms is synthesized in good yield. Its racemate form is well characterized by chiral HPLC analysis. The molecule bears sterically hindered geometry and has potential for stereochemical properties normally exhibited by BINOLs. The molecule has two ends with different ligating atoms in the form of hydroxy groups at one end and isoxazole ring heteroatoms on the other end. This feature may be useful for molecular recognition of both hard and soft cations. [ABSTRACT FROM AUTHOR]

The synthesis of a GSK 2nd generation inhibitor of the hepatitis C virus, by enantioselective 1,3-dipolar cycloaddition between a leucine derived iminoester and tert-butyl acrylate, was studied. The comparison between silver(I) and gold(I) catalysts in this reaction was established by working with chiral phosphoramidites or with chiral BINAP. The best reaction conditions were used for the total synthesis of the hepatitis C virus inhibitor by a four step procedure affording this product in 99% ee and in 63% overall yield. The origin of the enantioselectivity of the chiral gold(I) catalyst was justified according to DFT calculations, the stabilizing coulombic interaction between the nitrogen atom of the thiazole moiety and one of the gold atoms being crucial.

Catalytic hydrogenation of 3,5-bis-arylidenetetramic acids, known for their biological activity, has been developed. The chemoselective ruthenium-catalyzed reduction of the exocyclic carbon-carbon double bonds on pyrrolidine-2,4-dione ring system, containing other reducible functions, has been investigated. Depending on the substrate the yield of the hydrogenation process can reach up to 95%. The structural elucidation has been established using NMR and HRMS spectral data.

Chiral organic compounds in the photoexcited state are potential chiral luminophores. Photoluminescence properties of these compounds can be measured using circularly polarised luminescence (CPL) spectroscopy. Axially chiral binaphthyl BINAP in CHCl 3 solution or the KBr-dispersed state exhibits no significant CPL signal. Herein, we report the first CPL spectrum of BINAP by doping into a poly(methyl methacrylate) (PMMA) organic polymeric matrix. For comparison, CPL data of BINAPO, a structural analogue of BINAP, were collected. Contrarily to BINAP, BINAPO showed a clear CPL signal in all three states. [ABSTRACT FROM AUTHOR]

Potential atropisomeric ligands, diphenylphosphane derivatives of bis-triazoles, were synthesized by direct phosphanylation of the starting bis-triazoles with chlorodiphenylphosphane. Their crystal structure was elucidated by X-ray diffractional analysis. The conformations of these compounds were modeled by DFT calculations. [ABSTRACT FROM AUTHOR]

Six metal complexes based on AuI, PdII, or PtII with functionalized ( S)-4, 4′- or 5, 5′-bis(3-pyridyl)-2, 2′-bis(diphenylphosphanyl)-1, 1′-binaphthyl ligands ( L1, L2) have been prepared and fully characterized. According to single-crystal X-ray analysis, the AuI complexes ( S)-[Au2Cl2( L1)] ( 1) and ( S)-[Au2Cl2( L2)] ( 2) show an almost linear Cl-Au-P arrangement, and the PdII and PtII complexes ( S)-[PdCl2( L1)] ( 3), ( S)-[PdCl2( L2)] ( 4), ( S)-[PtI2( L1)] ( 5), and ( S)-[PtI2( L2)] ( 6) exhibit distorted square-planar geometries. [ABSTRACT FROM AUTHOR]

ABSTRACT BINAP-metal complexes were prepared as extractant for liquid-liquid extraction (ELLE) of amino-(4-nitro-phenyl)-acetic acid (NPA) enantiomers. The influence of process variables, including types of organic solvents and metal precursor, concentration of ligand, pH, and temperature on the efficiency of the extraction, were investigated experimentally. An interfacial reaction model was established for insightful understanding of the chiral extraction process. Important parameters required for the model were determined. The experimental data were compared with model predictions to verify the model prediction, It was found that the interfacial reaction model predicted the experimental results accurately. By modeling and experiment, an optimal extraction condition with pH of 7 and host (extractant) concentration of 1 mmol/L was obtained and high (αop) of 3.86 and performance factor ( pf) of 0.1949 were achieved. Chirality 26:79-87, 2014. © 2013 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Equilibrium study on enantionselective extraction of 2-chlorophenylglycine (CPG) enantiomers with S-BINAP-metal complexes as selector was performed. A reactive extraction model with an interfacial reaction of CPG enantiomers with S-BINAP-metal complex was established. The extraction system shows good selectivity towards CPG enantiomers. [(S-BINAP)Cu(CH3CN)][PF6] (BINAP-Cu) exhibits the highest selectivity among the selectors studied. Efficiency of the extraction depends, often strongly, on a number of process variables, including types of organic solvents and metal precursors, concentration of the selector, the pH, and the temperature. The model quantitatively predicts extraction performance as a function of key operating parameters, providing a simple computational approach to process optimization. High enantioselectivity of 3.01 was obtained. [ABSTRACT FROM AUTHOR]

The enantioselective extraction of 4-nitro-phenylalanine (Nphy) was studied with metal-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) complexes as the chiral selector. The complex with palladium (BINAP-Pd) exhibits the highest selectivity out of the selectors studied, which is solubilised in the organic phase and preferentially extracts d-Nphy from the aqueous phase. Efficiency of extraction depends, often substantially, on a number of process variables, including types of organic solvents and metal precursors, concentration of ligand, pH, and temperature. A reactive extraction model was established to interpret the experimental data. The equilibrium formation constants and other important parameters required by the model were determined experimentally. The equilibrium formation constants were 6.73 and 1.93 for d-Nphy and l-Nphy. By way of modelling and experiment, an optimal extraction condition with pH of 7 and BINAP-Pd concentration of 1 mmol L was obtained with enantioselectivity ( α) of 3.37, which was close to the maximum of 3.48, and a performance factor (pf) of 0.195. The model was verified experimentally with excellent results. [ABSTRACT FROM AUTHOR]

Asymmetric catalysis is the preferred method for the synthesis of pure chiral molecules in the fine chemical industry. Cellulose has long been sought as a support in enantioselective catalysis. Dialdehyde cellulose (DAC) is produced by the selective oxidation of cellulose and is used to bind 5,5′-diamino Binap by forming a Schiff base. Here, we report the synthesis of modified cellulose-supported Rh as a novel biomass-supported catalyst and the characterization of its morphology, composition, and thermal stability. DAC-BINAP-Rh was a very effective catalyst in the asymmetric hydrogenation of enamides and could be easily recycled. This work provides a novel supported catalyst that broadens the applications of cellulose in asymmetric catalysis. [ABSTRACT FROM AUTHOR]

Abstract: Several crystal structures and a theoretical DFT structure of the important catalyst (BINAP)PdCl2 (BINAP: 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) have been determined. The conformational flexibilities of the BINAP backbone and of the phenyl rings do not seem to be coupled. Two novel parameter have been introduced that define the Π–Π stacking between the phenyl and biaryl rings in systems similar to the BINAP ligand, as well as the delta angle that is sensitive to the important interaction of the exchangeable ligands of the palladium with the equatorial phenyl rings of the BINAP. Furthermore, the calculated bite angle is 3° larger than the experimentally determined bite angles. [Copyright &y& Elsevier]

A continuous-flow process for the asymmetric hydrogenation of methyl propionylacetate as a prototypical β-keto ester in a biphasic system of ionic liquid and supercritical carbon dioxide (scCO2) is presented. An established ruthenium/2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) catalyst was immobilised in an imidazolium-based ionic liquid while scCO2 was used as mobile phase transporting reactants in and products out of the reactor. The use of acidic additives led to significantly higher reaction rates and enhanced catalyst stability albeit at slightly reduced enantioselectivity. High single pass conversions (>90%) and good enantioselectivity (80-82% ee) were achieved in the first 80 h. The initial catalyst activity was retained to 91% after 100 h and to 69% after 150 h time-on-stream, whereas the enantioselectivity remained practically constant during the entire process. A total turnover number of ∼21,000 and an averaged space-time yield (STYav) of 149 g L−1 h−1 were reached in a long-term experiment. No ruthenium and phosphorus contaminants could be detected via inductively coupled plasma optical emission spectrometry (ICP-OES) in the product stream and almost quantitative retention by the analysis of the stationary phase was confirmed. A comparison between batch-wise and continuous-flow operation on the basis of these data is provided. [ABSTRACT FROM AUTHOR]

Glycine-derived azlactones react with maleimides using (S)- or (R)-dimeric BinapAuTFA complexes affording the corresponding cycloadducts in good yields and high enantioselections (up to 99% ee). The intermediate carboxylic acids are treated with trimethylsilyldiazomethane and isolated as Δ¹-pyrroline methyl esters. These cycloadducts are transformed into exo-proline derivatives by reduction with NaBH3CN in acidic media. On the other hand, N-benzoylalanine-derived oxazolone reacts with tert-butyl acrylate providing the cycloadduct with the ester group at the 3-position with a trans-relative configuration with respect to the methyl ester group. [ABSTRACT FROM AUTHOR]

Catalytic hydrogenation of 3,5-bis-arylidenetetramic acids, known for their biological activity, has been developed. The chemoselective ruthenium-catalyzed reduction of the exocyclic carbon-carbon double bonds on pyrrolidine-2,4-dione ring system, containing other reducible functions, has been investigated. Depending on the substrate the yield of the hydrogenation process can reach up to 95%. The structural elucidation has been established using NMR and HRMS spectral data. [ABSTRACT FROM AUTHOR]

Abstract: 3,3′-Disubstituted xylBINAP derivatives were applied to inter- and intramolecular asymmetric Heck/Mizoroki reactions. The results from these reactions were compared to those obtained with (R)-xylBINAP, (S)-BINAP and 3,3′-disubstituted BINAP derivatives. Catalysts derived from 3,3′-disubstituted xylBINAP ligands were found to be most effective in the arylation of 2,3-dihydrofuran in terms of reaction times, conversions, and product enantioselectivity. [ABSTRACT FROM AUTHOR]

Abstract: A facile and microwave accelerated reaction of 1-chloro-3-(4-chlorophenyl)isoquinoline with various heterocyclic amines, catalyzed by Pd, in the presence of BINAP additive and sodium carbonate as the base, leads to the formation of 3-(4-chlorophenyl)-1-(1H-1,2,3-triazol-1-yl)isoquinoline, 3-(4-chlorophenyl)-1-(1H-imidazol-1-yl)isoquinoline and 3-(4-chlorophenyl)-1-(1H-1,2,4-triazol-1-yl)isoquinoline via Buchwald protocol in good yields. Similarly pyrazolylisoquinolines are also reported. [Copyright &y& Elsevier]

Abstract: New 3-(heteroaryl)aminocoumarin derivatives were synthesized from 3-aminocoumarin, applying optimized Buchwald–Hartwig amination conditions using Palladium acetate, Cesium carbonate, and BINAP in 1,4-dioxane employing elevated temperature conditions and under an argon atmosphere. The target heteroarylaminocoumarin derivatives were obtained in moderate to good yields ranging from 56% to 98%. The procedure described could be widely employed for the preparation of new heterocyclic compounds when one of the core moieties is coumarin and has the potential to be active drug candidates. [Copyright &y& Elsevier]

Abstract: Fast semipreparative HPLC enantioseparation of four axially chiral biscarbostyrils (4,4′-bisquinoline-2-ones) using ULMO as a π-acidic Pirkle type chiral stationary phase leads to two racemizing pairs (1,2; k obs 1.6×10−4 and 3.0×10−4 s−1 at 28°C) and two stable ones (3,4). 3 was stabilized by a crown ether linkage from pos. 6 to 6′, and 4 had sterically demanding bromo substituents in pos. 3 and 3′. On-column generated temperature-dependent chromatograms of 1 and 2 were fitted with Auto-DHPLCy2k and DCXplorer. For cpd 2 both programs delivered similar ΔG values of 90 and 93kJ/mol, well comparable with the 99kJ/mol calculated with the B3LYP/6-31G (d) procedure. At temperatures of high conversion DCXplorer delivered inconsistent series of rate constants for the more tailing and less resolved tetramethoxy derivative 1. We connect this problem with an almost impossible halfwidth calculation of tailing peak pairs which are weakly resolved. However, this problem could be observed only in the case of tetramethoxy derivative 1. Stochastic generated data of Auto-DHPLCy2k could be used at a lower percentage of conversion only while the theoretical plate model did not deliver useful data at temperatures of very low conversion but fitted well high conversion chromatogram series of 1 and 2. [Copyright &y& Elsevier]

Abstract: Biscarbostyrils (4,4′-bisquinolones) can be synthesized from 4-chloro-2-quinolinones using a Pd-catalyzed one-pot borylation/Suzuki cross-coupling protocol or via Ni(0)-mediated reductive homocoupling. The electronic spectra of biscarbostyrils 4b–8 exhibit unusual properties in comparison to the corresponding carbostyrils 1–3. Similar absorption spectra are accompanied by red-shifted emission maxima up to 520nm. Unsubstituted biscarbostyril 4b displays the unusual property of a 2500cm−1 fluorescence redshift in water as compared to dimethylsulfoxide instead of an expected 800cm−1 blueshift. In order to further improve redshifts and fluorescence quantum yields, varying substitution patterns were created. In bisquinolone 7, an additional diphenylphosphinoxide substitution in position 3 and 3′ (15c) increased the quantum yield to 20% and the epsilon value to 25,000. A crown ether linkage from position 6 to 6′ in biscarbostyrils improved the emission maximum from 470 to 500nm, but the fluorescence quantum yield was raised only from 3% to 6%. Time-dependent density functional calculations of absorption and emission spectra of selected derivatives show good agreement with the corresponding experimental data. Especially, the unusual large Stoke’s shift observed for biscarbostyrils as well as their rather low fluorescence quantum yields can be rationalized on the basis of these calculations. Like 1,1′ binaphthalenes the biscarbostyril structures are axially chiral and can be functionalized in position 3 and 3′ with diphenylphosphine. Most of the racemates were baseline HPLC separated on the Pirkle type ULMO column, with separation factors of up to 2.4 for BINAP type intermediate 15a. [Copyright &y& Elsevier]

Abstract: The combination of palladium chloride with BINAP shows high efficiency in the decarboxylative cross-coupling reactions of arenecarboxylic acids with aryl iodides. The reactions proceed smoothly to generate the corresponding biaryl compounds in good to excellent yields. [Copyright &y& Elsevier]

[Display omitted] Herein reported is the convenient and efficient strategy for the preparation of binaphthyl-based phosphines through direct modification to the commercially available 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) with sodium. In the absence of 15-crown-5-ether, a cyclic sodium dinapthylphospholide intermediate is mainly generated. With 15-crown-5-ether, P-Ph bonds are selectively cleft by Na to produce binaphthyl-based disodium phosphides. The mechanism of selective formation of sodium dinapthylphospholide or binaphthyl-based disodium phosphides is proposed. [ABSTRACT FROM AUTHOR]

Abstract: Two different organometallic ligand substitution reactions were investigated: (1) an achiral reactive system consisting of Rh4(CO)12 +PPh3 ⇌Rh4(CO)11PPh3 +CO in n-hexane under argon; and (2) a chiral reactive system consisting of Rh4(CO)12 +(S)-BINAP⇌Rh4(CO)10BINAP+2CO in cyclohexane under argon. These two reactions were run at ultra high dilution. In both multi-component reactive systems the concentrations of all the solutes were less than 40ppm and many solute concentrations were just 1–10ppm. In situ spectroscopic measurements were carried out using UV–vis (Ultraviolet–visible) spectroscopy and UV–vis CD spectroscopy on the reactive organometallic systems (1) and (2), respectively. The BTEM algorithm was applied to these spectroscopic data sets. The reconstructed UV–vis pure component spectra of Rh4(CO)12, Rh4(CO)11PPh3 and Rh4(CO)10BINAP as well as the reconstructed UV–vis CD pure component spectra of Rh4(CO)10BINAP were successfully obtained from BTEM analyses. All these reconstructed pure component spectra are in good agreement with the experimental reference spectra. The concentration profiles of the present species were obtained by performing a least square fit with mass balance constraints for the reactions (1) and (2). The present results indicate that UV–vis and UV–vis-CD spectroscopies can be successfully combined with an appropriate chemometric technique in order to monitor reactive organometallic systems having UV and Vis chromophores. [Copyright &y& Elsevier]

Abstract: We have achieved the first catalytic enantioselective synthesis of planar-chiral metacyclophanes by means of cationic Rh(I)/(S)-xyl-H 8-BINAP or (R)-H 8-BINAP complex-catalyzed inter- and intramolecular alkyne cyclotrimerizations. This highly enantioselective catalysis represents a versatile new method for the preparation of planar-chiral metacyclophanes. [Copyright &y& Elsevier]

Bromination of (R)-2,2'-(diphenylphospnino)-1,1'-binaphthyl (BINAP) in [Hmim]PF6 ionic liquid was performed with N-halosuccinimides at 110°C during 12 h, affording the 4,4'-dibromoBINAP in high yield. The ionic liquid was recycled four times without modification of selectivity or efficiency. [ABSTRACT FROM AUTHOR]

Abstract: The allylic substitution of (E)-1,3-diphenylallyl acetate (1a) with dimethyl malonate was investigated on Pd/Al2O3 modified by (R)- and (S)-BINAP, ()-Chiraphos, (R)-C3-Tunephos, and (R)-Solphos. Stable performance of Pd/Al2O3 required its reduction in hydrogen before the allylic substitution reaction, which was carried out under Ar. The enantioselectivity of the Pd/Al2O3-BINAP system [58–60% ee to (S)-2] was independent of the reaction temperature (60 and 120 °C), and only 300 ppm BINAP related to 1a was required. According to UV–vis analysis, only a small fraction of BINAP was adsorbed on Pd/Al2O3. At 120 °C, full conversion and 94% chemoselectivity were achieved in 6 h. For comparison, analogous soluble Pd–BINAP complexes were poorly efficient and afforded low ee to the opposite enantiomer of the product at 60 °C or above. Electron microscopy could detect no restructuring of Pd in Pd/Al2O3 during the reaction. Surprisingly, the addition of BINAP induced a significant rate acceleration (by a factor of almost 7 at 60 °C) and also improved the chemoselectivity of Pd/Al2O3. Among the diphosphine ligands tested, (R)-Solphos was the most effective (67% ee). An important advantage of the Pd/Al2O3–BINAP system is that it can transform not only the allyl acetate 1a, but also the corresponding allyl alcohol 1b without the application of any additive. [Copyright &y& Elsevier]

Our research group was the first to discover that cationic rhodium(I)/BINAP-type bisphosphine complexes are versatile new catalysts for highly chemo-, regio-, and enantioselective [2+2+2] cycloadditions. The high chemo- and regioselectivity of these �cycloadditions enabled efficient catalytic synthesis of substituted benzenes, cyclophanes, and nitrogen heterocycles. Furthermore, enantioselective variants of these cycloadditions were also developed that realized efficient catalytic constructions of axial, planar, central, and spiro chirality. 1Introduction 2 Chemo- and Regioselective [2+2+2] Cycloadditions 2.1 [2+2+2] Cycloaddition of Terminal Alkynes 2.2 [2+2+2] Cycloaddition of Two Different Alkynes 2.3 [2+2+2] Cycloaddition of α,ω-Diynes with Alkynes 2.4 [2+2+2] Cycloaddition of Alkynes with Isocyanates, Isothiocyanates, and Carbon Disulfide 2.5 [2+2+2] Cycloaddition of Alkynes with Nitriles 3 Enantioselective [2+2+2] Cycloadditions 3.1 Construction of Axial Chirality 3.2 Construction of Planar Chirality 3.3 Construction of Central Chirality 3.4 Construction of Spiro Chirality 4 Summary [ABSTRACT FROM AUTHOR]

Abstract: Electronic effects of electron-donating and electron-withdrawing substituents at the para position of the phenyl moieties of BINAP ligands were studied towards asymmetric hydrogenation of α-(acylamino)acrylic acids. Enantiomeric excesses varied as a linear relationship towards Hammett coefficients σ p of electron-donating groups between 0 and −0.63. [Copyright &y& Elsevier]

Abstract: A catalytic asymmetric aldol reaction of alkenyl trichloroacetates with aldehydes was achieved using dibutyltin dimethoxide and BINAP·silver(I) complex as catalysts in a mixed solvent consisting of THF and MeOH. Various optically active β-hydroxy ketones were diastereoselectively obtained not only from aromatic and α,β-unsaturated aldehydes but also from an aliphatic aldehyde with good enantioselectivity up to 92% ee. [Copyright &y& Elsevier]

Abstract: Some optically active β-hydroxymethyl-γ-butyrolactone derivatives, useful building blocks for the synthesis of several natural products and biologically active compounds, were obtained in good yields and variable optical purity (2–100% e.e.) from the corresponding 4-(hydroxymethyl)furan-2(5H)-one by enantioselective hydrogenation with chiral ruthenium or rhodium BINAP complexes. [Copyright &y& Elsevier]

Abstract: Pd(OAc)2-(±)-tol-BINAP-catalyzed arylation reaction of aromatic aldehydes with arylboronic acids in the absence of CHCl3 is described. [Copyright &y& Elsevier]

Abstract: The influence of perfluoroalkyl chains on the coordination chemistry of monodentate and bidentate binaphthyl-based ligands, MonoPhos and BINAP, has been evaluated, and a single-crystal X-ray structural determination of [Cp*RhCl2((R)-MonoPhos)] obtained. In spite of its size, the binaphthyl backbone is not sufficient to completely insulate the phosphorus donor atoms from the electronic effects of the perfluoroalkyl groups, and additional spacer units are required. [Copyright &y& Elsevier]

Abstract: The solid-state structures for two complexes, 7 and 8, are reported. Complex 7 was prepared by treating Ru(OAc)2(Binap) with two equivalents of HBArF in toluene solution, and represents only the second solid-state structure of a Binap complex, in which the Binap is a 6e donor to the Ru(II). The bonding is maintained in solution as shown via 13C NMR studies. The unusual cation 8, as an salt, arises from prolonged reaction of Ru(OAc)2(Binap) with wet HBF4 (and, subsequently, added HSbF6) in 1,2-dichloroethane. [Copyright &y& Elsevier]