Chiral Bis(N‐sulfonylamino)phosphine‐ and TADDOL‐Phosphite‐Oxazoline Ligands: Synthesis and Application in Asymmetric Catalysis

A series of N,P‐ligands has been prepared, containing a chiral oxazoline ring and as a second chiral unit a bis(N‐sulfonylamino)phosphine group embedded in a diazaphospholidine ring or a cyclic phosphite group derived from TADDOL. These modular ligands are readily synthesized from chiral amino alcohols and chiral 1,2‐diamines or TADDOLs. Palladium and iridium complexes derived from these ligands were found to be efficient catalysts for enantioselective allylic alkylation and olefin hydrogenation, respectively.     

Chiral Polyamino Alcohols via Hydroaminomethylation: A New Class of Polyamines for Dendritic Cores and Ligand Precursors

In this contribution, the synthesis of a new class of chiral polyamino alcohols (PAA) via a two‐step hydroaminomethylation/hydrolysis procedure is reported. The chiral polyamines are obtained by hydroaminomethylation of N‐olefinic oxazolidinones with different amines in first step followed by hydrolysis of the resulting polyamines to give the chiral PAA in the second step. The dendritic chiral PAA (Mw=1300–1400 g mol⁻¹) are also synthesized efficiently through a multifold hydroaminomethylation/hydrolysis procedure. Furthermore, chiral PAA are investigated as ligands in ruthenium‐catalyzed asymmetric hydrogen transfer reduction of acetophenone to 1‐phenyl alcohol.     

A High‐Throughput Screening Approach for the Determination of Additive Effects in Organozinc Addition Reactions to Aldehydes

The effects of additives in phenylzinc addition reactions to an aldehyde have been studied using an automated high‐throughput screening approach. With 2‐bromobenzaldehyde as test substrate and N,N‐dibutylnorephedrine (dbne) as chiral ligand, an improvement of 20% ee over the catalyzed reaction in the absence of the additive was observed. The described results enable a novel access towards chiral diarylmethanols using commercially available substrates, reagents and ligands as well as fast, automated techniques.     

A convenient synthesis of macroporous polymer‐supported supernucleophilic reagent and linear macromolecules

N,N′‐Bis(4‐pyridinyl)piperazine and N‐(4‐pyridinyl)piperazine have been prepared by treatment of piperazine with 4‐chloropyridine. N,N′‐Bis(4‐pyridinyl)piperazine (bis‐DMAP) is similar to a couple of 4‐(N,N‐dimethylamino)pyridine (DMAP). N‐(4‐Pyridinyl)piperazine as reactive group can be linked onto the macroporous polymeric carrier producing a polymer‐bound catalyst. A linear epoxy polymer containing the supernucleophilic functional groups have been synthesized by reaction of epichlorohydrin and 4‐aminopyridine. The linear polymeric catalysts have been braced by the macroporous resin to obtain a polymer‐supported linear polymeric catalyst. It is found that catalytic activity of bis‐DMAP approaches that of DMAP. The activity of the polymer‐supported linear polymeric catalyst is higher than that of the polymer‐bound catalyst in the acetylation of tert‐butyl alcohol, as monitored by gas–liquid chromatography. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 593–597, 2000     

Synthesis and application of polymer–clay nanocomposite‐supported dichromate oxidizing agent

A hybride polymer–clay nanocomposite supported dichromate reagents was prepared. Direct interaction of poly(styrene‐co‐N‐methyl‐4‐vinylpyridinium) iodide with sodium montmorillonite (MMT) through ion exchange between sodium cations in MMT and pyridinium ions in the copolymer afforded a polymer–clay nanocomposite (3). The resulting nanocomposite was reacted with potassium dichromate to form the nanocomposite‐supported reagents (4). The structure of the resulting nanocomposite was characterized by elemental analysis, infrared spectroscopy, X‐ray diffraction and transmission electron microscopy. The dispersion of the MMT particles in the polymer matrix was confirmed using scanning electron microscopy. X‐ray mapping for silicon in the nanocomposite revealed uniform distribution of Si in the polymer matrix. The effectiveness of these materials has been tested for oxidation of saturated primary, secondary and benzylic alcohols to their corresponding aldehydic and ketonic compounds in addition to oxidation of quinol to the corresponding quinone. Importantly, there is almost no formation of side‐product of this process. POLYM. COMPOS., 36:2066–2075, 2015. © 2014 Society of Plastics Engineer     

Dendritic Chiral Phosphine Lewis Bases‐Catalyzed Asymmetric Aza‐Morita–Baylis–Hillman Reaction of N‐Sulfonated Imines with Activated Olefins

A series of polyether dendritic chiral phosphine Lewis bases was synthesized, and successfully applied to the asymmetric aza‐Morita–Baylis–Hillman reaction of N‐sulfonated imines (N‐arylmethylidene‐4‐methylbenzenesulfonamides) with methyl vinyl ketone (MVK), ethyl vinyl ketone (EVK), and acrolein to give the adducts in good to excellent yields along with up to 97 % ee, which are more effective than our previously reported original chiral phosphine Lewis bases. In addition, the dendrimer‐supported chiral phosphine Lewis bases can be easily recovered and reused.     

Cyclometalated N‐Heterocyclic Carbene‐Platinum Catalysts for the Enantioselective Cycloisomerization of Nitrogen‐Tethered 1,6‐Enynes

Platinum(II) complexes which combine six‐membered N‐heterocyclic carbene‐containing metallacyclic units and monodentate chiral phosphines have been prepared. The key step of their synthesis is the intramolecular oxidative addition of N‐2‐iodobenzylimidazolylidene‐platinum(0)‐diene complexes in the presence of the chiral phosphorus ligands. The platinum(II) metallacycles have been used as well‐defined pre‐catalysts for the enantioselective cycloisomerization of nitrogen‐tethered 1,6‐enynes into 3‐azabicyclo[4.1.0]hept‐4‐enes. High enantiomeric excesses have been obtained with either Monophos or phenyl‐Binepine based catalysts (ees=82–96%), although phenyl‐Binepine outperforms Monophos in these reactions. The absolute configuration of the final 3‐azabicyclo[4.1.0.]heptenes has been established by X‐ray diffraction studies. The method has been extended then to the cycloisomerization of dienynes with enantiotopic vinyl groups. An (S)‐phenyl‐Binepine‐platinum(II) complex allows total diastereoselectivity and high enantioselectivity levels to be attained in these reactions (ees up to 95%) which represent the first enantioselective desymetrizations achieved via enyne cycloisomerizations.     

Modular Phosphine‐Aminophosphine Ligands Based on Chiral 1,2,3,4‐Tetrahydro‐1‐naphthylamine Backbone: A New Class of Practical Ligands for Enantioselective Hydrogenations

A series of new chiral phosphine‐aminophosphine ligands [(R)‐HW‐Phos] has been prepared from (R)‐1,2,3,4‐tetrahydro‐1‐naphthylamine through a two‐step procedure, and successfully applied in the rhodium‐catalyzed asymmetric hydrogenation of various functionalized olefins such as α‐enol ester phosphonates, α‐enamido phosphonates, (Z)‐β‐(acylamino)acrylates and so on. Excellent enantioselectivities have been achieved in the hydrogenation of most substrates tested, demonstrating the high potential of these newly developed phosphine‐aminophosphine ligands in asymmetric catalysis. The present research also discloses that these newly developed phosphine‐aminophosphine ligands are more efficient than that derived from (S)‐1‐phenylethylamine, suggesting that the increased rigidity conferred by a cyclohexyl fragment in these phosphine‐aminophosphine ligands has a positive effect in the asymmetric induction.     

Surface modification of temperature‐responsive polymer particles by an electrically conducting polyaniline shell layer

In this research an attempt was made to prepare biocompatible electrically conductive composite polymer particles in view of their wide applications in biotechnology. Temperature‐sensitive polymer particles have applications as drug carriers, bioseparators, bioreactor cell activators and diagnostic reagents. So a combination of diverse properties in a single polymer composite is expected to increase its application potential. Here temperature‐responsive poly(N‐isopropyl acrylamide‐methyl methacrylate‐N,N′‐methylene‐bis‐acrylamide) (P(NIPAM‐MMA‐MBAAm)) core particles were prepared by emulsion copolymerization without using any stabilizer. In a second step seeded chemical oxidative polymerization of different amounts of aniline was carried out in the presence of submicron‐sized core particles to obtain P(NIPAM‐MMA‐MBAAm)/polyaniline composite particles. For a comparative study, reference polyaniline particles were prepared by chemical oxidative polymerization. Fourier transform IR spectroscopy, UV?visible spectroscopy, thermal and X‐ray diffraction analyses showed that composite particles prepared with higher aniline content (0.8 g) per unit mass (g) of core particles had high surface coverage compared with lower aniline content (0.1 g). © 2013 Society of Chemical Industry     

Chiral Phosphinopyrrolyl‐Oxazolines: A New Class of Easily Prepared,Modular P,N‐Ligands

Chiral 2‐(N‐phosphinopyrrol‐2‐2)oxazolines (PyrPHOX ligands) are readily prepared from 2‐cyanopyrrole by condensation with a chiral amino alcohol and subsequent reaction with dialkyl‐ or diaryl‐chlorophosphines. Iridium complexes of these ligands proved to be highly efficient catalysts for the enantioselective hydrogenation of olefins. With unfunctionalized arylalkenes and ethyl cinnamate enantiomeric excesses of 70–99% were obtained.     

Hexahydropyrrolo[2,3‐b]indoles: A New Class of Structurally Rigid Tricyclic Skeleton for Oxazaborolidine‐Catalyzed Asymmetric Borane Reduction

A new class of structurally rigid tricyclic chiral ligands based on the hexahydropyrrolo[2,3‐b]indole skeleton has been rationally designed and the catalytic abilities in asymmetric catalysis have been shown in the enantioselective borane reduction of prochiral ketones to afford the chiral alcohols in excellent yields and high enantioselectivities (up to 97% ee).     

Iron‐Catalyzed Highly Enantioselective Reduction of Aromatic Ketones with Chiral P2N4‐Type Macrocycles

Novel P₂N₄‐donors containing chiral 22‐membered macrocyclic ligands have been synthesized and the structures have been determined by an X‐ray diffraction study. The catalytic systems in situ generated from triiron dodecarbonyl, Fe₃(CO)₁₂, and the chiral macrocyclic ligand exhibited high activity (TOF up to 1940 h⁻¹) and excellent enantioselectivity with up to 99% ee in the asymmetric transfer hydrogenation of various aromatic ketones.     

Evaluation of Ligands for Ketone Reduction by Asymmetric Hydride Transfer in Water by Multi‐Substrate Screening

Various ligands for the ruthenium‐catalyzed enantioselective reduction of ketones in water have been investigated. Multi‐substrate reactions have been carried out for the comparison of various proline amides and aminoalcohol ligands. Two sets of six aromatic ketones have been selected in order to evaluate the enantiomeric excesses of all the resulting alcohols by a single chromatographic analysis. The proline amide derivative prepared from (1R,2S)‐cis‐aminoindanol revealed as the best ligand for most of the ketones used in the multi‐substrate reductions. This ligand has been employed for the enantioselective reduction of a variety of other aromatic ketones and in all cases the enantiomeric excesses were improved compared to those obtained with phenylprolineamide used in our previous work.     

Simple,Mild, and Practical Esterification,Thioesterification, and Amide Formation Utilizing p‐Toluenesulfonyl Chloride and N‐Methylimidazole

We have developed an efficient method for the esterification or thioesterification of equimolar amounts of carboxylic acids and alcohols or thiols using a novel reagent, p‐toluenesulfonyl chloride (TsCl) together with N‐methylimidazole. The present method is simple, mild, and reactive, uses readily available and economical reagents. The choice of amine is critical for the present method. The amine, N‐methylimidazole, has two roles: (i) as an HCl scavenger for the initial smooth generation of mixed anhydrides between carboxylic acids and TsCl and (ii) successive formation of highly reactive ammonium intermediates from mixed anhydrides. This method could be applied to various types of carboxylic acids, alcohols, and thiols: a) several functionalities were tolerated; b) two N‐Cbz amino acids were smoothly esterified without racemization; and c) the labile 1β‐methylcarbapenem key intermediate and a pyrethroid insecticide, prallethrin, were successfully prepared. The related amide formation between carboxylic acids and primary or secondary amines was also performed. The proposed reaction mechanism involves a novel method for producing the reactive acylammonium intermediates. The production of these intermediates was rationally supported by a careful ¹H NMR monitoring study.     

Reusable Chiral Dicationic Chromium(III) Salen Catalysts for Aminolytic Kinetic Resolution of trans‐Epoxides

A series of new recyclable chiral dicationic chromium(III) salen complexes 1 – 10 bearing different substituents, viz., hydrogen, methyl, tert‐butyl, triphenylphosphinomethyl, triethylaminomethyl, methylimidazolium, methylpyridinium, methyl‐N,N‐dimethylpyridinium at the 3,3′‐ and 5,5′‐ positions of the salen unit with (1S,2S)‐(+)‐1,2‐diaminocyclohexane, (1S,2S)‐(−)‐1,2‐diphenyl‐1,2‐diaminoethane, and (S)‐(−)‐1,1′‐binaphthyl‐2,2′‐diamine collars have been synthesized and characterized by various physico‐chemical methods. These complexes were used as catalysts for the highly enantioselective aminolytic kinetic resolution of racemic trans‐epoxides with different anilines as nucleophiles at room temperature. With the use of catalyst 3 , anti‐β‐amino alcohols were obtained in excellent yields (>99% with respect to the nucleophile) and enantioselectivities (ee>99%) with the concomitant recovery of corresponding epoxides in high optical purity (ee up to >99%) and quantitative yields in 12 h. The catalyst 3 is recyclable in the aminolytic kinetic resolution process and worked well up to six cycles with retention of enantioselectivity.     

Ferrocene‐Based Chiral Phosphine‐Triazines: A New Family of Highly Efficient P,N Ligands for Asymmetric Catalysis

The presence of the additional heterocyclic nitrogen atoms in chiral P,N ligands has an important influence on the asymmetric catalysis, and a clear trend was observed in the present research that the enantioselectivity and reactivity were significantly increased by raising the number of heterocyclic nitrogen atoms in these P,N ligands. Through finely tuning the number of heterocyclic nitrogen atoms, a new family of ferrocene‐based chiral phosphine‐triazine ligands with three heterocyclic nitrogen atoms has been developed and successfully applied in Pd‐catalyzed asymmetric allylic substitution. Up to 99% ee with 99% yield of allylic alkylation products and 94% ee of allylic amination products have been obtained by the use of ligand (R_c,S_p)‐ 1f with a 4,6‐diphenoxy‐1,3,5‐triazine moiety.     

Simple Chiral Diaminobinaphthyl Dilithium Salts for Intramolecular Catalytic Asymmetric Hydroamination of Amino‐1,3‐dienes

Simple and easily accessible chiral lithium amide salts are reported as efficient (pre)catalysts for the diastereo‐ [up to (E:Z)=92:8] and enantioselective [up to 72% ee (E)] hydroamination/cyclisation of conjugated primary aminodienes. These chiral lithium salts are straightforwardly prepared by in situ combination of an N‐substituted (R)‐(+)‐1,1′‐binaphthyl‐2,2′‐diamine ligand and a commercial methyllithium solution. Information on the solid‐state structure of these salts was obtained by X‐ray analysis of a single crystal.     

Catalytic Asymmetric Alkynylation and Arylation of Aldehydes by an H8‐Binaphthyl‐Based Amino Alcohol Ligand

A novel chiral H₈‐1,1′‐binaphthyl‐based amino alcohol ligand (1R_a,2S,3R)‐ 2 has been synthesized and applied in the direct nucleophilic addition of organozincs (alkynylzinc and arylzinc prepared in situ) to aldehydes, yielding the corresponding optically active propargylic alcohols and diarylmethanols in high yields and good to excellent enantioselectivities. For the asymmetric arylation reaction, one catalyst (1R_a,2S,3R)‐ 2 can afford both enantiomers of many pharmaceutically interesting diarylmethanols by a proper combination of various arylzinc reagents and aldehydes.     

Diastereoselective Synthesis of N‐Substituted Planar Chiral Ferrocenes Using a Proline Hydantoin‐Derived Auxiliary

An N‐substituted ferrocene bearing a proline‐derived chiral directing group undergoes diastereoselective lithiation–electrophile quench to give planar chiral products in >95:5 dr. The starting material is synthesized by imidation of iodoferrocene with L ‐proline hydantoin, followed by hydrosilylation. Although the auxiliary is stable to lithium bases of the types RLi and R₂NLi, the ortho‐substituted products may be converted to solely planar chiral derivatives with simple reagents thanks to a labile triethylsilyloxy moiety.     

Asymmetric Synthesis with N‐Heterocyclic Carbenes. Application to the Copper‐Catalyzed Conjugate Addition

Chiral N‐heterocyclic carbenes are good ligands for the copper‐catalyzed conjugate addition of dialkylzinc reagents to various Michael acceptors. With as little as 4% of chiral ligand, the enantioselectivity may reach 93% on cycloheptenone.