Preparation of Polymer-Supported Chiral 1,2-Diamine as an Efficient Ligand for Asymmetric Hydrogenation Catalyst

An enantiopure 1,2-diamine having two phenolic hydroxy groups was synthesized, and attached to chloromethylated poly(styrene) through a benzyl ether linkage. The polymer-supported Ru precatalysts were prepared from the polymeric chiral 1,2-diamine and RuCl₂/BINAP complex. In the presence of t-BuOK the polymeric catalyst system worked well in asymmetric hydrogenation of aromatic ketones in a mixed solvent of 2-propanol and DMF. The insoluble polymeric catalyst was readily separated from the reaction mixture and reused at least several times without loss of the catalytic activity.     

Preparation of the enantiopure 1,2-diamine monomer and its polymerization: The efficient polymeric chiral ligand of an asymmetric hydrogenation catalyst

An enantiopure 1,2-diamine monomer possessing a p-vinylbenzyl group as a polymerizable group was synthesized from chiral 1,2-bis(p-hydroxyphenyl)-N,N′-bis(tert-butoxycarbonyl)-1,2-diaminoethane. The chiral monomer was copolymerized with styrene, and this was followed by the deprotection of the tert-butoxycarbonyl group, which yielded the polymer-supported chiral 1,2-diamine. The polymeric catalyst system was established with the polymeric chiral 1,2-diamine complexed with 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl/RuCl₂. In the presence of potassium tert-butoxide (t-BuOK), the polymeric catalyst system worked well in the asymmetric hydrogenation of aromatic ketones. The corresponding chiral secondary alcohols were obtained in quantitative yields with a high level of enantioselectivity. The insolubility of the catalyst, caused by the crosslinked structure of the polymer, made it recyclable. The polymeric catalyst was reused several times without a loss of catalytic activity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4556–4562, 2004     

Synthesis of chiral iridium complexes immobilized on amphiphilic polymers and their application to asymmetric catalysis

This article details the enantioselective catalytic performance of crosslinked, polymer immobilized, Ir‐based, chiral complexes for transfer hydrogenation of cyclic imines to chiral amines. Polymerization of the achiral vinyl monomer, divinylbenzene, and a polymerizable chiral 1,2‐diamine monosulfonamide ligand followed by complexation with [IrCl₂Cp*]₂ affords the crosslinked polymeric chiral complex, which can be successfully applied to asymmetric transfer hydrogenation of cyclic imines. Polymeric catalysts prepared from amphiphilic achiral monomers have high catalytic activity in the reaction and can be used both in organic solvents and water to give chiral cyclic amines with a high level of enantioselectivity (up to 98% ee). The asymmetric reaction allows for reuse of the heterogeneous catalyst without any loss in activity or enantioselectivity over several runs. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3037–3044     

Synthesis of Novel Polymers with a Chiral 1,2-Diamine Moiety by Polycondensation and their Application to Catalyst for Asymmetric Hydrogenation of Aromatic Ketones

Summary: Novel polymers with chiral 1,2-diamine moiety were successfully synthesized by polycondensation of N-Boc protected enantiopure 1,2-diamine bearing two phenol groups ( S , S )-4 , bisphenol derivatives, and dibromides, followed by deprotection of N-Boc moiety. Hydrogenation of acetophenone was performed with use of polymeric catalyst system prepared from the polymer-supported chiral 1,2-diamine and RuCl₂/(S)-BINAP. The reaction proceeded smoothly even in 2-propanol to give 1-phenylethanol in quantitative yield with high level of enantioselectivity. Furthermore, various other aromatic ketones could be asymmetrically hydrogenated by the polymeric catalyst system.     

Chiral solvating agents for carboxylic acids based on the salen moiety

A series of chiral salen C₂-symmetric aminophenols 1–4, which were derived from (1R,2R)- or (1S,2S)-1,2-diphenylethane-1,2-diamine with the corresponding salicylic aldehyde through a [2+2] condensation reaction, have been prepared. The NMR studies demonstrated that they can function as chiral solvating agents for the determination of the enantiomeric purity of chiral carboxylic acids.     

Crystal structure and magnetic properties of catena-poly[bromido[trans (1S,2S)/(1R,2R)-cyclohexane-1,2-diamine copper(II)]-μ3-bromido]

Catena-poly[bromido [trans(1S,2S)/(1R,2R)-1,2-cyclohexane-1,2-diamine copper(II)]-μ₃-bromido], compound 1, exhibits a one-dimensional, coordination polymer structure in which chiral organic ligands are coordinated to a central inorganic ladder. In the structure layers of polymers of different chirality alternate, forming a racemic crystal. Strong, charge assisted hydrogen bonds link neighbouring polymers to form a two-dimensional hydrogen bonded sheet. Below 10 K weak antiferromagnetic interactions are observed between the copper(II) ions.     

Novel chiral tetraaza ligands: synthesis and application in asymmetric transfer hydrogenation of ketones

Novel chiral tetraaza ligands, N¹,N²-bis(2-(piperidin-1-yl)benzylidene)cyclohexane-1,2-diamine 1 and N¹,N²-bis(2-(piperidin-1-yl)benzyl)cyclohexane-1,2-diamine 2, have been synthesized and fully characterized by analytical and spectroscopic methods. The structure of (R,R)-1 has been established by X-ray crystallography. Asymmetric transfer hydrogenation of aromatic ketones with the catalysts prepared in situ from [IrHCl₂(COD)]₂ and the chiral tetraaza ligands in 2-propanol gave the corresponding optically active secondary alcohols in high conversions and good ees (up to 91%) under mild reaction conditions.     

Chiral diphenylselenophosphoramides: a new class of chiral ligands for the titanium(IV) alkoxide-promoted addition of diethylzinc to aldehydes

Chiral C₂-symmetric diphenylselenophosphoramides 1 and 2 were prepared from the reaction of diphenylselenophosphinic chloride with (1R,2R)-(−)-1,2-diaminocyclohexane and (1R,2R)-(+)-1,2-diphenylethylenediamine, respectively, in high yields. Another novel chiral ligand 3 was prepared from the reaction of diphenylselenophosphinic chloride with (R)-(+)-1,1′-binaphthyl-2,2′-diamine using butyllithium as the base. The ligands were used as catalytic chiral ligands in the titanium(IV) alkoxide-promoted enantioselective addition reaction of diethylzinc to aldehydes.     

Chiral diphenylthiophosphoramides: a new class of chiral ligands for the silver(I)-promoted enantioselective allylation of aldehydes

Chiral C₂-symmetric diphenylthiophosphoramides 1 and 2 were prepared in high yields from the reaction of diphenylthiophosphinic chloride with (1R,2R)-(−)-1,2-diaminocyclohexane and (1R,2R)-(+)-1,2-diphenylethylenediamine, respectively. Another novel chiral ligand 4 was prepared from reaction of diphenylthiophosphinic chloride with (R)-(+)-1,1′-binaphthyl-2,2′-diamine using butyllithium as a base. They were used as catalytic chiral ligands in the silver(I)-promoted enantioselective allylation reaction of aldehydes with allyltributyltin.     

Two chiral mononuclear and one-dimensional cadmium(II) complexes constructed by (1R,2R)-N1,N2-bis(pyridinylmethyl)cyclohexane-1,2-diamine derivatives: Effect of positional isomerism

Reactions of (1R,2R)-N¹,N²-bis(pyridinylmethyl)cyclohexane-1,2-diamine derivatives, (1R,2R)-2-bpcd and (1R,2R)-3-bpcd [(1R,2R)-2-bpcd = (1R,2R)-N¹,N²-bis(pyridin-2-ylmethyl)cyclohexane-1,2-diamine, (1R,2R)-3-bpcd = (1R,2R)-N¹,N²-bis(pyridin-3-ylmethyl)cyclohexane-1,2-diamine], with CdI₂ in an analogous way led to the formation of a chiral discrete mononuclear complex and a chiral one-dimensional polymeric chain, respectively, which may be attributed to the positional isomerism of the ligands. The chiral organic ligands and complexes display luminescent properties indicating that they may have a potential application as optical materials. Powder second-harmonic generation (SHG) efficiency measurement shows that the SHG efficiency of the complexes is approximately 0.3 and 0.45 times that of KDP, respectively.     

Anion directed templated synthesis of mono- and di-Schiff base complexes of Ni(II)

Two sets of Schiff base ligands, set-1 and set-2 have been prepared by mixing the respective diamine (1,2-propanediamine or 1,3-propanediamine) and carbonyl compounds (2-acetylpyridine or pyridine-2-carboxaldehyde) in 1:1 and 1:2 ratios, respectively and employed for the synthesis of complexes with Ni(II) perchlorate and Ni(II) thiocyanate. Ni(II) perchlorate yields the complexes having general formula [NiL₂](ClO₄)₂ (L = L¹ [N¹-(1-pyridin-2-yl-ethylidine)-propane-1,3-diamine] for complex 1, L² [N¹-pyridine-2-ylmethylene-propane-1,3-diamine] for complex 2 or L³ [N¹-(1-pyridine-2-yl-ethylidine)-propane-1,2-diamine] for complex 3) in which the Schiff bases are mono-condensed terdentate whereas Ni(II) thiocyanate results in the formation of tetradentate Schiff base complexes, [NiL](SCN)₂ (L = L⁴ [N,N′-bis-(1-pyridine-2-yl-ethylidine)-propane-1,3-diamine] for complex 4, L⁵ [N,N′-bis(pyridine-2-ylmethyline)-propane-1,3-diamine] for complex 5 or L⁶ [N,N′-bis-(1-pyridine-2-yl-ethylidine)-propane-1,2-diamine] for complex 6) irrespective of the sets of ligands used. Formation of the complexes has been explained by anion modulation of cation templating effect. All the complexes have been characterized by elemental analyses, spectral and electrochemical results. Single crystal X-ray diffraction studies confirm the structures of four representative members, 1, 3, 4 and 5; all of them have distorted octahedral geometry around Ni(II). The bis-complexes of terdentate ligands, 1 and 3 are the mer isomers and the complexes of tetradentate ligands, 4 and 5 possess trans geometry.     

Enantioselective synthesis of chiral 1,2-diamines by the catalytic ring opening of azabenzonorbornadienes: application in the preparation of new chiral ligands

In the presence of a rhodium catalyst (5 mol %) generated in situ from [Rh(cod)Cl]₂ and (S,S′)-(R,R′)-C₂-ferriphos-tolyl, the asymmetric ring-opening reaction of N-Boc-azabenzonorbornadienes with dibenzylamine proceeded with excellent enantioselectivity (up to >99% ee) to give the corresponding 1,2-diamine scaffolds in high yields. The sequential deprotection of the ring-opened products and treatment with tartaric acid gave the enantiomerically pure 1,2-diamine tartrate salts. These salts were used for the preparation of new chiral ligands such as the salen-type ligands and Trost-type ligands.     

New chiral metal complexes based on 2-ethoxymethylidene-3-oxo-3-polyfluoroalkylpropionates

Ethyl 2-ethoxymethylidene-3-oxo-3-polyfluoroalkylpropionates reacted with (1S,2S)-1,2-diphenylethane-1,2-diamine to give diethyl 2,2′-{[(1S,2S)-diphenylethane-1,2-diyl]bis[iminomethylidene]}bis(3-oxo-3-polyfluoroalkyl)alkanoates which were used as ligands to obtain chiral complexes with transition metals.     

Axially dissymmetric binaphthyldiimine chiral salen-type ligands for copper-catalyzed asymmetric aziridination

Axially dissymmetric chiral salen-type ligands 1–4 and 7 were prepared from the reaction of (R)-(+)-1,1′-binaphthyl-2,2′-diamine with 2,6-dichlorobenzaldehyde, 2,3-dichlorobenzaldehyde, 3,4-dichlorobenzaldehyde or salicylaldehyde in high yields, respectively. The catalytic asymmetric aziridination of alkenes has been examined using these novel chiral ligands. Excellent enantioselectivity in the aziridination of cinnamates has been achieved using the C₂-symmetric chiral ligand 1.     

Chemoenzymatic synthesis of enantiopure geminally dimethylated cyclopropane-based C2- and pseudo-C2-symmetric diamines

Enantiopure (−)-(1S,3S)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxamide 2 and (+)-(1R,3R)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid 3 were easily obtained from a multigram scale biotransformation of racemic amide or nitrile in the presence of Rhodococcus erythropolis AJ270 whole cell catalyst under very mild conditions. Coupled with efficient and convenient chemical manipulations, comprising mainly of the Curtius rearrangement, oxidation, and reduction reactions, chiral C₂-symmetric (1S,2S)-3,3-dimethylcyclopropane-1,2-diamine 6 and ((1R,3R)-3-(aminomethyl)-2,2-dimethylcyclopropyl)methanamine 8 and pseudo-C₂-symmetric (1S,3S)-3-(aminomethyl)-2,2-dimethylcyclopropanamine 11 were prepared. These were also transformed into the corresponding chiral salen derivatives 12, 13, and 14, respectively, in almost quantitative yields.     

An efficient chemoenzymatic method to prepare optically active primary-tertiary trans-cycloalkane-1,2-diamines

Optically active trans-N-Boc-cyclopentane- and cyclohexane-1,2-diamines (7) were prepared by a chemoenzymatic method from the corresponding (±)-trans-N,N-diallylcycloalkane-1,2-diamine. These mono-carbamates 7 (ee=99%) were used as the starting materials in the syntheses of different vicinal primary-tertiary diamines. Thus, by means of a simple three-step sequence involving a reductive-amination of an aromatic aldehyde with 7, N-methylation and finally, cleavage of the Boc group, several trans-N-(arylmethyl)-N-methylcyclopentane- and cyclohexane-1,2-diamines were obtained in high yields.     

Peroxidative bromination and oxygenation of organic compounds: Synthesis, X-ray crystal structure and catalytic implications of mononuclear and binuclear oxovanadium(V) complexes containing Schiffbase ligands

Treatment of of (R,R)-N,N-salicylidene cyclohexane 1,2-diamine(H₂L¹) in methanol with aqueous NH₄VO₃ solution in perchloric acid medium affords the mononuclear oxovanadium(V) complex [VOL¹(MeOH)]·ClO₄ (1) as deep blue solid while the treatment of same solution of (R,R)-N,N-salicylidene cyclohexane 1,2-diamine(H₂L¹) with aqueous solution of VOSO₄ leads to the formation of di-(μ-oxo) bridged vanadium(V) complex [VO₂L²]₂ (2) as green solid where HL² = (R,R)-N-salicylidene cyclohexane 1,2-diamine. The ligand HL² is generated in situ by the hydrolysis of one of the imine bonds of HL¹ ligand during the course of formation of complex [VO₂L²]₂ (2). Both the compounds have been characterized by single crystal X-ray diffraction as well as spectroscopic methods. Compounds 1 and 2 are to act as catalyst for the catalytic bromide oxidation and C-H bond oxidation in presence of hydrogen peroxide. The representative substrates 2,4-dimethoxy benzoic acid and para-hydroxy benzoic acids are brominated in presence of H₂O₂ and KBr in acid medium using the above compounds as catalyst. The complexes are also used as catalyst for C-H bond activation of the representative hydrocarbons toluene, ethylbenzene and cyclohexane where hydrogen peroxide acts as terminal oxidant. The yield percentage and turnover number are also quite good for the above catalytic reaction. The oxidized products of hydrocarbons have been characterized by GC Analysis while the brominated products have been characterized by ¹H NMR spectroscopic studies.     

Chiral sensing of Eu(III)‐containing achiral polymer complex from chiral amino acids coordination induction

The β‐diketonate‐based achiral polymer P‐1 could be synthesized by the polymerization of 3,7‐dibromo‐2,8‐dimethoxy‐5,5‐dioctyl‐5H‐dibenzo[b,d]silole ( M1 ) with (Z)?1,3‐bis(4‐ethynylphenyl)?3‐hydroxyprop‐en‐1‐one ( M2 ) via typical Sonogashira coupling reaction. The β‐diketonate unit in the main chain backbone of P‐1 can further coordinate with Eu(TTA)_x [TTA^? = 4,4,4‐trifluoro‐1‐(thiophen‐2‐yl)butane‐1,3‐dionate anion, X = 1, 2, 3] to afford corresponding Eu(III)‐containing polymer complexes. The resulting achiral polymer complex P‐2 (X = 2) can exhibit strong circular dichroism (CD) response toward both N‐Boc‐l and d‐ proline enantiomers. The CD signal was preliminarily attributed to coordination induction between chiral N‐Boc‐proline and the Eu(III) complex moiety. The linear regression analysis of CD sensing shows a good agreement between the magnitude of molar ellipticity and concentration of chiral N‐Boc‐l or d‐ proline, which indicates this kind Eu(III)‐containing achiral polymer complex can be used as a chiral probe for enantioselective recognition of N‐Boc‐l or d‐ proline enantiomers based on Cotton effect of CD spectra. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3080–3086     

Synthesis, crystal structure and antibacterial activity of a group of mononuclear manganese(II) Schiff base complexes

Five mononuclear complexes of manganese(II) of a group of the general formula, [MnL(NCS)₂] where the Schiff base L = N,N′-bis[(pyridin-2-yl)ethylidene]ethane-1,2-diamine (L¹), (1); N,N′-bis[(pyridin-2-yl)benzylidene]ethane-1,2-diamine (L²), (2); N,N′-bis[(pyridin-2-yl)methylidene]propane-1,2-diamine (L³), (3); N,N′-bis[(pyridin-2-yl)ethylidene]propane-1,2-diamine (L⁴), (4) and N,N′-bis[(pyridin-2-yl)benzylidene]propane-1,2-diamine (L⁵), (5) have been prepared. The syntheses have been achieved by reacting manganese chloride with the corresponding tetradentate Schiff bases in presence of thiocyanate in the molar ratio of 1:1:2. The complexes have been characterized by IR spectroscopy, elemental analysis and other physicochemical studies, including crystal structure determination of 1, 2 and 4. Structural studies reveal that the complexes 1, 2 and 4 adopt highly distorted octahedral geometry. The antibacterial activity of all the complexes and their respective Schiff bases has been tested against Gram(+) and Gram(−) bacteria.     

Synthesis and properties of a monomeric and a μ-oxo-bridged dimeric iron(III) complex with a tetradentate pyridine amide in-plane ligand. X-ray structure of [Fe(bpc)Cl(DMF)] [H2bpc=4,5-dichloro-1,2-bis(pyridine-2-carboxamido)benzene]

The controlled nucleophilic halide displacement reaction of [NEt₄][Fe(bpc)Cl₂] [H₂bpc=4,5-dichloro-1,2-bis(pyridine-2-carboxamido) benzene] with AgClO₄ in MeCN afforded a crystalline iron(III) complex Fe(bpc)Cl·H₂O 1. The mixed chloro-dimethylformamide (DMF) axially ligated complex [Fe(bpc)Cl(DMF)] (obtained during recrystallization of 1 from DMF; however, it loses DMF quite readily to revert back to 1) has been structurally characterized. It belongs to only a handful of mononuclear high-spin iron(III) complexes having deprotonated picolinamide ligand. The iron(III) centre is co-ordinated in the equatorial plane by two pyridine nitrogens and two deprotonated amide nitrogens of the ligand, and two axial sites are co-ordinated by a chloride ion and a DMF molecule. The metal atom has a distorted octahedral geometry. Reaction of 1 with [ⁿBu₄N][OH] in MeOH afforded a μ-oxo-bridged diiron(III) complex, [Fe(bpc)]₂O·DMF·2H₂O, 2. The spin state and the co-ordination environment of the iron(III) centres in 1 and 2 have been determined by temperature-dependent (25–300 K) magnetic susceptibility measurements in the solid state (Faraday method) and Mössbauer spectral studies at 300 K. Complex 1 behaves as a perfect S=5/2 system, in the solid-state as well as in DMF solution. The two iron(III) centres in 2 are antiferromagnetically coupled (J=−117.8 cm⁻¹) and the bridged dimeric structure is retained in DMF solution. Bridge-cleavage reactions of 2 have been demonstrated by its ready reaction with mineral acids such as HCl and MeCO₂H to generate authentic S=5/2 complexes, [Fe(bpc)Cl₂]⁻ and [Fe(bpc)(O₂CMe)₂]⁻, respectively.