36 results about "Chiral ligand" patented technology

The application relates to a chiral NSiN ligand based on a phenyloxazoline skeleton, a preparation method and application thereof, wherein the chiral NSiN ligand is prepared from a chiral phenyloxazoline bromide with R or S configuration through lithiation and silylation. The chiral NSiN ligand can be used in transition metal catalyzed asymmetric synthesis, and is used in catalyzing an allylic sulfonylation reaction with a cobalt catalyst, and shows high reaction activity and high stereoselectivity.

The invention discloses a method for preparing a chiral benzhydrol compound through asymmetric hydrogenation of o-amido benzophenone under catalysis of rhodium. The chiral rhodium catalyst is generated in situ from a metal rhodium salt and a chiral phosphine-phosphoramidite ligand in various solvents. Compared with other methods for synthesizing chiral benzhydrol, the method has the characteristics of cheap catalyst, easiness in preparation of chiral ligand, mild reaction conditions, simplicity and convenience in operation, high yield, high enantioselectivity and the like, and can be applied to large-scale preparation of chiral benzhydrol compounds. The method is also suitable for efficient preparation of the rice plant growth regulation inhibitor (S)-Inabenide, the yield can reach 92%, the enantioselectivity can reach 96%, and the method has good industrial application prospects.

The application discloses a rhodium-catalyzed desymmetrization hydroformylation method for constructing polychiral center carbon ring nucleosides. The method for constructing polychiral center carbon ring nucleosides comprises the following steps: under the condition of an inert atmosphere, an acetylacetone dicarbonyl rhodium metal precursor and a chiral ligand are added into an organic solvent to prepare a catalyst solution, the catalyst solution is mixed with a substrate, and a reaction is carried out under the condition of a hydrogen atmosphere and a carbon monoxide atmosphere; after the reaction is completed, filtration and purification are carried out, and polychiral center cycloalkyl aldehyde is obtained; and the aldehyde group is converted to obtain the polychiral center carbon ring nucleosides. The method for constructing polychiral center carbon ring nucleosides has the advantages of high selectivity, wide substrate compatibility, high reaction efficiency, easy conversion of products, and the like. The whole reaction process can obtain polychiral center cycloalkyl aldehyde in one step with extremely high enantioselectivity and diastereoselectivity, the aldehyde group is converted, polychiral center carbon rings can be obtained with high yield, high dr value and high ee value, and the method is simple and easy to operate.

The application discloses a method for detecting glutathione by using manganese-based chiral nanomaterials, and belongs to the field of chemical engineering, specifically to the field of analytical chemistry technology. The method comprises the following steps: taking a dispersion liquid of manganese-based chiral nanomaterials as a detection reagent, mixing the detection reagent with a sample containing glutathione to be detected, and comparing a circular dichroism spectrum signal with a standard curve to obtain the concentration of the sample containing glutathione to be detected; wherein a chiral ligand of the manganese-based chiral nanomaterials is ribose. Based on the circular dichroism spectrum detection, the detection wavelength band used is in the visible light region, is not easy to be disturbed, is sensitive, and the resolution can reach 3 muM, and the detection limit is 1.5 muM, which has important significance and value for promoting the development of the fields of optics, life science, medicine and the like.

This invention provides a class of general-purpose chiral catalysts containing a cinchona primary amine arylformamide skeleton, along with their preparation methods and applications, belonging to the field of catalytic materials technology. The chiral catalysts provided by this invention link cinchona primary amine with oxazole / thiazole / imidazolium formamide structural units capable of coordination. Through the coordination of the oxazole / thiazole / imidazolium and amide coordinating groups with the central metal, they act as chiral ligands to catalyze a wider range of asymmetric reactions. They can also be used alone as chiral small-molecule catalysts for cinchona-like tertiary amine (thiourea) and square amides to catalyze asymmetric organic reactions. Furthermore, they can achieve synergistic (co-catalytic) catalysis of small molecules and metals in the same reaction system through different combinations. These chiral catalysts can be widely used as Lewis bases, Lewis acids, or small-molecule chiral catalysts and chiral ligands, possessing potential scientific and applied value in chiral sciences such as asymmetric catalysis, chiral synthesis, and chiral resolution.

The application discloses a kind of photocontrol chiral ligand based on diarylethene, structural general formula is as shown in following formula:After the photocontrol chiral ligand based on diarylethene synthesized in the application and rhodium catalyst coordination, when catalyzing asymmetric carbon hydrogen amidation at room temperature, higher reaction yield and higher ee value can be obtained by using ligand in open loop state to catalyze, and lower reaction yield and lower ee value can be obtained by using ligand in light stable state to catalyze.The application makes up the deficiency that there is currently lack of photo-thermal bistable photocontrol catalyst in the field of photocontrol asymmetric catalysis, and widens the application of diarylethene in photocontrol asymmetric catalysis.

The present invention relates to the field of pesticide chemistry technology, and in particular, to a method for selectively and asymmetrically hydrogenating 4-substituted-1,2-dihydroquinoline and use thereof. The present invention discloses a selective, asymmetric hydrogenation reaction conducted on 4-substituted-1,2-dihydroquinoline in the presence of a chiral ligand and a rhodium catalyst. The selective, asymmetric hydrogenation method features ease to operate, a higher conversion rate, and higher enantioselectivity.

This invention belongs to the field of chemical catalysis technology, and discloses a class of bridged carboxylic acid-containing bifunctionalized phosphine ligands or their racemates or enantiomers, as well as their preparation methods and applications. The bridged carboxylic acid-containing bifunctionalized phosphine ligands or their racemates or enantiomers of this invention have the structures shown in Formulas I-V: wherein, R 1 R' is a C1-C5 straight-chain alkyl group; R' is any one of substituted or unsubstituted aryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl. The bridged carboxylic acid-containing bifunctionalized phosphine ligand of this invention, with biphenyl as its backbone, achieves complete transfer of facet chirality to axial chirality through a desymmetry reaction via precise chiral recognition and control. The resulting chiral ligand exhibits advantages such as high reactivity, good enantioselectivity, and a wide substrate adaptability. It is particularly effective in palladium-catalyzed asymmetric C-H bond-activated arylization reactions of halogenated compounds and can be applied to asymmetric C-H bond-activated arylization reactions.

This invention provides a method for preparing chiral N-tert-butylsulfonamide compounds. The method uses N-tert-butylsulfonylimide as a starting material, employs Mn(CO)₅Br and a chiral PNN ligand as catalysts, and an alcohol as a solvent. A hydrogenation reaction occurs in this homogeneous catalytic system, yielding axially chiral diaryl nitrophenol compounds in high yield (99%) and with high ee values ​​(>99%). This reaction has the advantages of high efficiency, mild conditions, and environmental friendliness. The obtained chiral N-tert-butylsulfonamide can be deprotected with a sulfonyl protecting group to obtain the corresponding chiral primary amine.

The application discloses an axially chiral cyclopentenyl and indole-naphthyl compound and a preparation method and application thereof, and the structural formula of the compound is shown in formula 3 and formula 5. The formula 3 compound is obtained by stirring and reacting formula 1 and formula 2 compounds under the action of a chiral phosphoric acid catalyst. The formula 5 compound is obtained by synthesizing the formula 3 compound in two steps. Through biological activity testing, the formula 3 compound has significant cytotoxic activity on PC-3 cancer cells. Through model reaction verification, the formula 5 compound can be used as a chiral ligand or a chiral organic catalyst, and is respectively applied to catalyzing asymmetric allyl coupling reaction and catalyzing asymmetric (4+1) cycloaddition reaction. The method for preparing the axially chiral cyclopentenyl and indole-naphthyl compound is simple in operation, mild in reaction condition, economical and easy in raw material, high in optical purity of the prepared axially chiral compound, high in yield and good in application prospect.

The application discloses a preparation method of chiral manganese dioxide enantiomer nanozyme and application thereof, and belongs to the technical field of functional material synthesis. The preparation method comprises the following steps: placing a mixture alkaline aqueous solution containing a manganese source, a chiral ligand, a template agent and an alkali in a closed container, and reacting to obtain the chiral manganese dioxide enantiomer nanozyme; the chiral ligand is selected from L-tartaric acid and / or D-tartaric acid; and the template agent is selected from a cationic surfactant. The chiral manganese dioxide nanozyme prepared in the application has significant peroxidase activity and oxidase activity.

This invention provides a rhodium-based heterogeneous chiral catalyst that is easy to recycle and its preparation method. The invention first successfully prepares a heterogeneous chiral catalyst support through 6-bromohexylation, chiral ligand amination, and phosphineation. Then, a filamentous spun product CM3-P is prepared using an electrospinning process. Finally, Rh(I) is loaded to obtain a filamentous Rh-based catalyst. The rhodium-based heterogeneous chiral catalyst prepared by this invention is a filamentous product, which is easy to recycle in industrial production and has good industrial adaptability.

The application discloses a kind of chiral iron-based nanowires and its preparation method, belong to nanometer material synthesis technical field.The method includes the following steps: the mixture containing iron source, chiral ligand, polyhydric alcohol solvent, base, amine reducing agent is alkaline aqueous solution, reaction, obtains the chiral iron-based nanowires;Chiral ligand is selected from L-cystine and / or D-cystine.This application method is simple, and the morphology of product is uniform, easy to realize large-scale preparation, the two iron-based nanowires of L and D configuration synthesized are all in ultraviolet-visible light region Good circular dichroism spectrum symmetry, for preparing having enantiomeric chiral nanometer material and researching chiral small molecule induced chiral nanometer material synthesis has guiding significance.

The application discloses a manganese-based chiral enantiomeric nanowire and a preparation method thereof, and belongs to the technical field of nanometer material synthesis. The method comprises the following steps: placing a mixture alkaline aqueous solution containing a template agent, a manganese source, a chiral ligand and an alkali in a closed container, and reacting to obtain the manganese-based chiral enantiomeric nanowire. The chiral ligand is selected from L-histidine and / or D-histidine; and the template agent is selected from a cationic surfactant. The two manganese-based superparticles of L and D configurations synthesized in the application have good chiral optical activity in a visible light region, circular dichroism spectrum presents very good symmetry, and the method has important research significance for preparing enantiomeric chiral nanowires by using a surfactant as a template and for researching a chiral ligand-induced chiral nanometer material assembly mechanism.

The invention discloses a method for preparing a chiral amine compound through asymmetric hydrogenation of ruthenium catalyzed imine. The chiral ruthenium catalyst is a chiral metal ruthenium complex prepared by reacting metal ruthenium salt with a chiral phosphine-phosphoramidite ester ligand and chiral diamine in a solvent and carrying out column chromatography. Compared with other chiral amine synthesis methods, the method provided by the invention has the characteristics of cheap catalyst, easy preparation of chiral ligand, mild reaction conditions, simple operation, high yield and enantioselectivity and the like, and can be applied to large-scale preparation of chiral amine compounds. The method is also suitable for synthesis of the key intermediate of the herbicide (S)-metolachlor, the yield can reach 92%, the enantioselectivity can reach 90%, and the method has good industrial application prospects.

This invention belongs to the field of crystal material preparation technology, and particularly relates to a chiral heterometallic oxy-cluster material and its preparation method. The method includes the following steps: reacting a metal-organic cage with a chiral ligand and a heterometallic compound via a solvothermal reaction to obtain the chiral heterometallic oxy-cluster material; wherein the metal-organic cage is selected from at least one of PTC-101, PTC-101(Zr), and PTC-102(Hf), and the heterometal is selected from one or more of calcium, copper, and zinc. The preparation method of this invention is simple and can synthesize high-purity materials in large quantities.

This invention discloses a cobalt-catalyzed migration asymmetric spirocyclic cyclocyclization method for quinoline compounds. This method utilizes a cobalt and ligand combination catalysis to achieve migration asymmetric spirocyclic cyclocyclization of quinoline compounds, belonging to the fields of organic chemistry and medicinal chemistry. Under the influence of a cobalt source, chiral ligands, achiral ligands, reducing agents, and additives, this invention enables the reaction of aryl / alkenyl-substituted quinolines / intramolecularly migrating quinolines with different alkynes in organic solvents, yielding a series of spirocyclic chiral dihydroquinoline compounds with excellent enantioselectivity and good yields. This invention only requires different ligands to regulate the reaction, enabling migration asymmetric dearomatization spirocyclic cyclocyclization from aryl to aryl, migration asymmetric dearomatization spirocyclic cyclocyclization from aryl to alkenyl, and intramolecular migration asymmetric dearomatization spirocyclic cyclocyclization reactions. It has a wide substrate applicability and produces diverse product structures, providing a novel and universal method for the systematic synthesis of chiral spirocyclic dihydroquinoline compounds.

Disclosed herein are methods for preparing tertiary alcohols from optionally substituted phenyl ketones or optionally substituted pyridyl ketones, the methods comprising the use of chiral ligands and boron trifluoride etherate. The tertiary alcohols can be used to prepare synthetic forms of natural products and / or drugs.

The present application relates to a kind of chiral six-tooth nitrogen-containing binuclear ligand, the present application is first synthesized chiral diamine as parent skeleton, the binuclear chiral ligand containing pyridine and chiral oxazoline unit, use chiral diamine as chiral skeleton to tie two pyridine oxazoline groups, wherein chiral diamine and chiral oxazoline unit have (S) or (R) configuration chiral center carbon.The synthesis method of ligand is obtained by five steps or six steps reaction with simple available raw materials.The ligand is functional ligand, can be able to with two same or different metal coordination, in reaction binuclear jointly activates substrate or mononuclear activates substrate, another metal as ligand influences catalytic center activity.This kind of binuclear catalyst is expected to realize the reaction that conventional mononuclear catalyst is difficult to realize by unique metal-metal bond, and be applied to many asymmetric catalytic reactions, with good application prospect.

This invention relates to a method for synthesizing the sitafloxacin intermediate 5-benzyl-7(S)-tert-butoxycarbonylamino-5-azaspiro[2,4]heptane. The method uses 1-benzylmethylpyrrolidine-2,4-dione as the starting material and proceeds through five steps: cyclization, oxime formation, chiral asymmetric reduction, salt formation, and amino protection to obtain the target product. Specifically, the cyclization reaction uses an alkylating agent and a base to construct a spirocyclic structure; the oxime reaction introduces a methoxyimino group via methoxyamine hydrochloride; the chiral asymmetric reduction uses a catalytic system composed of a chiral ligand and a boron reagent to construct the chiral center, followed by purification via maleic acid salt formation; and finally, the amino group is protected with di-tert-butyl dicarbonate to obtain the target product. This invention offers high atom economy, good process scalability, simple operation, controllable cost, and high product purity, providing a reliable intermediate synthesis scheme for the efficient preparation of sitafloxacin active pharmaceutical ingredient.

The application discloses a kind of chiral 7-azaindoline amide compounds, its synthesis method and application, belong to organic chemistry synthesis and medical technology field, the compound has with N-[3-phenyl-3-(diphenyl phosphoryl) propionyl] Substituted 7-azaindoline as basic skeleton Structural characteristics;Its synthesis method is: under room temperature condition, copper salt is dissolved in organic solvent with chiral ligand (L) Stirring mixing, then sequentially adding α, β-unsaturated 7-azaindoline amide (I), diphenyl phosphine (II) And base, after stirring reaction, the target product is obtained by separation and purification;The compound provided by the application can be efficiently converted into other novel 7-azaindoline derivatives by simple reaction, and has potential application value in the field of medicinal chemistry and asymmetric catalysis;The synthesis method provided by the application has the advantages of simple operation, mild reaction condition, wide substrate applicability, high yield and high enantioselectivity.

The application discloses a method for preparing chiral secondary alcohol through alternating current catalytic asymmetric electrophilic cross-coupling reaction. The method comprises the following steps: mixing azafused aryl triflate, aldehyde, electrolyte, nickel catalyst, ligand and sacrificial agent in a solvent in a protective atmosphere, and then carrying out asymmetric electrophilic cross-coupling reaction under alternating current condition, and then carrying out post-treatment to obtain the chiral secondary alcohol compound. The asymmetric cross-coupling reaction of azafused aryl triflate and aldehyde substrate is catalyzed by alternating current, and the asymmetric cross-coupling of various aryl (class) halides and aldehydes can be realized; the alternating current is used to improve the mass transfer efficiency, reduce the electrode corrosion and inhibit the reduction hydrogenation. In addition, the synthesis product can be used as a chiral ligand, and the practicability of the product in asymmetric catalysis is proved, and the product has wide development prospect. The electrochemical synthesis method has the characteristics of mild reaction condition, cleanness and greenness and simple reaction operation.

The application discloses a kind of chiral ligand PPBOX, its preparation method and application in asymmetric catalytic conversion, specifically related to a kind of compound as shown in formula I as chiral ligand in reaction, the reaction is reaction A, reaction B or reaction C;Reaction A: copper catalyst catalyzed tension release driven remote leaving group participated asymmetric propargyl amination, reaction B: copper catalyst catalyzed tension release driven remote leaving group participated asymmetric alkylation reaction, reaction C: copper catalyst catalyzed asymmetric propargyl enoxy. Such chiral ligand has excellent catalytic efficiency and stereoselective effect in the three types of asymmetric conversion reactions.

The application provides a chiral catalyst containing a chiral pyrrolidine and oxamide skeleton, a preparation method and application. The catalyst prepared by the application has simple structure, easy-to-obtain starting chiral raw materials, simple synthesis route and process, and is easy to separate and purify. The target chiral catalyst contains a chiral pyrrole ring skeleton, has typical structure and functional characteristics of a chiral small molecule catalyst, and also contains an oxamide structural unit, has structure characteristics and functions of a chiral ligand and a chiral Lewis acid. Since the chiral pyrrolidine and the chiral oxamide skeleton are simultaneously contained, the target chiral catalyst also has all the functional characteristics generated by the synergistic or joint action of the two. The target chiral catalyst can be widely used as a new type of Lewis base, Lewis acid, multifunctional small molecule chiral catalyst, hydrogen bond donor, chiral ligand functional compound, and has potential scientific and application values in asymmetric catalysis, chiral synthesis, chiral resolution, chiral substances and other chiral sciences, alone or in cooperation with a central metal.

This invention relates to the field of nanomaterials technology and discloses a chiral Cu 2‑x S-quantum dots, their preparation methods, and applications: In an aqueous phase, a copper source and a complexing agent are mixed and reacted to obtain a copper complex solution. A sulfur source and a dextrorotatory penicillamine chiral ligand are added to the copper complex solution. The mixed reaction solution is heated to carry out nucleation and growth reactions. After centrifugation and drying of the precipitate, chiral Cu with high photothermal conversion efficiency is obtained. 2‑x S-quantum dots. This invention is the first to use dextrorotatory penicillamine, which has a significant steric hindrance effect, as a chiral ligand during the growth of quantum dots. Its unique molecular structure induces the formation of a specific surface coordination environment and chiral structure. This structure can significantly enhance the absorption of near-infrared light by quantum dots and promote the non-radiative relaxation conversion of light energy into heat energy, greatly improving photothermal conversion performance. This provides an efficient and feasible technical solution for the practical application of chiral quantum dots in the field of tumor photothermal therapy.

The present invention relates to the field of asymmetric catalysis and organic synthesis, and specifically provides a general method for generating axial chirality by means of a chiral companion strategy. The features and concept of the method are: a chiral aromatic tertiary amine compound without a nitrogen chiral center is subjected to intramolecular chiral oxidation to induce the formation of a new aromatic tertiary amine N-oxide (NO) chiral center. Due to the structural rigidity of the chiral aromatic tertiary amine N-oxide compound, when the steric hindrance of different substituents Rb and Rs connected to ortho positions of an aromatic ring is relatively large, the rotation of the aromatic ring is hindered, and new rotation-hindered axial chirality is generated while an aromatic tertiary amine chiral N-oxide center is formed. By means of the method and by regulating the structural and functional characteristics of the different substituents Rb and Rs, various axial chiral ligands, chiral small-molecule catalysts, pharmaceutical and agrochemical intermediates, and chiral synthons can be prepared. The present invention has important scientific and application values for the design, synthesis, and application of chiral ligands, chiral catalysts, especially ligands and catalysts containing axial chirality, and chiral compounds having special functions.

This application relates to a synthetic method and application of cycloaddition intermediates, belonging to the field of organic synthesis technology. Using 4-cyano-2-methoxybenzaldehyde, isopropyl malonate, 4-amino-2-ethoxy-5-methylpyridine, and substituted propionaldehyde as starting materials, a core framework is efficiently constructed via Knoevenagel condensation, ammonolysis, imine condensation, and Povarov cycloaddition reactions. A chiral phosphoric acid catalyst or chiral ligand is introduced during the Povarov cycloaddition to directly induce the formation of the desired (4S)-configuration chiral center. The synthetic route of this application features strong convergence, mild reaction conditions, readily available starting materials, excellent stereoselectivity, and high overall yield, with a diastereomeric ratio (dr) > 95:5. It does not require high temperature, high pressure, or noble metal catalysis, enabling large-scale, green industrial production. This overcomes the technical shortcomings of existing technologies, such as long synthetic steps, poor stereoselectivity control, low resolution efficiency, and high production costs.

The application discloses a chiral pyrroloimidazolone-xanthene-triphenylphosphine ligand. The application generates a target product chiral pyrroloimidazolone-xanthene-triphenylphosphine ligand through condensation reaction of corresponding prolyl arylamine 1 and triphenylphosphine xanthene formaldehyde 2. The ligand comprises a triphenylphosphine group, a xanthene group and a chiral pyrroloimidazolone group. The chiral pyrroloimidazolone group can provide a chiral cavity environment, the xanthene group can provide a rigid skeleton, and the phosphorus atom of the triphenylphosphine group belongs to an electron-rich coordination site, can form coordination with metal, thereby generating a chiral ligand metal phosphine complex, and the application in catalyzing asymmetric allyl alkylation of alcohol. Therefore, the ligand has important application value in the field of asymmetric catalytic synthesis, and the synthesis method is very economical and simple. The ligand also has good air stability, wide applicability and good compatibility for various substituents.

This invention discloses a capillary electrochromatographic column for the separation of chiral tyrosine and its preparation method, belonging to the field of chemical synthesis and analytical technology. It includes a capillary and a composite coating fixed to the inner wall of the capillary. The composite coating comprises chiral metal-organic frameworks (CMOFs) and chiral molecularly imprinted polymers (CMIPs) modified on the surface of the CMOFs. The CMOFs are formed by coordination reaction between MIL-101 (Cr) and L-tyrosine as a chiral ligand. The composite coating (CMIP@CMOF) is a multi-level composite structure formed by in-situ polymerization of the CMOFs as a support in a system containing a crosslinking agent, functional monomer, initiator, and L-tyrosine as a template molecule. The separation system constructed by this coated column exhibits excellent separation performance, with a resolution (Rs) of 5.83 and a selectivity factor (α) of 1.33 for DL-tyrosine enantiomers.

The application discloses a strong coordination PNN trident chiral ligand based on anti-position effect and application thereof in free radical asymmetric functionalization and related reactions, and belongs to the technical field of organic chemistry. The strong coordination PNN trident chiral ligand has unique structure and properties, can effectively solve the poisoning problem of strong coordination substrates such as heterocyclic compounds on the catalyst, and significantly improves the catalytic efficiency and enantioselectivity in the reaction process of the substrates. The strong coordination PNN trident chiral ligand can be used in free radical asymmetric functionalization reactions catalyzed by cheap metals, and is especially suitable for asymmetric azidation reactions. Meanwhile, the application discloses synthesis and application of the strong coordination PNN trident chiral ligand in molecules such as vascular non-inflammatory protein-1 inhibitor (Vanin-1), Ontazolast, natural product Conulothiazole A, calcium ion channel antagonist TTA-A8 and the like. The application has significant theoretical innovation and good practical application value.