383results about "Asymmetric syntheses" patented technology

The invention provides a novel chiral ferrocene bridged binaphthyl skeleton phosphine ligand and application thereof. The ligand has the advantages of low cost, simplicity in synthesis, air stability and the like. The ligands have good catalytic activity and enantioselectivity in the asymmetric hydrogenation reaction of ketone, and have certain industrial application prospects in the synthesis of pharmaceutical molecules.

The invention belongs to the technical field of organic electroluminescent materials, and particularly discloses a paracyclophane-based purple light chiral host material and application thereof. Paracyclophane is used as a molecular structure center, two paracyclophane derivatives are constructed, and the novel purple light chiral main body material is synthesized by combining indole carbazole groups on the periphery. Because the periphery is combined with an indolocarbazole group, the excellent photophysical property of indolocarbazole can be fully utilized, and through separation of cycloarane, intermolecular conjugation is broken, a novel purple light material is constructed, emission of 372 nm is realized, relatively high S1 and T1 energy levels are obtained, a chiral signal is provided for participation of cycloarane, and the material has a wide application prospect. The important significance is provided for constructing a novel chiral main body material.

To provide a novel stereoselective method for producing a cyclic dinucleotide derivative that can be used for an antibody-immunostimulator conjugate, and a production intermediate thereof, and to provide methods for producing a cyclic dinucleotide-linker and antibody-immunostimulator conjugate using the production method.SOLUTION: The present invention relates to a method that makes it possible to produce, in large amounts and with high yield, a cyclic dinucleotide derivative having a desired steric configuration, by using an optically active phosphitylation agent twice, during coupling and cyclization.SELECTED DRAWING: None

The present application provides a synthetic process for production of lipoxin B4 and analogues thereof, which is modular and scalable, thus permitting synthesis of large quantities of LXB4 and analogues thereof, including radiolabeled analogues. Also provided are intermediate compounds that are useful in the synthetic process for production of lipoxin B4 and analogues thereof.

This invention discloses a chiral [oxyindole-pyrrolidine-β-lactam] bispirocyclic compound containing trifluoromethyl groups, with the following structural formula: The preparation includes the following steps: 1. Sequentially adding a metal catalyst, a chiral ligand, a base, indigo-derived trifluoromethylimine ylide, and 3-methylene β-lactam, followed by the addition of an organic solvent to obtain a mixture. The mixture is stirred at a reaction temperature of 0℃ to 50℃. 2. After the reaction is complete, the chiral [oxyindole-pyrrolidine-β-lactam] bispirocyclic compound containing trifluoromethyl groups is obtained through post-processing. The chiral [oxyindole-pyrrolidine-β-lactam] bispirocyclic compound containing trifluoromethyl groups prepared in this application lays a material foundation for in-depth drug activity research based on new drug development.

The invention discloses a chiral 1, 4-diazabicyclo [3.1. 1] heptane derivative as well as a synthesis method and application of the chiral 1, 4-diazabicyclo [3.1. 1] heptane derivative. According to the invention, a 1-azabicyclo [1.1. 0] butane derivative is taken as a raw material, under the catalytic action of a chiral iridium complex, the 1-azabicyclo [1.1. 1] butane derivative and an N-allyl carbonate derivative are subjected to [3 + 2] cycloaddition reaction, a series of chiral 1, 4-diazabicyclo [3.1. 1] heptane skeletons with diversified structures are constructed with high stereoselectivity, and the obtained product has the potential of further derivatization. The method has the advantages of easily available raw materials, mild reaction conditions, simplicity and convenience in operation, good functional group compatibility and the like.

The invention provides an efficient method for asymmetric hydroarylation of internal olefin. The method provided by the invention has the advantages of high yield, simple operation, mild reaction conditions, strong chiral control ability and wide substrate applicability, and has high academic and application values.

The present invention relates to the preparation of amino acid derivatives VII, including the use of catalysts. The structure of the catalyst disclosed by the invention can be shown as a formula (VI), or the catalyst is loaded on a molecular sieve, and the structure of the catalyst is shown as a formula (I). The invention also discloses preparation of the catalyst and intermediates thereof. A plurality of molecules prepared by the method are all of brand new structures, and are of great significance.

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 invention discloses a benzoxphosphine ligand and a complex and application thereof. The structure of the benzoxphosphine ligand is shown as a formula (I), in the formula (I), R1 is alkyl or aryl substituted oxazolidinyl or imidazoline, R2 is alkyl and / or aryl, and R3 is at least one of fluorine, carbazolyl and 2, 6-dimethoxyphenyl. According to the benzoxphosphine ligand disclosed by the invention, the metal iridium complex can be used as a catalyst to be applied to an asymmetric hydrogenation reaction of alpha-phenyl vinyl diethyl phosphate, and has excellent activity and relatively high enantioselectivity; moreover, the benzoxphosphine ligand disclosed by the invention can be directly synthesized from simple and easily available chiral aldehyde, and the preparation method is simple and easy to operate.

The application belongs to the technical field of chemical synthesis, and specifically provides a chiral hydroxyphosphonate, a preparation method and application thereof. The chiral hydroxyphosphonate has a structure as shown in formula II: each R is independently H, an alkyl group, an alkenyl group, an alkynyl group or a halogenated alkyl group; Ar is an aromatic ring or a heteroaromatic ring; X is a bond, -O-, -N(R 1 )- 2 q , -S(=O) m -; the chiral hydroxyphosphonate is obtained by reducing an alpha phosphonate substituted benzocycloalkanone compound through an asymmetric hydrogenation method, has two chiral centers, and has a yield of up to 99% and an enantiomeric selectivity of up to 99%. The chiral hydroxyphosphonate has wide application potential and value in skin tissue soothing, repairing, anti-aging and the like.​

The invention discloses a preparation method of an optically pure mepivacaine hydrochloride intermediate. According to the method, N-(2, 6-dimethylphenyl) pyridine carboxamide is used as a starting material, hydrogenation reduction is carried out in the presence of a ligand and a catalyst to obtain the mepivacaine hydrochloride intermediate ((S)-N-(2, 6-dimethylphenyl) piperidine-2-carboxamide), the ee value of the obtained mepivacaine hydrochloride intermediate can reach 93%, the yield can reach 95%, post-treatment is simple, and the method is suitable for industrial production. The method is very suitable for large-scale workshop production. The ligand used in the invention is cheap and easily available, and can be refined and recovered through column chromatography, and the catalytic effect of the recovered ligand is consistent with that of a newly purchased ligand.

The present invention provides a [Ru(OAc)2(ligand)] catalyst of formula I, where R 1 is C 1~6 alkyl, and R 3 is hydrogen or C 1~6 alkyl, and R 4 is hydrogen or C 1~6 The [Ru(OAc)2(ligand)] catalyst is a versatile hydrogenation catalyst. TIFF2025525346000011.tif57128

This invention belongs to the field of organic synthesis technology and relates to a precursor of an obisec key intermediate and a method for preparing the key intermediate. The method involves a [4+2] cycloaddition reaction of 4-trifluoromethylaniline, propionaldehyde, and N-vinylformamide under the catalysis of chiral phosphoric acid, yielding the obisec key intermediate precursor with high enantioselectivity. N -((2) R 4 S )-2-ethyl-6-trifluoromethyl-1,2,3,4-tetrahydroquinoline-4-yl)formamide; subsequently, the key intermediate of obisetri can be obtained through a deprotection reaction under acidic conditions. The method provided by this invention uses a small amount of chiral catalyst and commercially available reagents to efficiently obtain the key intermediate of obisetri in just two steps. R 4 S )-2-ethyl-6-trifluoromethyl-1,2,3,4-tetrahydroquinoline-4-amine; under mild conditions without the need for chiral resolution, the utilization of starting materials is greatly improved, thereby significantly increasing the yield of the target product and the economic efficiency of the process.

The application provides a kind of plane chiral boronic acid compound based on cycloaralkane skeleton and its synthesis method and application, the plane chiral compound has the structure shown in formula I;R 1 It is selected from one of C1-C8 alkyl, C1-C8 alkoxy, C1-C20 aryloxy.R 2 It is selected from one of hydrogen, fluorine, methyl, ethyl, methoxy, ester group, nitro group, phenyl, benzyl, tert-butyl, isopropyl.The application can effectively synthesize plane chiral boronic acid catalyst based on cycloaralkane skeleton, and the plane chiral boronic acid catalyst based on cycloaralkane skeleton can realize diol desymmetrization reaction.

The application belongs to the technical field of asymmetric catalytic synthesis, and particularly relates to an alpha-carbon chiral phosphine compound and a preparation method thereof. In a protective gas atmosphere, an asymmetric boron protonation reaction is carried out on a dienyl phosphine oxide compound shown in a structure of formula II, pinacol borate, a copper (I) catalyst, a chiral ligand, an organic alkaline compound and a proton additive in a polar organic solvent to obtain an alpha-carbon chiral phosphine compound shown in a structure of formula I; the chiral ligand is a cyclic phosphine ligand (S, S)-Ph-BPE or a cyclic phosphine ligand (R, R)-Ph-BPE. The preparation method provided by the application can synthesize the alpha-carbon chiral phosphine compound shown in the structure of formula I with high yield and excellent enantioselectivity, the synthesis method is simple and low in cost, and the alpha-carbon chiral phosphine compound can be further converted into a new optically active product.

The application discloses a kind of solid supported manganese catalyst and its preparation method and application, the preparation process of the catalyst includes complexing organic ligand with metal manganese salt, forms catalytic active unit, and then polymerizes with comonomer, obtains the solid supported manganese catalyst as shown in formula I or II.The solid supported manganese catalyst belongs to heterogeneous chiral catalyst, with higher catalytic activity and excellent enantioselectivity (ee value is as high as 98.3%), because it is insoluble in reaction solvent, easy to separate and recover with reaction system, with good stability.And it can be combined with continuous flow catalysis, maintain high catalytic activity for a long time, can be applied in the asymmetric epoxidation reaction of alpha, beta-unsaturated carbonyl compound.

Provided is a method for efficiently producing a fluorinated alkyl compound by directly converting an aliphatic alkylamine widely existing in nature into a fluorine substituent, the method being characterized in that an alkylamine compound in which at least one amino group is bonded to an alkyl carbon is reacted with a deamination-fluorination agent to produce the fluorinated alkyl compound.

The invention discloses an efficient synthesis method of ephedrine hydrochloride, and belongs to the technical field of pharmaceutical chemistry synthesizing.A self-synthesized chiral zinc oxide nanoflower composite catalyst is added in the synthesis process of the ephedrine hydrochloride, and the composite catalyst has a chiral function, is large in pore and surface area, easy to recover and not prone to blockage, and can be used for preparing a chiral zinc oxide nanoflower catalyst. Compared with a traditional Lewis acid type catalyst, the catalyst has the advantages that keto groups in ephedrine hydrochloride synthesis can be precisely reduced, and hexadecyl trimethyl ammonium bromide is intercalated on the surface, so that the catalyst is not easy to agglomerate in a catalytic system, and the yield of a product is further improved; according to the composite catalyst, through hexadecyl trimethyl ammonium bromide, the surface hydrophilicity and hydrophobicity of the composite catalyst are regulated and controlled, the composite catalyst is dispersed more uniformly and makes contact with a compound II more sufficiently, the speed and selectivity of a reductive amination reaction are improved, and the hexadecyl trimethyl ammonium bromide can intercalate mica lamellas, so that the mica lamellas are peeled off, the interlayer spacing is increased, and therefore the composite catalyst is more stable in performance. And the reaction sites are increased, so that the catalytic active center is loaded more stably.

The application belongs to the technical field of organic chemical synthesis, and particularly relates to a nitrogen center chiral base derivative, a preparation method and application thereof. The preparation method of the nitrogen center chiral base derivative provided by the application can effectively synthesize a base with only a nitrogen chiral center by using a tetrahydrodibenzo-diazocine compound as a raw material and through chiral phosphoric acid catalyzed amination reaction. Moreover, the synthesis method provided by the application has the advantages of high efficiency, simple steps and strong enantioselectivity, is suitable for industrialized production of chiral bases and derivatives thereof, and provides a new approach for research and application of chiral compounds. Meanwhile, the base derivative prepared by the application is a base molecule with a nitrogen center chirality, and has wide application prospects in the fields of molecular recognition, DNA binding, supramolecular chemistry, material science, asymmetric catalysis and drug development.

The invention relates to the technical field of organic luminescence, and discloses a binaphthylamine derivative as well as a preparation method and application thereof. According to the organic compound based on the binaphthylamine derivative, a series of D-A structure molecules are synthesized by taking a binaphthylamine-containing group as a donor structure and connecting different diphenyl sulfone derivative receptors, and the organic compound has relatively high quantum yield and can be applied to the fields of organic electroluminescent devices, fluorescent probes, asymmetric catalysis, information storage and the like.

The invention provides a preparation method of a novel chiral thiourea / phosphine bifunctional organic catalyst with a cis-cyclic 1, 2-phosphinamine skeleton and application of the novel chiral thiourea / phosphine bifunctional organic catalyst in an asymmetric catalytic reaction. The chiral organic catalyst is prepared by taking cis chiral 2-(diphenylphosphine)-1, 2, 3, 4-tetrahydro-1-naphthylamine and an isothiocyanate compound as raw materials through a one-step reaction under a mild condition. The chiral thiourea / phosphine bifunctional organic catalyst is simple to prepare and stable in property, and shows excellent catalytic activity and stereoselectivity in an asymmetric hydrosilylation reaction of o-amido benzophenone.

The invention aims to establish a synergistic catalytic system in which catalysts cannot coexist. The amide chiral catalyst is prepared through a series of synthesis. The hollow mesoporous COF-carboxylic acid / chiral amide multi-catalyst is prepared by a hydrothermal method. The morphology and the structure of the material are characterized by using a scanning electron microscope, a transmission electron microscope, an X-ray diffractometer, a specific surface instrument, an infrared spectrometer and the like, an asymmetric tandem-addition reaction is catalyzed to construct a chiral acetal compound, high performance liquid chromatography analysis is combined, and multiple catalysts are continuously recycled. Results show that the hollow mesoporous COF-carboxylic acid / chiral amide multi-catalyst not only has good morphology, excellent specific surface area and high porosity, but also enables contradictory catalysts to coexist for synergistic catalysis. The catalyst can be used for rapidly catalyzing an asymmetric tandem-addition reaction, high selectivity of ee = 99% and high yield of 98% are achieved, and the catalyst can be repeatedly used for 10 times. The method is green, environment-friendly, low in cost and suitable for concerted catalysis of catalysts which cannot coexist.

This invention discloses an amorphous aluminum-nickel catalyst synergistically modified with rare earth and chiral ligands and its application in asymmetric hydrogenation, belonging to the field of catalyst technology. The catalyst comprises nickel, aluminum, boron, rare earth elements, and chiral ligands, and possesses an amorphous structure. The chiral ligands coordinate with nickel atoms on the catalyst surface through their coordinating atoms, with the rare earth elements located within the coordination range of the ligands, forming a nickel-ligand-rare earth bridging structure that synergistically regulates the stereoelectronic environment of the catalytic center. The catalyst preparation method includes steps such as chemical reduction and double quenching to prepare an amorphous alloy precursor, gradient alkaline leaching activation to form a porous structure, chiral ligand modification, and passivation protection. The catalyst of this invention can be used in the asymmetric hydrogenation reaction of unsaturated compounds such as unsaturated ketones, aromatic ketones, and imines, achieving high conversion rates and high enantioselectivity, and can be recycled multiple times without significant performance degradation, showing promising industrial application prospects.

The application discloses a kind of plane chiral [2.2] paracyclophanane monophosphine ligand pEPCP and preparation method and application thereof, it is related to chemical catalysis technical field, and its technical scheme main points are as follows: including racemate or enantiomer, the structural formula-I of the monophosphine ligand pEPCP of the application is as follows: [2.2] paracyclophanane skeleton containing monophosphine ligand pEPCP of the application, with two benzene rings in para position by two ethylene connection unique big steric hindrance, electron-rich rigid skeleton, different types ether substituent group is introduced in structure, change the electron cloud density and steric hindrance of aromatic ring directly connected by phosphine ligand.In addition, ether substituent group can also be used as weak coordination group, participate in adjusting ligand chelate dihedral angle.This makes metal, ligand and substrate form the most suitable coordination environment in catalytic process, so that corresponding catalytic reaction has the advantages such as high reactivity, good enantioselectivity, substrate universal range is wide, especially suitable for transition metal catalyzed asymmetric coupling reaction, with economic practicability and industrial application prospect.

The present invention relates to an asymmetric catalytic hydrogenation synthesis method for a brivaracetam intermediate. The synthesis method comprises the step of: in a hydrogen atmosphere, in a solvent, a compound represented by formula I is subjected to asymmetric hydrogenation reduction in the presence of an alkali and a catalyst which is formed by a planar chiral metallocene ligand and a ruthenium salt to form a compound as represented by formula II, wherein the reaction formula is shown below. In the present invention, the catalyst used in the asymmetric catalytic hydrogenation synthesis method has low cost, the conversion rate of raw materials is high, and the DR value of the obtained final product can reach 99: 1 or above; and the present invention is suitable for industrial production

The present invention provides chiral pyridinium salt carbonyl catalysts and methods for their preparation and use. The general structural formula of the catalyst is [Formula 1] TIFF2026501952000195.tif36170[where, R 1 Structural formula of [chemical 2] TIFF2026501952000196.tif25170X 1-6 is N or CR 6-11 Including, R 2 , R 4 , R 6-11 is hydrogen, C 1~24 alkyl groups, alkoxy groups, [C3] TIFF2026501952000197.tif7170 groups, [C4] TIFF2026501952000198.tif14170, [C5] TIFF2026501952000199.tif14170 [6] TIFF2026501952000200.tif14170, CO2R d , halogen, nitro group, cyano group or trifluoromethyl group, R 3 is a substituted or unsubstituted C 1~24 The alkyl group may be substituted with halogen or C 1~10 Alkyl groups of C 3~10 cycloalkyl or aryl group, C 1~8 carbonyl group, C 1~8 a sulfonyl group or a phosphoryl group of C 1~10 The carbonyl group includes an aldehyde group, a ketocarbonyl group, an estercarbonyl group, a carboxyl group, or an amide group; R 5 Structural formula of [C7] TIFF2026501952000201.tif18170X - is an anion] Compared with the prior art, the catalyst of the present invention can be used in the biomimetic aldol reaction of amino acid derivatives to synthesize a series of β-hydroxy-α-amino acid compounds with extremely high enantioselectivity.

The embodiment of the invention relates to the technical field of synthesis of organic compounds, and particularly discloses a tryptophan derivative and a preparation method thereof, and the tryptophan derivative comprises the following raw materials: 4-methyl phenyl sulfonyl indole, 4-methyl-5-oxazolone and a proper amount of chiral catalyst. According to the embodiment of the invention, sulfuryl indole can be converted into a vinyl imine intermediate with unstable chemical properties after being treated by an alkaline reagent, and then 5-oxazolone is used as a nucleophilic reagent and is added onto the vinyl imine intermediate to synthesize the alpha, beta-substituted tryptophan derivative. According to the synthetic route provided by the embodiment of the invention, the raw materials are cheap and easy to obtain, the price is low, the reaction steps are simple, the conditions are mild, the yield is also greatly improved, the problems of harsh related synthetic reaction conditions and lower yield in the existing scheme for preparing the tryptophan derivative by adopting a chemical synthesis method are solved, and the synthetic route has a wide market prospect.

The present invention provides a method for preparing bedaquiline by continuous flow at low temperature, and the prepared product. This preparation method includes the following steps S1 to S3. Step S1: Feed liquid A and feed liquid B are subjected to a first continuous flow reaction by continuous flow to obtain reaction liquid D. Step S2: Reaction liquid D and feed liquid C are subjected to a second continuous flow reaction by continuous flow, with the reaction residence time of the first continuous flow reaction being 30 to 600 seconds, and the reaction residence time of the second continuous flow reaction being 30 to 200 seconds. Step S3: Quenching. The preparation method of the present invention has a high yield, and pure bedaquiline with a purity of 99.8% or more can be obtained by simply working up the crude product obtained by preparing bedaquiline by the method of the present invention.