47 results about "Regioselectivity" patented technology

This invention discloses a ruthenium catalyst supported on a phosphine-containing porous organic polymer and its preparation method. The phosphine-containing porous organic polymer serves as both a support and a solid ligand. The phosphine-containing porous organic polymer ligand is a random copolymer, and its structure can be represented by general formula I. The ruthenium catalyst supported on the phosphine-containing porous organic polymer according to this invention has a large specific surface area and contains a hierarchical porous structure, enabling efficient direct preparation of alcohols from olefins via reductive hydroformylation, and is easily recyclable. It exhibits excellent activity and regioselectivity in the direct preparation of alcohols from olefins via reductive hydroformylation, with an alcohol selectivity of nearly 90% and a high ratio of straight-chain alcohols to branched-chain alcohols.

The application discloses a kind of using cobalt catalyst by unreported double migration coupling strategy, realizes migration asymmetric nitrogen hetero Nozaki-Hiyama-Kishi (aza-NHK) reaction, and the selective preparation α-chiral (E)-allyl amine starting from simple and easy to obtain ortho halogen phenyl ethylene or corresponding E / Z-alkyl bromide or its mixture belongs to the field of organic chemistry and medicinal chemistry.The application under the action of metal cobalt source, ligand, organic additive, inorganic additive etc., makes cyclic sulfonamide and ortho alkenyl substituted aryl halide or alkenyl halide react in organic solvent, to obtain a series of polysubstituted olefins with excellent regioselectivity, stereoselectivity and good yield, which can be used as active drug molecules and important synthetic intermediates.The application uses cheap transition metal cobalt as catalyst, and uses ortho alkenyl substituted aryl iodine and cyclic sulfonamide as raw material, and the reaction condition is warm, simple operation, and good functional group compatibility.

The invention belongs to the technical field of biochemistry, and particularly relates to a method for catalytically synthesizing a chiral nitrogen heterocyclic compound by a biological enzyme. The invention develops a method for obtaining a chiral nitrogen heterocyclic compound with high enantioselectivity by catalyzing an easily-obtained N-acyloxy amine compound as a nazein precursor to carry out C (sp3)-H amination cyclization reaction by taking an enzyme containing heme as a catalyst. The enzyme catalysis method is mild in reaction condition, simple in technical requirement, wide in substrate universality, high in product enantioselectivity and green, efficient and economical in synthesis process. The nitrogen-containing heterocyclic compound prepared by the method disclosed by the invention has the advantages of better reaction yield, excellent regioselectivity, wide substrate range and good functional group compatibility, and can be applied to synthesis and modification of some drug intermediates.

The application discloses an alcohol dehydrogenase mutant and application thereof in enzymatic synthesis of a loratadine intermediate. A plurality of alcohol dehydrogenase mutants are developed, and a loratadine chiral intermediate is obtained through an enzyme catalytic synthesis method based on the mutants, wherein the reaction condition is mild, the environment is friendly, the reaction has high regional selectivity and stereoselectivity, the reaction conversion rate is high, the chiral purity of the product is high, the enzyme consumption is low, the preparation cost is low, the method is suitable for industrial production, the method avoids the problems of difficult chiral resolution and heavy metal residue in a product in a conventional method, and the method makes up for the deficiencies of a traditional chemical method.

The application discloses a kind of by density functional theory reveals the calculation method of micro-mechanism and selectivity source of palladium catalysis olefin amine 1,2-diarylation reaction, belong to the intersection technical field of organic synthesis and computational chemistry. Including constructing molecular structure;The configuration optimization and calculation are carried out to molecular structure, obtain thermodynamic data;The geometric configuration of intermediate and transition state in each step is calculated, the change of gibbs free energy is obtained, the connection relationship of transition state and corresponding reactant, product is determined;According to thermodynamic data and connection relationship, reaction path diagram is drawn, and reaction mechanism is determined;According to reaction mechanism, the step of determining the selectivity of reaction region, enantioselectivity and chemical selectivity is determined, and selectivity control strategy is analyzed and output. By simulation, the key intermediate and transition state structure of each element step of reaction is determined, the reaction energy barrier of each element step is quantified, the transition state action mechanism determining the selectivity of reaction region, enantioselectivity and chemical selectivity is analyzed in depth, to provide theoretical guidance for the design of high-efficiency catalyst and the optimization of reaction condition.

This invention belongs to the field of organic chemical synthesis technology, specifically relating to a method for synthesizing 2-fluoro-3-aminobenzoic acid, an important chemical intermediate. Specifically, o-nitroaniline is condensed with hydrated trichloroacetaldehyde and hydroxylamine hydrochloride to obtain 2-(hydroxyimino)-N-(2-nitrophenyl)acetamide; the resulting product undergoes an intramolecular Beckmann rearrangement to generate 7-nitroindigo; 7-nitroindigo undergoes Bayer-Villedge oxidation to generate 2-amino-3-nitrobenzoic acid; 2-amino-3-nitrobenzoic acid undergoes diazotization and halogenation reactions to generate 2-fluoro-3-nitrobenzoic acid or 2-chloro-3-nitrobenzoic acid; 2-fluoro-3-nitrobenzoic acid can be further reduced by nitro to obtain 2-fluoro-3-aminobenzoic acid; or, 2-chloro-3-nitrobenzoic acid can be esterified to obtain 2-chloro-3-nitrobenzoic acid ester, which can then be fluorinated, saponified, and reduced to obtain 2-fluoro-3-aminobenzoic acid. The raw materials of this invention are low in cost and readily available, and the entire reaction route has specific regioselectivity, making it suitable for industrial production.

The present application belongs to the field of enzyme catalysis and bioengineering technology, and relates to a cytochrome P450 enzyme CYP153C3 and application thereof. The amino acid sequence of the enzyme is shown in SEQ ID NO. 1 of the sequence listing. The nucleotide sequence of the DNA molecule encoding the enzyme is shown in SEQ ID NO. 2 of the sequence listing. The cytochrome P450 enzyme CYP153C3 provided by the present application has catalytic activity on C8-C14 chain length saturated fatty acids, various unsaturated fatty acids and short-chain alkanes (octane, decane); meanwhile, the enzyme shows excellent ω-1 hydroxylation capacity on saturated fatty acids, unsaturated fatty acids and alkane substrates, has high regioselectivity, and can be used for green bio-manufacturing of high-value hydroxyl fatty acids and hydroxyl alkane compounds.

The present application relates to the chemical technology field, specifically to a kind of preparation method of high-purity o-vanillin.The method uses o-methoxyphenylamine as starting material, with chloral hydrate and hydroxylamine hydrochloride is condensed, hydroxylamine oximation reaction, and cyclization reaction is carried out under strong acid condition, and compound 2 is generated;Compound 2 is oxidized under strong base condition, and compound 3 is generated;Compound 3 is esterified with primary alcohol to generate corresponding ester, and then reduction hydrogenation reaction is carried out under the action of strong reducing agent, and compound 4 is generated;Compound 4 is reacted with oxidizing agent in the presence of nitroxyl radical catalyst, and compound 5 is generated;Compound 5 carries out diazotization hydrolysis reaction, and o-vanillin is generated.The method avoids the problem of regioselectivity of traditional formylation reaction through specific reaction sequence, eliminates the generation of isomer impurities from the source, realizes the efficient, environmentally friendly, economic synthesis of high-purity o-vanillin, and provides high-quality raw material guarantee for downstream pharmaceutical.

This invention discloses an indoline fused heterocyclic compound, its preparation method, and its applications, belonging to the field of pharmaceutical synthesis technology. The method includes the following steps: using quinone imine monoketal and α,β-unsaturated cycloalkenyl ether as raw materials, and employing a Brønsted acid-phosphonic acid catalyst, a Brønsted acid-catalyzed [3+2] tandem cyclization reaction is carried out to obtain the indoline fused heterocyclic compound. The method provided by this invention features readily available raw materials and mild conditions, while also exhibiting high regioselectivity, chemoselectivity, and atom economy. The product can be efficiently separated by column chromatography, providing an excellent pathway for the large-scale preparation of this type of compound. Furthermore, the indoline fused heterocyclic compound provided by this invention has a significant inhibitory effect on the growth of human cervical cancer cells (HeLa), demonstrating good antitumor biological activity, which is of great positive significance for promoting the development of antitumor drugs.

The application discloses a method for synthesizing dibenzyl-alpha,alpha-diphenylamine compounds, and belongs to the technical field of organic synthesis. The method uses aromatic dialdehyde, 2-cyclohexenone and benzylamine as raw materials, and carries out a heating reaction in an organic solvent in the presence of titanium tetrachloride. After the reaction is completed, an N,N'-dibenzyl-substituted dibenzyl-alpha,alpha-diphenylamine intermediate is separated and purified. The intermediate is subjected to hydrogenation and debenzylization by using Pd-C / H2, and after separation and purification, the dibenzyl-alpha,alpha-diphenylamine compound is obtained. The preparation process is mild and simple, and the problems of low chemical selectivity and low regioselectivity in traditional synthesis are avoided. In addition, the aryl compatibility of the aromatic dialdehyde is good, and the atomic economy is high, thereby providing raw material support for new drug screening and monomer synthesis of organic functional materials.

This invention provides a liver-targeting glycoligand molecule modified with dual-antenna GalNAc and its drug delivery system. This liver-targeting glycoligand molecule and its drug delivery system, through ASGPR recognition, can maximize the concentration of therapeutic drugs in liver tumor parenchymal cells, thereby improving the targeting of drug distribution, increasing the therapeutic index, reducing systemic toxicity, and improving patient survival time and quality of life. The liver-targeting glycoligand molecule of this invention is synthesized using an enzymatic synthesis method, which involves fewer synthesis steps, mild enzymatic reaction conditions, high regioselectivity, high reaction efficiency, is environmentally friendly, and has low production costs, making it highly promising for industrialization.

This invention discloses a C5-position selective photocatalytic hydrogenation dechlorination method for 4,5-dichloropyridazinone. The method includes: dissolving 4,5-dichloropyridazinone (Formula I), a photocatalyst, and an organic amine reducing agent in an organic solvent under inert gas protection, and reacting under visible light irradiation to obtain 4-chloropyridazinone (Formula II); wherein R is selected from aryl, heteroaryl, alkyl, benzyl, or acylalkyl; the photocatalyst is disodium eosin Y or tetrabromofluorescein; the organic amine reducing agent is N,N-diisopropylethylamine; the organic solvent is DMF, DMSO, or acetonitrile; and the visible light wavelength is 420-520 nm. This method has advantages such as high regioselectivity, mild reaction conditions, and a wide range of applicable substrates.

This invention discloses a method for preparing alkenyl triazole compounds. Under the action of a base, alkynyl sulfonium salts and triazole compounds are reacted in an organic solvent at room temperature and pressure for 2–5 h to obtain alkenyl triazole compounds. This invention utilizes a diamine reaction at room temperature, requiring no additional catalyst or oxidant, exhibiting excellent functional group tolerance and broad substrate applicability, while also demonstrating good chemoselectivity, regioselectivity, and stereoselectivity. The reaction system is free of toxic metal catalysts, simple to operate, and demonstrates excellent functional group tolerance and broad substrate applicability. The raw materials used are inexpensive and readily available, exhibiting good atom economy and step economy, providing a new strategy for the synthesis of triazole series compounds. The entire reaction process is mild, with high product selectivity, simple operation, and environmental friendliness, conforming to the principles of green chemistry.

The application belongs to the technical field of polymer chemical synthesis, and provides a method for constructing a polar monomer regioselectivity analysis prediction model in copolymerization of ethylene and polar monomers catalyzed by an alpha-diaimine Pd(II) complex, which comprises obtaining transition state energy difference ΔG of 1,2-insertion mode and 2,1-insertion mode of each polar monomer under catalysis of the alpha-diaimine Pd(II) complex, obtaining quantum chemical parameter values corresponding to each polar monomer, and constructing a calculation model of reaction energy difference ΔG of two different insertion modes of each polar monomer under catalysis of the alpha-diaimine Pd(II) complex with respect to the quantum chemical parameters corresponding to each polar monomer. The polar monomer regioselectivity analysis model of the alpha-diaimine Pd(II) complex in copolymerization of ethylene and polar monomers constructed by the method can realize accurate analysis of the regioselectivity of the alpha-diaimine Pd(II) complex in insertion of each polar monomer.

This invention provides a method for synthesizing γ / δ-heteroaryl-substituted alkyl sulfone derivatives. Under an inert gas atmosphere, an unactivated olefin containing a heteroaryl group (as shown in Formula 1), an electrophilic reagent EX, a photocatalyst, a cobalt catalyst, a proton source, and a basic substance are dissolved in an organic solvent. The reaction is stirred under light irradiation at 420–450 nm. The resulting reaction solution is post-treated to obtain the γ / δ-heteroaryl-substituted alkyl sulfone derivative (as shown in Formula 3). The method exhibits high yield, high regioselectivity, mild reaction conditions, and uses simple, readily available, inexpensive, stable, odorless, and environmentally friendly raw materials, making it a promising candidate for practical applications.

The application discloses a Wacker type oxidation preparation method of methyl ketone. The method comprises the following steps: adding a hydrocarbon compound, a palladium catalyst, a ligand and an oxidant into an alcohol solvent, and performing heating treatment under a protective atmosphere to obtain a methyl ketone compound, wherein the oxidant is an Oxone oxidant, and the ligand is 2-phenyl-1H-benzo[d]imidazole. The preparation method provided by the application has high catalytic activity of the catalytic system, and the catalyst loading is as low as 0.1-1 mol%, thereby greatly reducing the cost of noble metals. The ligand used has a simple structure and is convenient to synthesize, and high catalytic activity and high regioselectivity are realized. The Oxone used as the green oxidant has good water solubility and friendly by-products, the reaction is performed at 50-60 DEG C under normal pressure, the solvent used is cheap and low-toxic, and the condition is mild, safe and easy to scale up. The method has a wide applicable range of substrates, excellent functional group compatibility, single product and simple separation and purification.

This invention discloses a method for preparing 2,6-dihydroxybenzoic acid. Specifically, this invention uses resorcinol as a starting material, which reacts with hydrogen and formic acid derivatives (supported metals such as ruthenium, rhodium, palladium, platinum, iridium, and nickel) under the action of a catalyst to efficiently generate 1,3-cyclohexanedione. 1,3-cyclohexanedione then reacts with carbon dioxide under the action of a base to generate a carboxylic acid intermediate; this reaction exhibits specific regioselectivity. The carboxylic acid intermediate undergoes dehydrogenation aromatization under the action of a catalyst (supported metals such as ruthenium, rhodium, palladium, platinum, iridium, and nickel) to generate 2,6-dihydroxybenzoic acid. This invention exhibits specific regioselectivity, generating only the desired 2,6-dihydroxybenzoic acid, avoiding the generation of 2,4-dihydroxybenzoic acid byproducts reported in current literature. Compared with existing technologies, this invention has advantages such as simplicity, high selectivity, high atom economy, high yield, green and pollution-free operation, and ease of industrialization.

The application provides a chiral carbene ligand, a preparation method thereof and application in asymmetric synthesis, the chiral carbene ligand catalyzes asymmetric hydroarylation reaction of various kinds of olefin substrates such as aryl olefin, alpha-olefin and diene, and aryl bromine or aryl chloride, and synthesizes four kinds of drug molecules or drug molecule intermediates in one step. The chiral carbene ligand has a flexible chain structure, is self-adapting, can effectively adapt to different transition metal centers and substrate configurations, and improves the universality and selectivity of the catalytic system; the raw material used in the preparation method of the chiral carbene ligand is easy to obtain, the synthesis route is short, and post-treatment is simple; various reagents can exist stably at normal temperature and pressure without special treatment; only by regulating the nickel catalyst and the new chiral carbene ligand, high regioselectivity and enantioselectivity of the chiral benzyl-containing compound can be realized; the asymmetric synthesis method can obtain the target product in one step, and greatly reduces the production cost of synthesizing the compound.

The application discloses a method for photocatalytic synthesis of aryl alkyl ketone and beta-deuterated aryl alkyl ketone compounds, and belongs to the field of organic synthesis. The method comprises the following steps: under the condition of a composite catalytic system of a photocatalyst, a cobalt catalyst and a ligand, aryl carbinol and olefin are subjected to hydrogen transfer and coupling reaction in an inert gas atmosphere and an organic solvent to obtain aryl alkyl ketone compounds. The application provides a new method for photocatalytic synthesis of dialkyl ketone. The application uses aryl carbinol olefin and hydrocarbon as starting materials, utilizes a catalytic system of a photocatalyst / cobalt catalyst, and realizes rapid construction of aryl alkyl ketone compounds through hydrogen transfer and coupling reaction of aryl carbinol and olefin. The method has the advantages of mild conditions, high economic efficiency of steps, good regioselectivity and wide substrate range.

The application discloses an organic boron reagent alpha-boryl oxime compound and a preparation method and application thereof, and belongs to the technical field of organic synthesis. N The alpha-boryl oxime compound is prepared by reacting a heterocyclic carbene borane adduct and a nitroso compound in an organic solvent. N The alpha-boryl oxime compound is prepared by simultaneously introducing an oxime group and a boron group functional group into both ends of the olefin with high selectivity through the boro-oximation reaction of the heterocyclic carbene borane, the nitrosamine compound and the olefin. The reaction avoids the use of a photosensitizer and a transition metal, has very good functional group tolerance and substrate universality, and also has good chemical selectivity, regioselectivity and stereoselectivity; the product alpha-boryl oxime compound can be efficiently used to synthesize various useful compounds through simple conversion, the types of the organic boron reagent are expanded, and the application prospect is good.

The application discloses a method for photocatalytic synthesis of thioester compounds and belongs to the field of organic synthesis. The method comprises the following steps: under the condition of a photocatalyst, primary alcohol, S8 and olefin are subjected to hydrogen transfer and coupling reaction in an inert gas atmosphere and an organic solvent, so that thioester compounds are obtained. The application provides a new method for photocatalytic synthesis of thioester. The application uses primary alcohol, S8 and olefin as starting materials, and realizes rapid construction of thioester compounds through hydrogen transfer and coupling reaction of primary alcohol, S8 and olefin under the condition of photocatalysis. The method has the advantages of mild conditions, high economy, good regioselectivity and wide substrate range; S8 can be used as a sulfur source to participate in the construction of thioester and also can be used as a hydrogen acceptor to promote the dehydrogenation of primary alcohol, thereby avoiding the use of an additional oxidant or hydrogen acceptor, and meanwhile, the use of malodorous and unstable mercaptan can be avoided.

The application discloses a method for synthesizing 3-butenoic acid compounds based on allyl carbon hydrogen bond carboxylation reaction and belongs to the technical field of organic synthesis. The method comprises the following steps: mixing an olefin reaction substrate, a photosensitizer, a copper catalyst and an alkaline substance, then adding an organic solvent under a CO2 atmosphere, and stirring under visible light irradiation to prepare 3-butenoic acid compounds. The application realizes the light / copper synergistic catalysis of the CO2 participating allyl carbon hydrogen bond carboxylation reaction, and a series of 3-butenoic acid compounds are prepared with high selectivity and high atomic economy. The method has the characteristics of cheap and easily available raw materials, wide reaction substrate range, good functional group compatibility, mild reaction conditions, good chemical and regional selectivity and the like, and has a wide application prospect.

This application discloses a nonspecific peroxidase CsaUPO derived from *Cladorrhinum samala*, whose amino acid sequence is shown in SEQ ID NO:1. This enzyme efficiently catalyzes the 4,5β-epoxidation of testosterone to produce 4,5β-epoxidized testosterone, achieving a conversion rate of 98% and a separation yield of 90%, without producing hydroxylation byproducts, and exhibiting excellent regioselectivity. This application also discloses the gene encoding CsaUPO, the recombinant plasmid pPICZA-CsaUPO containing this gene, a recombinant Pichia pastoris engineered strain, and its application in steroid epoxidation. The nonspecific peroxidase CsaUPO disclosed in this application possesses advantages such as high catalytic efficiency, specific regioselectivity, a simple reaction system, and environmental friendliness, providing a new enzymatic resource for the site-directed epoxidation modification of steroid drugs.

The application is a preparation method and application of a zeolite encapsulated Rh-based catalyst with geometric and chemical synergistic effect. The method adopts one-pot hydrothermal synthesis, under the dual action of KOH alkali etching and structure guiding, in-situ constructs microporous-mesoporous hierarchical pore S-1 molecular sieve with nanosheet layer alternately stacking characteristics, and introduces silicon hydroxyl nest defect site into the molecular sieve framework, realizes multi-level morphology and K + The application also discloses a preparation method and application of a zeolite encapsulated Rh-based catalyst with geometric and chemical synergistic effect. + Chemical microenvironment synergy construction. The synthesis method is simple, the conditions are mild in propylene hydroformylation reaction, the prepared KRh@HS-S-1 catalyst has microporous-mesoporous hierarchical pore structure with nanosheet layer alternately stacking characteristics, and the pore channel is distributed with K + Modified chemical microenvironment, realizes the synergistic improvement of activity and regioselectivity.

This invention provides a method for the rearrangement nitrogen insertion reaction of indole phosphonium salts and tert-butyl (p-toluenesulfonyloxy) carbamate under potassium carbonate-promoted conditions, synthesizing a series of 3-aminoindole compounds. The technical solution of this invention has the following significant advantages: it eliminates the need for expensive metal catalysts, significantly reducing production costs; the reaction conditions are mild and simple, and the reaction can be carried out efficiently at room temperature with only the addition of a base and an amine source, achieving excellent chemoselectivity, regioselectivity, broad functional group compatibility, and excellent atom economy.

The invention relates to a method of producing 4,4'-methylene diphenyl dicarbamate of formula I, characterized in that molten O-methyl-N-phenyl carbamate of formula II is reacted with anhydrous derivatives of formaldehyde in the presence of acidic catalysts, where the molar ratio of the reagents is (2-10):1:(0.25-2) and the reaction is carried out at a temperature of 50-150°C. The technical result is a novel and improved method of producing 4,4'-MDC by a regioselective reaction with a high yield.