56 results about "Transfer hydrogenation" patented technology

The invention belongs to the field of material preparation and chemical engineering, and particularly relates to an N-doped modified MOFs (Metal-Organic Frameworks) derived core-shell nanoreactor as well as a preparation method and application thereof. The preparation method comprises the following steps: taking cobalt as a node metal, synthesizing an N-doped modified MOFs material with an organic ligand and a nitrogen source through a hydrothermal reaction, then coating the surface of the material with porous silicon dioxide, and preparing the N-doped modified MOFs derived core-shell nanoreactor through a two-step calcination method. The MOFs derived core-shell nanoreactor prepared by the invention has a large specific surface area, a rich pore structure and excellent catalytic activity and stability, and is high in catalytic activity, good in recycling stability and suitable for large-scale popularization and application when being used as a catalyst for alpha, beta-unsaturated aldehyde transfer hydrogenation.

The invention discloses chiral boryl alcohol and a preparation method thereof, and belongs to the technical field of organic synthesis. The preparation method comprises the following step: in the presence of a catalyst and a transfer hydrogenation reagent, carrying out selective transfer hydrogenation reaction on acyl boron to generate chiral boryl alcohol. According to the method disclosed by the invention, the core skeleton of the chiral boryl alcohol is prepared with high selectivity through asymmetric transfer hydrogenation of acyl boron, the synthetic route is direct, and the atom economy is high; raw materials and catalysts are cheap and easy to obtain, reaction conditions are mild, operation is simple, and reaction is efficient.

The invention discloses a metal-free catalyst, a preparation method and application of the metal-free catalyst in preparation of benzyl alcohol through transfer hydrogenation of biomass-based benzaldehyde, and the catalyst is a nitrogen-doped carbon catalyst; in the catalyst, nitrogen is used as a Lewis alkaline site, and does not contain a Lewis acidic site and a # imgabs0 # acidic site. According to the preparation method of the metal-free nitrogen-doped carbon-based catalyst, the metal-free nitrogen-doped carbon-based catalyst (MF-NC) can be prepared through solvothermal self-assembly and pyrolysis processes by virtue of a structure regulator and taking a ZIF material as a sacrificial template, the preparation process is simple, the surface appearance is controllable, and the metal-free nitrogen-doped carbon-based catalyst has a relatively high specific surface area. The obtained MF-NC can efficiently and selectively convert benzaldehyde into benzyl alcohol through a Lewis alkaline site mediated MPV transfer hydrogenation reaction by taking cheap and renewable bioethanol as an in-situ hydrogen donor and a reaction solvent.

The invention discloses a high-efficiency transfer hydrogenation method of non-activated olefin, which comprises the following steps: adding a non-activated alkenyl amide compound, nickel acetylacetonate dihydrate, phenylsilane, water and cesium pivalate into an organic solvent 1, 4-dioxane, reacting at room temperature under a nitrogen condition for 12 hours, and after the reaction is completed, filtering to obtain a filtrate, namely the high-efficiency transfer hydrogenation method of the non-activated olefin. And performing post-treatment (extraction and column chromatography separation) to obtain the corresponding alkyl chloride compound. According to the method, phenylsilane and water are directly used as hydrogen sources, direct use of hydrogen can be avoided, operation is easy and convenient, and efficient construction of C (sp3)-C (sp3) bonds can be achieved through transfer hydrogenation of non-activated olefin. The conversion reaction conditions are extremely mild, and the reaction activity is high; the method has the advantages of excellent atom economy and step economy, wide substrate application range, good functional group compatibility and the like. It is worthy that the synthesis method is also suitable for later-stage modification of medicine molecules, and the druggability of the molecules is expected to be further improved.

The invention relates to a preparation method of an N-substituted-3-hydroxy azetidine compound, and belongs to the field of medical intermediates. According to the invention, cheap and easily available N-substituted-3-hydroxy azetidine or 3-hydroxy azetidine is used as a raw material, and in the presence of a metal catalyst, hydrogenation (transfer hydrogenation) deprotection and reductive amination one-pot reaction are carried out on the raw material and various aldehydes to obtain the target N-substituted-3-hydroxy azetidine compound. The method overcomes the defects that in the prior art, when the target N-substituent-3-hydroxy azetidine compound is prepared, the steps are tedious (6-7 steps are needed for reaction to obtain the product), dangerous reagents (LiAlH4 and the like) are used, the preparation reaction conditions are harsh (no water, no oxygen and high temperature), the yield is low and the like, and provides beneficial reference for industrial amplification.

The application belongs to the technical field of catalysts, and discloses a supported ruthenium nanocluster catalyst Ru / CNT@CN, a preparation method and application thereof. The catalyst takes carboxylated carbon nanotubes as a carrier, has a carbon nitride shell outside the carrier, and has ruthenium nanoclusters inlaid on the surface of the carbon nitride shell in situ. The preparation steps are as follows: (1) a mixed acid solution composed of concentrated nitric acid and concentrated sulfuric acid is used to perform oxidation treatment on multi-walled carbon nanotubes, and the carbon nanotubes are washed and dried to obtain carboxylated carbon nanotubes, denoted as CNT; (2) first, the CNT, DCD, Ru metal salt and water are stirred at 50-100 DEG C for 2-12 h to obtain a dispersion liquid; then, the dispersion liquid is frozen with liquid nitrogen and subjected to freeze-drying treatment to obtain a catalyst precursor CNT@DCD-Ru; finally, the CNT@DCD-Ru is annealed at 500-700 DEG C for 2-8 h in a hydrogen-inert gas mixed atmosphere to obtain the target catalyst Ru / CNT@CN. The catalyst is applied in the hydrogen production by ammonia borane hydrolysis or the transfer hydrogenation reaction of nitroaromatic compounds. The catalyst prepared by the application has excellent catalytic activity and stability.

The present application relates to the field of drug synthesis, in particular to a novel intermediate, a method for preparing the same and application thereof. The structural formula of the novel intermediate provided by the present application is as expressed by formula I:where R is a secondary amine protection group. Based on the possible biogenic pathway of morphine derivatives, the present application realizes the efficient synthesis of morphine derivatives through the strategy of biomimetic synthesis, taking the asymmetric transfer hydrogenation reaction and the intramolecular oxidative dearomatization Heck reaction in the process of preparing the intermediate as the key reactions of total synthesis. Using the novel intermediate provided by the present application to synthesize morphine derivatives has the characteristics of significantly reducing the synthesis steps, improving the yield, reducing the discharge of three wastes and reducing the production cost.

The present disclosure provides methods of synthesizing a compound of Formula I. The method includes an asymmetric transfer hydrogenation to produce an intermediate and then carrying forward the single or enriched enantiomer through the remainder of the synthesis of a compound of Formula I. Also disclosed is an alternative route for attaching the heterocyclic ring.

The invention provides an SBA-16-DC-UiO-66 composite material as well as a preparation method and application thereof, and belongs to the technical field of transfer hydrogenation reaction catalyst materials. According to the invention, 3-(triethoxy silyl) propyl succinic anhydride is used as a carboxyl functional reagent and is subjected to co-condensation with tetraethoxysilane to prepare the double-carboxyl functional mesoporous silica SBA-16-DC with adjustable aperture, high specific surface area and excellent hydrothermal stability, metal ion binding sites of the carrier are increased, and the mesoporous silica SBA-16-DC has the advantages of high specific surface area, high specific surface area and excellent hydrothermal stability. Steric hindrance is provided for UiO-66 growth to inhibit agglomeration, the mass transfer efficiency can be enhanced through a mesoporous confinement effect, and the efficiency of catalyzing a furfural transfer hydrogenation reaction and the yield of a catalytic product are remarkably improved; carboxyl on the surface of SBA-16-DC can effectively adsorb Zr < 4 + >, the dispersion uniformity and stability of the active component UiO-66 in the carrier are improved, the problems of agglomeration and loss are avoided, and the catalytic performance and stability of the composite material are remarkably improved.

The present invention discloses a method for asymmetric transfer hydrogenation synthesis of chiral flavanol compounds by dynamic kinetic resolution, and the catalyst used is a chiral ruthenium diamine complex. Through this method, asymmetric transfer hydrogenation of flavanone derivatives can be realized, and optically pure flavanol compounds containing three consecutive chiral centers can be obtained in high yield (the enantiomeric excess can reach 99%, and the diastereomeric ratio can reach >20:1). The present invention has high enantioselectivity and diastereoselectivity, is simple and easy to operate, the catalyst is commercially available, the reaction conditions are mild, the energy consumption is low, it is environmentally friendly and has good yield, and gram-scale experiments can be realized without loss of activity and enantioselectivity.

The invention relates to the field of medicine synthesis, in particular to a chiral tetrahydroquinoline compound and a preparation method thereof. According to the invention, a chiral phosphoric acid catalyst and Hanss ester are adopted to carry out asymmetric transfer hydrogenation on a chiral substituent group-containing 2-substituted quinoline substrate, and a series of novel chiral tetrahydroquinoline compounds containing intracyclic and extracyclic continuous chiral centers are prepared.

The application discloses a method for preparing furfuryl alcohol by furfural transfer hydrogenation. The active components Zr and Mg of the magnetic catalyst come from corresponding non-noble metal salt solution, and Fe is selected from oxides. The catalyst is prepared by a coprecipitation method. The method takes furfuryl alcohol as raw material, commercial isopropyl alcohol as hydrogen source and solvent, and carries out a closed reaction at 160-210 DEG C for 3-7 h under the stirring rate of 500 rpm, and then is cooled to room temperature to obtain the furfuryl alcohol. Under the optimal conditions, the conversion rate of furfuryl alcohol is 99.13%, and the yield of furfuryl alcohol is 92.50%. The catalyst preparation method is simple, low in price and good in cycle stability, the catalytic system is green and efficient, and has a wide application prospect.

The present invention discloses a method for the transfer hydrogenation reduction of fatty aldehydes, which relates to the technical field of fine organic chemical industry and comprises the following steps: Step S1, successively add α,β-unsaturated aldehyde, inert solvent, catalyst and hydrogen source into a high-pressure reaction vessel equipped with a condensation reflux device, after microwave-assisted treatment, carry out transfer hydrogenation reduction reaction at a certain temperature; Step S2, after the reaction is complete, cool to room temperature, filter to remove the catalyst, and rotary evaporate to remove the inert solvent and other low-boiling substances; the catalyst comprises an active component and an auxiliary component, the active component is a surface organic ionic salt modified palladium-carbon catalyst, and the auxiliary component is a nano rare earth oxide, and the mass ratio of the active component to the auxiliary component is (5-8):1. This method has high conversion rate, selectivity and yield.

This invention discloses a method for synthesizing ferrocene-isoquinoline and ferrocene-dihydroisoquinoline planar chiral compounds, belonging to the field of asymmetric catalysis technology. Using chiral phosphoric acid (CPA) as a catalyst, 1,4-dihydropyridine compound (HEH) as a hydrogen source, and racemic ferrocene-isoquinoline derivative (+ / -)-1 and ditert-butyl dicarbonate as substrates, two types of planar chiral ferrocene compounds are synthesized through asymmetric transfer hydrogenation resolution. The enantiomeric excess of the ferrocene-isoquinoline planar chiral compounds can reach 95%, while the enantiomeric excess of the ferrocene-dihydroisoquinoline carboxylic acid tert-butyl ester planar chiral compounds can reach 89%, with a resolution coefficient (S value) reaching 50. This invention achieves the hydrogenation kinetic resolution of ferrocene-isoquinoline compounds, is simple to operate, uses commercially available catalysts, operates under mild reaction conditions, and exhibits good resolution effects, showing excellent application prospects.

The invention discloses a non-activated olefin transfer hydrogenation method driven by a light / cobalt / mercaptan triple catalytic system. Olefin compounds and derivatives thereof are used as raw materials, bio-based gamma-terpinene is used as a hydrogen source, and catalytic circulation is realized through a hydrogen atom transfer (HAT) relay mechanism under the mild condition of visible light irradiation. The method is characterized in that (1) a dual-function activation mode of gamma-terpinene is created for the first time, wherein weak bonding diallyl C-H bonds (BDE = 76kcal / mol) synchronously provide hydrogen atoms and aromatization driving force; and (2) a three-catalyst synergistic system: an organic photosensitizer / cobalt-based catalyst / thiol reagent forms a cascade HAT pathway. (3) normal-temperature normal-pressure operation: high-pressure equipment is not needed, and the reaction time is less than 24 hours; the method breaks through the dependence of traditional hydrogenation on precious metal, high-pressure hydrogen and an oxidizing agent, realizes efficient hydrogenation of non-activated olefin, and provides a new way for synthesis of drug molecule intermediates.

The present invention belongs to the technical field of organic chemical preparation, and particularly relates to a method for synthesizing tetrahydroquinoline and its derivatives. In this method, in an organic solvent, using Hansch ester 1,4-dihydropyridine as a hydrogen source, and using N-aryl propargylamine as a starting material, under the action of a metal catalyst, tetrahydroquinoline and its derivatives are directly prepared in one step through a tandem reaction of intramolecular hydroarylation and transfer hydrogenation of alkynes. The present invention provides a synthesis method with mild reaction conditions, simple operation, few reaction steps, a wide substrate scope, and capable of directly obtaining tetrahydroquinoline and its derivatives through one-step reaction. The present invention overcomes the defects of the raw materials in the preparation of tetrahydroquinoline and its derivatives in the prior art, selects simple and easily preparable N-aryl propargylamine as the starting material, and can obtain the desired tetrahydroquinoline and its derivatives through one-step reaction.

The invention discloses a sea urchin-shaped copper-based catalyst and application thereof in vanillin transfer hydrodeoxygenation reaction, and belongs to the technical field of transfer hydrogenation reaction. The technical prejudice that a copper-based catalyst is not suitable for transfer hydrodeoxygenation reaction is broken through, the sea-urchin-shaped copper-based catalyst is obtained by reducing the unconventional sea-urchin-shaped porous structure copper silicate serving as a precursor, and the sea-urchin-shaped copper-based catalyst is proved to have better conversion rate and selectivity in vanillin transfer hydrodeoxygenation reaction; besides, compared with the carbon-modified urchin-shaped porous structure copper silicate serving as a precursor, the carbon-modified urchin-shaped porous structure copper silicate and the reduced urchin-shaped copper-based catalyst have better conversion rate and selectivity, and the catalytic performance of the carbon-modified urchin-shaped copper-based catalyst can be comparable with that of a noble metal catalyst.

Disclosed in the present invention are a polymeric diamine ligand, a diamine ligand, a preparation method therefor, and the use in catalytic synthesis of a chiral alcohol. Specifically provided in the present invention is a polymeric diamine compound, the polymeric diamine compound having a structural framework shown as formula I. A polymeric diamine metal chelate prepared from the polymeric diamine compound may be used as a catalyst in a transfer hydrogenation reaction to obtain chiral alcohol compounds having a plurality of substituents with a low catalyst loading and a high yield. Moreover, said reaction involves mild conditions, no alkali participation and simple operation and does not need special reactors.

A process for preparing 2,2,4,4-tetramethylcyclobutane-1,3-diol by reacting 2,2,4,4-tetramethylcyclobutanedione with isobutanol in the presence of a tandem transfer hydrogenation and Tischenko reaction catalyst.

The present invention belongs to the technical field of organic synthesis, and specifically discloses a method for preparing an upadacitinib intermediate WP3, comprising the following steps: using an ethanol / water mixed solution as a solvent, under a nitrogen range, heating a compound WP2 under the action of 10% palladium carbon, ammonium formate and hydrochloric acid to react, and after the reaction is completed, post-processing to obtain an intermediate WP3. The original research adopts a high-risk process for pressurized hydrogenation, which has high requirements for factory hardware. The present invention solves the limitation of high-pressure equipment by transfer hydrogenation. The present invention can effectively remove the above-mentioned impurities in the compound WP3 step through the free base separation operation of the compound WP3, and can well control the related substances in the API step without going through a refining process, thereby reducing the process cost. The present invention can also remove the pigments generated by the process through the free base separation operation of the compound WP3, thereby controlling the color of the upadacitinib API to off-white, and this color gradation control is much higher than the color control standard of the original research raw material drug, and improves product safety by controlling pigment impurities.

Disclosed is a process for preparing 2,2,4,4-tetramethylcyclobutane-1,3-diol by reacting 2,2,4,4-tetramethylcyclobutanedione with a secondary alcohol in the presence of a transfer hydrogenation catalyst.

The invention discloses a preparation method of chiral aryloxy substituted chiral diol, which comprises the following step: in the presence of a chiral catalyst and a transfer hydrogenation reagent, carrying out selective transfer hydrogenation reaction on aryloxy substituted asymmetric diketone to generate the chiral aryloxy substituted chiral diol. According to the method provided by the invention, the raw materials and the catalyst are cheap and easy to obtain, the reaction condition is mild, the operation is simple, and the reaction is efficient; through asymmetric transfer hydrogenation of aryloxy-substituted asymmetric diketone, the chiral aryloxy-substituted chiral diol core skeleton is prepared with high selectivity, the synthesis route is direct, and the atom economy is high.

The invention discloses a preparation method of a phosphorus and oxygen co-doped nitrogen-doped carbon core-shell structure catalyst and a method for preparing aromatic amine through transfer hydrogenation reduction of nitro-aromatic hydrocarbon, and the preparation method of the catalyst comprises the following steps: step (1), respectively dissolving heteroatom salt, zinc salt and dimethylimidazole in deionized water to obtain respective solutions, the preparation method comprises the following steps: adding organic amine into a dimethylimidazole solution, stirring, then adding a heteroatom salt solution, finally adding a zinc salt solution to obtain a mixed solution, reacting the mixed solution for a set time, centrifugally filtering and washing a reaction product, and carrying out vacuum drying to obtain a ZIF-8 precursor compound; and (2) calcining the ZIF-8 precursor compound at a high temperature in an inert atmosphere to obtain the phosphorus and oxygen co-doped nitrogen-doped carbon core-shell structure catalyst. According to the preparation method of the phosphorus and oxygen co-doped nitrogen-doped carbon core-shell structure catalyst disclosed by the embodiment of the invention, the prepared catalyst is low in cost, not easy to inactivate and high in catalytic reaction activity.

The application discloses a kind of defective type UiO-66 (Zr) nanometer catalyst and its preparation method and application, it is related to biomass catalytic conversion and metal organic framework material technical field, specifically includes: zirconium chloride, terephthalic acid and acid adjusting agent are added in N,N-dimethylformamide, solvent thermal reaction is carried out under the condition of 120-160 ℃ 3-5h, after centrifugation, washing and drying, defective precursor material is obtained;Defective precursor material is dispersed in organic solution and reflux elution is carried out, after centrifugation, washing and drying, defective type UiO-66 (Zr) nanometer catalyst is obtained.The application solves the problem that the material of UiO-66 (Zr) prepared by traditional method is poor in acid-base site synergy in furfural transfer hydrogenation reaction, low in catalytic efficiency and difficult to realize gram preparation, realizes 100% furfural conversion rate and 99.5% furfuryl alcohol selectivity.

According to the protonated COFs photocatalyst and the synthetic method of the aromatic hydroxylamine derivative thereof, imine B-COF is constructed, an imine bond linker is protonated through a protonation strategy to regulate and control a COFs skeleton microenvironment, so that efficient photocatalytic transfer hydrogenation reaction is realized, and the selectivity of an N-hydroxyaniline product is as high as 99%.

The invention discloses a preparation process of bumetanib. The preparation method comprises the following steps: carrying out nucleophilic substitution on 4-chloro-3-nitro-5-sulfamoyl benzoic acid serving as a starting material and phenol in a potassium hydroxide aqueous solution to obtain a compound with a structural formula Int01, carrying out transfer hydrogenation in a methanol-water mixed solvent by using palladium on carbon as a catalyst and ammonium formate as a hydrogen source, reducing nitro on the compound with the structural formula Int01 into amino, and carrying out recrystallization to obtain the compound with the structural formula Int01. The compound with the structural formula Int02 is obtained; the preparation method comprises the following steps: carrying out reductive amination on the compound with the structural formula Int02, n-butyraldehyde and sodium triacetoxyborohydride to obtain a bumetanib crude product, refining the bumetanib crude product in a glacial acetic acid and cyclohexane system, decolorizing the refined bumetanib crude product in methanol-water by using activated carbon, and crystallizing to obtain a pure bumetanib product. And mixing the pure bumetanib with mannitol, an alkaline regulator and taurine to prepare a finished product.

The invention provides a method for synthesizing 4, 4 '-diaminodiphenyl ether through catalytic transfer hydrogenation, which comprises the following steps: dispersing a raw material 4, 4'-dinitrodiphenyl ether and a hydrogen donor hydrazine hydrate in a solvent in the atmosphere of inert gas, adding ferric salt and water-containing activated carbon as catalysts, and synthesizing the 4, 4 '-diaminodiphenyl ether through catalytic transfer hydrogenation. The synthesis method provided by the invention is simple and convenient to operate and mild in reaction condition, can realize efficient conversion of the raw material 4, 4 '-dinitrodiphenyl ether, is simple in post-treatment process, and can obtain a 4, 4'-diaminodiphenyl ether product by filtering while hot and cooling and crystallizing the filtrate after the reaction is finished.

The present disclosure relates to novel intermediates in the synthesis of elacestrant and methods of making the same. The chiral compound N-(2-((1R,2S)-6-(benzyloxy)-1-hydroxy-1,2,3,4- tetrahydronaphthalen-2-yl)-5-methoxyphenyl)acetamide (Compound (I-1)), is prepared in two steps: (1) a Pd-catalyzed α-arylation of a ketone precursor, 6-(benzyloxy)-3,4-dihydronaphthalen- 1(2H)-one, (Compound (a-1)), with N-(2-bromo-5-methoxyphenyl)acetamide (Compound (b- 1)); and (2) the asymmetric transfer hydrogenation of the product from Step 1, N-(2-(6- (benzyloxy)-1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl)-5-methoxyphenyl)acetamide (Compound (c-1)), to produce N-(2-((1R,2S)-6-(benzyloxy)-1-hydroxy-1,2,3,4-tetrahydronaphthalen-2-yl)-5- methoxyphenyl)acetamide (Compound (I-1)). The chiral compound (R)-6-(2-amino-4- methoxyphenyl)-5,6,7,8-tetrahydronaphtalen-2-ol (Compound (d)) is produced from Compound (I-1) by two additional steps: 3) dehydroxylation and debenzylation of N-(2-((1R,2S)-6- (benzyloxy)-1-hydroxy-1,2,3,4-tetrahydronaphtalen-2-yl)-5-methoxyphenyl)acetamide (Compound (I-1)) to produce N-(2-(6-hydroxy)-1,2,3,4-tetrahydronaphtalen-2-yl)-5- methoxyphenyl)acetamide (Compound (III-1)); and 4) hydrolysis of N-(2-(6-hydroxy)-1,2,3,4- tetrahydronaphtalen-2-yl)-5-methoxyphenyl)acetamide (Compound (III-1)) to produce (R)-6-(2- amino-4-methoxyphenyl)-5,6,7,8-tetrahydronaphtalen-2-ol (Compound (d)).

The present invention discloses a sea urchin-shaped copper-based catalyst and its application in the transfer hydrogenation and deoxygenation reaction of vanillin, belonging to the technical field of transfer hydrogenation reactions. The present invention breaks the technical prejudice that copper-based catalysts are not suitable for transfer hydrogenation and deoxygenation reactions. By using copper silicate with a sea urchin-shaped porous structure as an unconventional copper-based catalyst precursor, a sea urchin-shaped copper-based catalyst is obtained by reduction. It has been verified that it has good conversion rate and selectivity in the transfer hydrogenation and deoxygenation reaction of vanillin. In addition, the sea urchin-shaped copper-based catalyst obtained by reducing copper silicate with a sea urchin-shaped porous structure modified by carbon as a precursor has better conversion rate and selectivity compared with the sea urchin-shaped copper-based catalyst obtained by using copper silicate with an unmodified sea urchin-shaped porous structure as a precursor, and its catalytic performance can be comparable to that of noble metal catalysts.

The invention discloses chiral boryl diol and a preparation method thereof, and belongs to the technical field of organic synthesis. The preparation method comprises the following step: in the presence of a catalyst and a transfer hydrogenation reagent, carrying out selective transfer hydrogenation reaction on diacyl boron to generate chiral boryl diol. According to the invention, through asymmetric transfer hydrogenation of diacyl boron, the core skeleton of chiral boryl diol is prepared with high selectivity, the synthetic route is direct, and the atom economy is high; raw materials and catalysts are cheap and easy to obtain, reaction conditions are mild, operation is simple, and reaction is efficient.