CN110624542A - Method for catalyzing olefin and amine anti-Ma hydrogen amination reaction - Google Patents

Method for catalyzing olefin and amine anti-Ma hydrogen amination reaction Download PDF

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CN110624542A
CN110624542A CN201910926800.9A CN201910926800A CN110624542A CN 110624542 A CN110624542 A CN 110624542A CN 201910926800 A CN201910926800 A CN 201910926800A CN 110624542 A CN110624542 A CN 110624542A
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olefin
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tin oxide
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何静
马晓丹
安哲
宋红艳
舒心
项顼
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Beijing University of Chemical Technology
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    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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Abstract

A method for catalyzing olefin and amine anti-Ma hydrogen amination reaction belongs to the field of green catalysis. Under the catalytic action of a catalyst, olefin and amine are subjected to hydroamination reaction in a solvent to obtain an anti-Ma hydroamination product; the catalyst consists of atomically dispersed Pt, highly dispersed Sn and a composite oxide, the solvent is isopropanol, toluene or acetonitrile, the reaction temperature is 30-100 ℃, and the reaction time is 0.5-24 h. The method has the advantages of mild reaction conditions, high atom economy, lower reactant cost, high catalytic efficiency and easy separation of products, and is suitable for industrial production.

Description

Method for catalyzing olefin and amine anti-Ma hydrogen amination reaction
Technical Field
The invention belongs to the field of green catalysis, and particularly provides a method for catalyzing an amination reaction of olefin and amine.
Background
The C-N bond is a very important chemical bond and widely exists in fine chemicals, drug intermediates and biomacromolecules, so that the development of an effective method for constructing the C-N bond has important significance. The amine can be prepared by nucleophilic substitution reaction of halogenated hydrocarbon and amine or Hofmann rearrangement reaction, but has the problems of complicated reaction, high requirement on equipment and the like. The addition reaction of carbon-carbon unsaturated bonds and N-H bonds, i.e. the hydroamination reaction, provides an economical and efficient process with 100% atomic utilization of the synthesized amine.
The hydroamination catalyst has a rare earth metal complex (J.Am.chem.Soc.1989,111, 4108-. Thus, transition metal complexes such as Au (org. Lett.2006,8,3537-3540), Ru (chem. Commun.1999, 1133-1134), Pt (Organometallics 2004,23,1264-1268) have gained more attention, with Pt catalysts exhibiting higher activity. However, the anti-Markov hydroamination reaction, which has been classified as ten major catalytic challenges, remains a challenge, and Rh (chem. Eur. J.1999,5, 1306) -1319), Ru (J.Am. chem. Soc.2004,126,2702-2703), Ir Science (2017,355, 727-730) complex catalysts have been reported in the literature, but additional organic acids, light sources, or hydrogen donating thiols, etc. are required.
Therefore, the development of a catalyst which is simple, feasible and effective in catalyzing the anti-Markov hydrogen amination reaction is of great significance.
Disclosure of Invention
The invention aims to provide a method for catalyzing olefin and amine anti-Ma hydrogen amination reaction.
In order to achieve the above object, the present invention provides a method for catalyzing olefin and amine anti-mahalanobis hydroamination reaction, which is characterized in that under the catalysis of a catalyst, olefin and amine undergo a hydroamination reaction in a solvent to obtain an anti-mahalanobis hydroamination product; the catalyst consists of composite oxides of Pt and Sn uniformly dispersed in atomic level, the solvent is isopropanol, toluene or acetonitrile, the reaction temperature is 30-100 ℃, and the reaction time is 0.5-24 h.
The specific reaction is as follows:
in the catalyst, Pt can be a single atom, a two-dimensional cluster, a three-dimensional cluster or a nano particle, Sn is uniformly dispersed in a composite oxide in the form of an oxide, and the composite oxide is preferably zinc gallium tin oxide, zinc aluminum tin oxide, zinc titanium tin oxide, magnesium gallium tin oxide or magnesium aluminum tin oxide.
The preparation method of the catalyst is preferably as follows: prepared by taking hydrotalcite (LDHs) as a precursor to load Pt. The hydrotalcite layer divalent cation is preferably Zn according to the composition of the composite oxide2+Or Mg2 +The higher cation is preferably Sn4+And Al3+、Ti4+Or Ga3+The molar ratio of divalent cations to high-valent cations is preferably (1-6): 1, a hydrotalcite precursor is loaded with a Pt salt, the Pt salt is preferably sodium chloroplatinate, platinum acetylacetonate or platinum tetraammine nitrate, the hydrotalcite precursor is calcined in a muffle furnace at the heating rate of 1-10 ℃/min and the temperature of 530-2Reducing in the atmosphere, controlling the reduction temperature at 300-900 ℃, the reduction heat preservation time at 1-5 h, and the heating rate at 1-10 ℃/min to obtain the corresponding catalyst.
The mass fraction of Pt in the catalyst is preferably 0.01-10.0%, and the mass fraction of Sn is preferably 0.01-15.0%.
The mole ratio of the catalyst Pt to the olefin is preferably 1: 1000-1: 50.
The molar ratio of the amine to the olefin is preferably 1: 1.0-1: 5.0.
The reaction temperature is preferably 50-100 ℃, and the reaction time is preferably 0.5-24 h.
The substrate olefin is preferably terminal olefin, preferably styrene, cyanostyrene, methyl styrene, methoxy styrene and 1-octene.
The substrate amine is preferably N-H organic matter, amine (secondary amine) with at least one active hydrogen, and is preferably pyrrolidine, 3-hexylamine, 1-pentylamine or aniline.
After the reaction is finished, the anti-Ma hydrogen amination product is obtained through post-treatment.
The post-treatment step is preferably: filtering, and purifying the filtrate by recrystallization, distillation, reduced pressure distillation, thin-layer chromatography or column chromatography to obtain the anti-Markov hydrogen aminated product.
The invention has the obvious advantages of simple and easy catalyst preparation method, high catalytic anti-Ma hydrogen amination selectivity up to 99 percent, high conversion rate up to 69 percent, cheap and easily obtained reaction raw materials, mild reaction conditions and high atom utilization rate.
Drawings
FIG. 1 is a scanning transmission electron micrograph and a power spectrum of the catalyst of example 1.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples. In the preparation of hydrotalcite (LDHs) precursor, metal ion salt in hydrotalcite is dissolved in water, and then mixed with sodium hydroxide and Na2CO3The mixed solution is dripped into water, the pH is controlled to be 9-11 in the dripping process, the mixed solution is stirred and crystallized for 12 hours at the temperature of 60 ℃, and then the mixed solution is washed.
Example 1
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.0045mol Al(NO3)3·9H2O and 0.0005mol SnCl4·5H2Dissolving O in 200ml deionized water to prepare mixed salt solution, and taking 0.05mol NaOH and 0.1mol Na2CO3Dissolving in 200ml deionized water to prepare an alkali solution, simultaneously dropwise adding the salt solution and the alkali solution into a four-neck flask containing 200ml deionized water at room temperature, controlling the pH to be about 10 in the dropwise adding process, stirring and crystallizing at 60 ℃ for 12 hours, filtering and washing the obtained solid until the pH is 7, and drying in a 60 ℃ oven for 10 hours to obtain ZnAlSn-LDHs。
And B: weighing 2g ZnAlSn-LDHs (prepared in step A), and soaking 0.0583g [ Pt (NH) in equal volume3)4](NO3)2The obtained aqueous solution is uniformly shaken, washed to remove physical adsorption ions, and dried for 12 hours at 80 ℃ to obtain Pt/ZnAlSn-LDHs. Heating the obtained Pt/ZnAlSn-LDHs in a muffle furnace at 5 ℃/min, preserving the temperature at 550 ℃ for 120min, cooling to room temperature, and putting the obtained product in a tube furnace H2Reducing at 550 ℃ for 240min to obtain the Pt/ZnAlSn-MMO. FIG. 1 is a scanning transmission electron micrograph and a power spectrum of the Pt/ZnAlSn-MMO catalyst obtained in example 1, and the atomically dispersed Pt and the highly dispersed Sn can be found.
And C: accurately weighing 0.6mmol of styrene, 0.3mmol of pyrrolidine, 50mg of catalyst and 1.5mL of isopropanol as solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature is 60 ℃, the reaction time is 8 hours, then the reaction product is cooled to room temperature, and the gas chromatography analysis is adopted, so that the anti-Markov selectivity is 99%, and the conversion rate is 69%. The product was isolated and purified by distillation under reduced pressure at 0.1Torr, 55 ℃.1H NMR(400MHz)δ/ppm＝1.80-1.83(td,J＝5.6Hz,J＝11.1Hz,4H),2.55(bs,4H),2.56-2.65(m, 2H),2.81-2.85(m,2H),7.20-7.26(m,3H),7.20-7.31(m,2H)。
Example 2
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.0045mol Al(NO3)3·9H2O and 0.0005mol SnCl4·5H2Dissolving O and 0.0005mol of sodium citrate in 80ml of deionized water, adding 0.1mol of urea, transferring the solution to a polytetrafluoroethylene high-pressure kettle, crystallizing for 24h at 120 ℃, filtering and washing the obtained solid until the pH value is 7, and drying in an oven at 60 ℃ for 10h to obtain ZnAlSn-LDHs-urea.
And B: weighing 2g ZnAlSn-LDHs (prepared in step A), and soaking in an equal volume of 0.0083g [ Pt (NH) ]3)4](NO3)2The obtained aqueous solution is uniformly shaken, washed to remove physical adsorption ions, and dried for 12 hours at the temperature of 80 ℃ to obtain Pt/ZnAlSn-LDHs-urea. Heating the obtained Pt/ZnAlSn-LDHs in a muffle furnace at 5 ℃/min, preserving the temperature at 550 ℃ for 120min,after cooling to room temperature, in a tube furnace H2Reducing for 120min at 320 ℃ to obtain the Pt/ZnAlSn-MMO-urea.
And C: accurately weighing 0.6mmol of styrene, 0.3mmol of pyrrolidine, 50mg of catalyst and 1.5mL of isopropanol as solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature is 60 ℃, the reaction time is 8 hours, then the reaction product is cooled to room temperature, and the gas chromatography analysis is adopted, so that the anti-Markov selectivity is 99%, and the conversion rate is 33%.
Example 3
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.0045mol Al(NO3)3·9H2O and 0.0005mol SnCl4·5H2Dissolving O in 200ml deionized water to prepare mixed salt solution, and taking 0.05mol NaOH and 0.1mol Na2CO3Dissolving the solid in 200ml of deionized water to prepare an alkali solution, simultaneously dropwise adding the salt solution and the alkali solution into a four-neck flask containing 200ml of deionized water at room temperature, controlling the pH to be about 10 in the dropwise adding process, stirring and crystallizing at 60 ℃ for 12 hours, filtering and washing the obtained solid until the pH is 7, and drying in an oven at 60 ℃ for 10 hours to obtain ZnAlSn-LDHs.
And B: weighing 2g ZnAlSn-LDHs (prepared in step A), and soaking in an equal volume of 0.0083g [ Pt (NH) ]3)4](NO3)2The obtained aqueous solution is uniformly shaken, washed to remove physical adsorption ions, and dried for 12 hours at 80 ℃ to obtain Pt/ZnAlSn-LDHs. Heating the obtained Pt/ZnAlSn-LDHs in a muffle furnace at 5 ℃/min, preserving the temperature at 550 ℃ for 120min, cooling to room temperature, and putting the obtained product in a tube furnace H2Reducing at 320 ℃ for 120min to obtain the catalyst.
And C: accurately weighing 0.6mmol of styrene, 0.3mmol of pyrrolidine, 50mg of catalyst and 1.5mL of isopropanol as solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature is 60 ℃, the reaction time is 8 hours, then the reaction product is cooled to room temperature, and the gas chromatography analysis is adopted, so that the anti-Markov selectivity is 99%, and the conversion rate is 44%.
Example 4
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.0045mol Al(NO3)3·9H2O and 0.0005mol SnCl4·5H2Dissolving O in 200ml deionized water to prepare mixed salt solution, and taking 0.05mol NaOH and 0.1mol Na2CO3Dissolving the solid in 200ml of deionized water to prepare an alkali solution, simultaneously dropwise adding the salt solution and the alkali solution into a four-neck flask containing 200ml of deionized water at room temperature, controlling the pH to be about 10 in the dropwise adding process, stirring and crystallizing at 60 ℃ for 12 hours, filtering and washing the obtained solid until the pH is 7, and drying in an oven at 60 ℃ for 10 hours to obtain ZnAlSn-LDHs.
And B: weighing 2g of ZnAlSn-LDHs (prepared in the step A), and soaking 0.0583g of Pt (C) in the same volume5H7O2)2And (3) uniformly shaking the ethanol solution, washing to remove physical adsorption ions, and drying at 80 ℃ for 12 hours to obtain the Pt/ZnAlSn-LDHs. Heating the obtained Pt/ZnAlSn-LDHs in a muffle furnace at 5 ℃/min, preserving the temperature at 550 ℃ for 120min, cooling to room temperature, and putting the obtained product in a tube furnace H2Reducing at 550 ℃ for 240min to obtain the Pt/ZnAlSn-MMO.
And C: accurately weighing 0.6mmol of styrene, 0.3mmol of pyrrolidine, 50mg of catalyst and 1.5mL of isopropanol as solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature is 60 ℃, the reaction time is 8 hours, then the reaction product is cooled to room temperature, and the gas chromatography analysis is adopted, so that the anti-Markov selectivity is 99%, and the conversion rate is 58%.
Example 5
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.0045mol Al(NO3)3·9H2O and 0.0005mol SnCl4·5H2Dissolving O in 200ml deionized water to prepare mixed salt solution, and taking 0.05mol NaOH and 0.1mol Na2CO3Dissolving the solid in 200ml of deionized water to prepare an alkali solution, simultaneously dropwise adding the salt solution and the alkali solution into a four-neck flask containing 200ml of deionized water at room temperature, controlling the pH to be about 10 in the dropwise adding process, stirring and crystallizing at 60 ℃ for 12 hours, filtering and washing the obtained solid until the pH is 7, and drying in an oven at 60 ℃ for 10 hours to obtain ZnAlSn-LDHs.
And B: weighing 2g ZnAlSn-LDHs (prepared in step A)Obtained), containing 0.0583g of [ Pt (NH) ] by equal volume impregnation3)4](NO3)2The obtained aqueous solution is uniformly shaken, washed to remove physical adsorption ions, and dried for 12 hours at 80 ℃ to obtain Pt/ZnAlSn-LDHs. Heating the obtained Pt/ZnAlSn-LDHs in a muffle furnace at 5 ℃/min, preserving the temperature at 550 ℃ for 120min, cooling to room temperature, and putting the obtained product in a tube furnace H2Reducing at 550 ℃ for 240min to obtain the Pt/ZnAlSn-MMO.
And C: accurately weighing 0.6mmol of styrene, 0.3mmol of 1-pentylamine, 50mg of catalyst and 1.5mL of isopropanol as a solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature is 60 ℃, the reaction time is 8 hours, then the reaction product is cooled to room temperature, and the gas chromatography analysis is adopted, so that the anti-Markov selectivity is 99%, and the conversion rate is 55%. The product was isolated and purified by distillation under reduced pressure at 0.1Torr at 90 ℃.1H NMR(400 MHz)δ/ppm＝0.86(t,J＝6.8Hz,3H),1.25-1.32(m,4H),1.44-1.49(m,2H), 2.58-2.62(t,J＝7.2Hz,2H),2.80-2.89(m,4H),7.20-7.22(m,3H),7.29-7.32 (m,2H)。

Claims (10)

1. A method for catalyzing olefin and amine anti-Ma's hydrogen amination reaction is characterized in that under the catalysis of a catalyst, olefin and amine generate hydrogen amination reaction in an organic solvent to obtain a higher amine compound; the catalyst consists of atomically dispersed Pt and highly dispersed Sn composite oxide, the reaction temperature is 30-100 ℃, and the reaction time is 0.5-24 h.
2. The method for catalyzing the anti-Markovnikou hydrogenation of olefins and amines as claimed in claim 1 wherein the catalyst comprises Pt as a single atom, two-dimensional cluster, three-dimensional cluster or nanoparticle and Sn as an oxide uniformly dispersed in a composite oxide, preferably zinc gallium tin oxide, zinc aluminum tin oxide, zinc titanium tin oxide, magnesium gallium tin oxide or magnesium aluminum tin oxide.
3. The method of claim 1 for catalyzing the reaction of an olefin with AminodeThe method is characterized in that the catalyst preparation method can be as follows: prepared by taking Layered Double Hydroxides (LDHs for short) as a precursor to load Pt; the hydrotalcite layer divalent cation is preferably Zn according to the composition of the composite oxide2+Or Mg2+The higher cation is preferably Sn4+And Al3+、Ti4+Or Ga3+The molar ratio of divalent cations to high-valent cations is preferably (1-6): 1, a hydrotalcite precursor is loaded with a Pt salt, the Pt salt is preferably sodium chloroplatinate, platinum acetylacetonate or platinum tetraammine nitrate, the hydrotalcite precursor is calcined in a muffle furnace at the heating rate of 1-10 ℃/min and the temperature of 530-2Reducing in the atmosphere, controlling the reduction temperature at 300-900 ℃, the reduction heat preservation time at 1-5 h, and the heating rate at 1-10 ℃/min to obtain the corresponding catalyst.
4. The method of claim 1, wherein the catalyst comprises 0.01-10.0 wt% of Pt and 0.01-15.0 wt% of Sn; the molar ratio of the catalyst Pt to the olefin is 1: 1000-1: 50; the molar ratio of the amine to the olefin is 1: 1.0-1: 5.0.
5. A process for the catalytic conversion of olefins and amines by tramadol hydroamination according to claim 1, wherein the solvent is isopropanol, toluene or acetonitrile.
6. The method of claim 1, wherein the substrate olefin is a terminal olefin, the substrate amine is an organic N-H compound, and the amine having at least one active hydrogen is a secondary amine.
7. The process of claim 1 wherein the substrate olefin is styrene, cyanostyrene, methylstyrene, methoxystyrene, 1-octene; the substrate amine is pyrrolidine, 3-hexylamine, 1-pentylamine, aniline.
8. The catalyst for catalyzing the anti-Markov hydroamination of olefin and amine is characterized by consisting of composite oxides of Pt and Sn with high dispersion degree at the atomic level, wherein the Pt is a single atom, a two-dimensional cluster, a three-dimensional cluster or a nano particle, the Sn is uniformly dispersed in the composite oxides in the form of oxides, and the composite oxides are preferably zinc gallium tin oxide, zinc aluminum tin oxide, zinc titanium tin oxide, magnesium gallium tin oxide or magnesium aluminum tin oxide.
9. The catalyst according to claim 8, wherein the mass fraction of Pt in the catalyst is 0.01 to 10.0%, and the mass fraction of Sn is 0.01 to 15.0%.
10. The method for preparing the catalyst of claim 8, wherein the catalyst is prepared by loading Pt on hydrotalcite (LDHs) as a precursor; the hydrotalcite layer divalent cation is preferably Zn according to the composition of the composite oxide2+Or Mg2+The higher cation is preferably Sn4+And Al3+、Ti4+Or Ga3+The molar ratio of divalent cations to high-valent cations is preferably (1-6): 1, a hydrotalcite precursor is loaded with a Pt salt, the Pt salt is preferably sodium chloroplatinate, platinum acetylacetonate or platinum tetraammine nitrate, the hydrotalcite precursor is calcined in a muffle furnace at the heating rate of 1-10 ℃/min and the temperature of 530-2Reducing in the atmosphere, controlling the reduction temperature at 300-900 ℃, the reduction heat preservation time at 1-5 h, and the heating rate at 1-10 ℃/min to obtain the corresponding catalyst.
CN201910926800.9A 2019-09-27 2019-09-27 Method for catalyzing olefin and amine anti-Ma hydrogen amination reaction Pending CN110624542A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114907215A (en) * 2022-05-29 2022-08-16 复旦大学 Catalytic decarbonylation hydroamination method of aromatic formamide and olefin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104148059A (en) * 2014-06-19 2014-11-19 北京化工大学 Reforming catalyst with high dispersion stability and preparation method thereof
US20150299073A1 (en) * 2010-12-31 2015-10-22 California Institute Of Technology Catalytic anti-markovnikov oxidation and hydration of olefins
CN109293706A (en) * 2018-11-29 2019-02-01 上海应用技术大学 The trivalent iridium imine composition of the dual key of nitrogen containing iridium, preparation method and applications
CN110204580A (en) * 2019-05-30 2019-09-06 上海应用技术大学 The nickelous imine composition of the nickeliferous dual bond structure of nitrogen and its preparation and application

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005077885A1 (en) * 2004-02-06 2005-08-25 Yale University Ruthenium-catalyzed hydroamination of olefins
CN104148120B (en) * 2014-06-19 2017-02-22 北京化工大学 Method for controlling high dispersion of metal centers for catalysts by using auxiliaries
CN110229045B (en) * 2019-06-26 2020-10-27 北京化工大学 Method for efficiently hydrogenating and converting furfuryl alcohol and high-dispersion supported Pt catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150299073A1 (en) * 2010-12-31 2015-10-22 California Institute Of Technology Catalytic anti-markovnikov oxidation and hydration of olefins
CN104148059A (en) * 2014-06-19 2014-11-19 北京化工大学 Reforming catalyst with high dispersion stability and preparation method thereof
CN109293706A (en) * 2018-11-29 2019-02-01 上海应用技术大学 The trivalent iridium imine composition of the dual key of nitrogen containing iridium, preparation method and applications
CN110204580A (en) * 2019-05-30 2019-09-06 上海应用技术大学 The nickelous imine composition of the nickeliferous dual bond structure of nitrogen and its preparation and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
XIAODAN MA ET AL: "Coordination-Unsaturated Sn (IV) and Single-atom Pt Synergetically Activating Amine and Alkene for Heterogeneous anti-Markovnikov Hydroamination", 《THE 8TH TOKYO CONFERENCE ON ADVANCED CATALYTIC SCIENCE AND TECHNOLOGY》 *
张攀科 等: "烯烃的反马氏氢胺化反应", 《安阳师范学院学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114907215A (en) * 2022-05-29 2022-08-16 复旦大学 Catalytic decarbonylation hydroamination method of aromatic formamide and olefin

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