CN110078658A - - two picolinamide catalyst of thiocarbamide and its preparation method and application - Google Patents
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- CN110078658A CN110078658A CN201910448668.5A CN201910448668A CN110078658A CN 110078658 A CN110078658 A CN 110078658A CN 201910448668 A CN201910448668 A CN 201910448668A CN 110078658 A CN110078658 A CN 110078658A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/40—Acylated substituent nitrogen atom
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
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- C07B2200/07—Optical isomers
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Abstract
The invention discloses a kind of-two picolinamide catalyst of thiocarbamide and its preparation method and application, and the structural formula of the catalyst is as follows:
Description
Technical field
The present invention relates to asymmetric catalytic technology fields, it is more particularly related to a kind of-two picolinamide of thiocarbamide
Catalyst.
Background technique
Design, the synthesis of chiral catalyst are one of most challenging projects of the field of asymmetric synthesis.Exploitation has new
The organic catalyst of clever skeleton has very important meaning for fields such as synthesis chemistry, the fully synthetic, pharmaceutical chemistry of natural products
Justice.Wherein, the organic bifunctional catalyst of metal-is a kind of new catalyst bone with multi-catalytic site, double catalysis modes
Frame.Because it has the characteristics that polygamy bit pattern, high catalytic performance, more catalytic activity active sites, attract in recent years increasingly
The attention of more researchers.For example, 2011, Dixon seminar (J.Am.Chem.Soc.2011,133,1710-1713)
Design synthesized one kind using quinine as the quinine of skeleton-bi triphenyl phosphine benzamide bifunctional catalyst, with silver oxide/
Quinine-picolinamide is the highly-solid selectively asymmetry cyclization that catalyst system realizes isonitrile and aldehyde compound.
2012, Nakamura seminar (J.Am.Chem.Soc.2012,134,19366-19369) reported a kind of novel quinine-
Picolinamide bifunctional catalyst and the ring-opening reaction that it is used for ethylenimine derivative and diphosphite.Although having had several
The organic bifunctional catalyst of the efficient metal-of class is reported and is used for the field of asymmetric synthesis, however, being based on cheap amino acid
Bifunctional catalyst, especially more hydrogen bond metal-organic bifunctional catalysts have not been reported.
Summary of the invention
It is an object of the invention to solve at least the above defect, and provide the advantages of at least will be described later.
It is a further object to provide a kind of-two picolinamide catalyst of thiocarbamide.
It is a further object to provide a kind of preparation methods of-two picolinamide catalyst of thiocarbamide.
In order to realize that these purposes and other advantages according to the present invention, the present invention provide a kind of-two picolinamide of thiocarbamide
Catalyst, which is characterized in that structural formula is as follows:
- two picolinamide catalyst of thiocarbamide can be passed through by double catalysis modes of more two pyridine coordinations of Hydrogenbond
Different metal centers and more hydrogen bonding sites activate different types of synthon, to reach the highly selective of target compound
Synthesize purpose.
Preferably, in-two picolinamide catalyst of thiocarbamide, the R is methyl, benzyl, isopropyl or tertiary fourth
One of base.
A kind of preparation method of-two picolinamide catalyst of thiocarbamide, wherein include:
Step 1: sequentially adding two pyridine first into the dichloromethane solution for (S)-amino acid that tertbutyloxycarbonyl is protected
Amine, 4- dimethylamino pyridine and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, normal-temperature reaction 12 after mixing
~24 hours, the first organic phase was obtained by extraction in residue；Resulting first organic phase is after washing, drying, concentration, through chromatographing
Separate and afford the two picolinamide intermediate of (S)-amino of tertbutyloxycarbonyl protection；
Step 2: the two picolinamide intermediate of (S)-amino that resulting tertbutyloxycarbonyl is protected using methylene chloride/
Trifluoroacetic acid system carries out de- tertbutyloxycarbonyl protection reaction and uses under zero degree ice bath after thin-layer chromatography tracks fully reacting
Ammonium hydroxide adjusts pH to 10~12, and then extraction is dried to obtain Second Organic Phase；
Step 3: the residue after the concentration of resulting Second Organic Phase is dissolved using tetrahydrofuran, it is then bis- with 3,5-
The reaction of (trifluoromethyl) phenyl isothiocyanate, is then concentrated, separates, affording-two picolinamide catalyst of thiocarbamide.
This preparation method has the characteristics that wide application range of substrates, chiral source are cheap and easy to get, synthesis step is few.
Reaction equation is as follows:
Preferably, in the preparation method of-two picolinamide catalyst of thiocarbamide, in the step 1, mixing
Process are as follows: stirred 12 hours under 20~25 DEG C of normal temperature conditions；
It is extracted using ethyl acetate；
It is washed using saturated salt solution；
Use methylene chloride: methanol=19: the eluant, eluent of 1 system is eluted.
Preferably, in the preparation method of-two picolinamide catalyst of thiocarbamide, in the step 2,20~
The protection reaction is carried out under the conditions of 25 DEG C, protecting the time of reaction is 6 hours；
It is extracted using ethyl acetate；
It is dried using anhydrous magnesium sulfate.
Preferably, in the preparation method of-two picolinamide catalyst of thiocarbamide, in the step 3,
The time of the Second Organic Phase and 3, bis- (trifluoromethyl) the phenyl isothiocyanate reactions of 5- is 12 hours；
Use methylene chloride: methanol=9: the eluant, eluent of 1 system is eluted.
Preferably, in the preparation method of-two picolinamide catalyst of thiocarbamide, the tertbutyloxycarbonyl protection
(S)-amino acid, two pyridyl-methanamines, 4- dimethylamino pyridine and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimine hydrochloric acid
The ratio between amount of substance of salt is 1.2: 1: 0.2: 1.5.
Preferably, in the preparation method of-two picolinamide catalyst of thiocarbamide, the tertbutyloxycarbonyl protection
(S)-two picolinamide intermediate of amino and 3, the ratio between amount of bis- (trifluoromethyl) the phenyl isothiocyanate substances of 5- are 1: 1.
Preferably, in the preparation method of-two picolinamide catalyst of thiocarbamide, the tertbutyloxycarbonyl protection
(S)-amino acid structure is as follows:
Wherein R is any one in methyl, benzyl, isopropyl and tert-butyl；
The structure of two pyridyl-methanamine is as follows:
The structure of the two picolinamide intermediate of (S)-amino of the tertbutyloxycarbonyl protection is as follows:
The structure of bis- (trifluoromethyl) phenyl isothiocyanates of 3,5- is as follows:
A kind of-two picolinamide catalyst of thiocarbamide, wherein as the application of chiral catalyst, can be applied to asymmetry
In michael addition reaction.
The present invention is include at least the following beneficial effects:
The double catalysis modes of-two picolinamide catalyst of thiocarbamide of the invention by more two pyridine coordinations of Hydrogenbond, energy
Different types of synthon is enough activated by different metal centers and more hydrogen bonding sites, to reach the height of target compound
Selectivity synthesis purpose.
Wide application range of substrates, chiral source are cheap in the preparation method of-two picolinamide catalyst of thiocarbamide of the invention
Be easy to get, synthesis step it is few.
- two picolinamide catalyst of thiocarbamide of the invention can be used for the asymmetry such as nitrostyrolene and diethyl malonate
In michael addition reaction.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, to enable those skilled in the art's reference say
Bright book text can be implemented accordingly.It should be understood that following embodiment is merely to illustrate the model of the present invention and is not intended to limit the present invention
It encloses.The content that the person skilled in the art in the field can make a thorough investigation of foregoing invention does nonessential modifications and adaptations.
Embodiment 1
Compound 3: the synthesis of the two picolinamide intermediate of (S)-amino of tertbutyloxycarbonyl protection:
The synthesis of compound 3a: to the two of N- tert-butoxycarbonyl-l-alanine 1a (0.61g, 3.2mmol, 1.2 times of equivalents)
Sequentially added in chloromethanes solution two pyridyl-methanamines (0.5g, 2.7mmol), 4- dimethylamino pyridine (DMAP, 65.8mg,
0.54mmol, 0.2 times of equivalent) and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCI, 0.62g,
3.2mmol, 1.2 times of equivalents).After mixture stirring at normal temperature 12 hours, organic phase, saturated common salt washing is extracted with ethyl acetate
It washs.Combined organic phase is separated after drying, concentration with column chromatography, and methylene chloride/methanol 19: 1 elutes to obtain the tertiary fourth oxygen of N-
Two pyridine carboxamide intermediate 3a of carbonyl-(L)-alanimamides, yield 82% (0.79g, 2.2mmol).
The synthesis of compound 3b: to N- tertbutyloxycarbonyl-L-phenylalanine 1a's (0.86g, 3.2mmol, 1.2 times of equivalents)
Sequentially added in dichloromethane solution two pyridyl-methanamines (0.5g, 2.7mmol), 4- dimethylamino pyridine (DMAP, 65.8mg,
0.54mmol, 0.2 times of equivalent) and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCI, 0.62g,
3.2mmol, 1.2 times of equivalents).After mixture stirring at normal temperature 12 hours, organic phase, saturated common salt washing is extracted with ethyl acetate
It washs.Combined organic phase is separated after drying, concentration with column chromatography, and methylene chloride/methanol 19: 1 elutes to obtain the tertiary fourth oxygen of N-
Two pyridine carboxamide intermediate 3b of carbonyl-(L)-phenylalanyl amine, yield 86% (1.0g, 2.3mmol).
The synthesis of compound 3c: to the two of N- tertbutyloxycarbonyl-Valine 1a (0.70g, 3.2mmol, 1.2 times of equivalents)
Sequentially added in chloromethanes solution two pyridyl-methanamines (0.5g, 2.7mmol), 4- dimethylamino pyridine (DMAP, 65.8mg,
0.54mmol, 0.2 times of equivalent) and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCI, 0.62g,
3.2mmol, 1.2 times of equivalents).After mixture stirring at normal temperature 12 hours, organic phase, saturated common salt washing is extracted with ethyl acetate
It washs.Combined organic phase is separated after drying, concentration with column chromatography, and methylene chloride/methanol 19:1 elutes to obtain the tertiary fourth oxygen of N-
Two pyridine carboxamide intermediate 3c of carbonyl-(L)-valine amide, yield 78% (0.81g, 2.1mmol).
The synthesis of compound 3d: to the tertiary Gamma Amino Butyric Acid 1a's of N- tertbutyloxycarbonyl-L- (0.75g, 3.2mmol, 1.2 times of equivalents)
Sequentially added in dichloromethane solution two pyridyl-methanamines (0.5g, 2.7mmol), 4- dimethylamino pyridine (DMAP, 65.8mg,
0.54mmol, 0.2 times of equivalent) and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCI, 0.62g,
3.2mmol, 1.2 times of equivalents).After mixture stirring at normal temperature 12 hours, organic phase, saturated common salt washing is extracted with ethyl acetate
It washs.Combined organic phase is separated after drying, concentration with column chromatography, and methylene chloride/methanol 19:1 elutes to obtain the tertiary fourth oxygen of N-
Two pyridine carboxamide intermediate 3d of carbonyl-(L)-tertiary fourth glutamine, yield 61% (0.66g, 1.6mmol).
Embodiment 2
Compound 6: the synthesis of-two picolinamide catalyst of thiocarbamide:
The synthesis of compound 6a: to two pyridine carboxamide intermediate of N- tertbutyloxycarbonyl-(L)-alanimamides (0.79g,
Trifluoroacetic acid (2.2mL) is added in methylene chloride (22mL) solution 2.2mmol).Reaction mixture takes off tertiary fourth oxygen at normal temperature
Carbonyl-protection 6 hours.After thin-layer chromatography (TLC) tracks fully reacting, under zero degree ice bath with ammonium hydroxide adjust pH value to 10~
12.Residue is extracted with ethyl acetate, and anhydrous magnesium sulfate is dry.It is dissolved after organic phase concentration with tetrahydrofuran, it is bis- that 3,5- is added
(trifluoromethyl) phenyl isothiocyanate (0.71g, 2.6mmol), reaction are concentrated after 12 hours, are separated with column chromatography, dichloro
Methane/methanol 9: 1 elutes to obtain compound 6a.White solid, yield 67% (0.77g, 1.5mmol).
The synthesis of compound 6b: to two pyridine carboxamide intermediate of N- tertbutyloxycarbonyl-(L)-phenylalanyl amine (1.0g,
Trifluoroacetic acid (2.3mL) is added in methylene chloride (23mL) solution 2.3mmol).Reaction mixture takes off tertiary fourth oxygen at normal temperature
Carbonyl-protection 6 hours.After thin-layer chromatography (TLC) tracks fully reacting, under zero degree ice bath with ammonium hydroxide adjust pH value to 10~
12.Residue is extracted with ethyl acetate, and anhydrous magnesium sulfate is dry.It is dissolved after organic phase concentration with tetrahydrofuran, it is bis- that 3,5- is added
(trifluoromethyl) phenyl isothiocyanate (0.74g, 2.8mmol), reaction are concentrated after 12 hours, are separated with column chromatography, dichloro
Methane/methanol 9: 1 elutes to obtain compound 6b.White solid, yield 63% (0.87g, 1.5mmol).
The synthesis of compound 6c: to two pyridine carboxamide intermediate of N- tertbutyloxycarbonyl-(L)-valine amide (0.81g,
Trifluoroacetic acid (2.1mL) is added in methylene chloride (21mL) solution 2.1mmol).Reaction mixture takes off tertiary fourth oxygen at normal temperature
Carbonyl-protection 6 hours.After thin-layer chromatography (TLC) tracks fully reacting, under zero degree ice bath with ammonium hydroxide adjust pH value to 10~
12.Residue is extracted with ethyl acetate, and anhydrous magnesium sulfate is dry.It is dissolved after organic phase concentration with tetrahydrofuran, it is bis- that 3,5- is added
(trifluoromethyl) phenyl isothiocyanate (0.68g, 2.5mmol), reaction are concentrated after 12 hours, are separated with column chromatography, dichloro
Methane/methanol 9: 1 elutes to obtain compound 6c.White solid, yield 66% (0.77g, 1.4mmol).
The synthesis of compound 6d: to two pyridine carboxamide intermediate of N- tertbutyloxycarbonyl-(L)-tertiary fourth glutamine (0.66g,
Trifluoroacetic acid (1.6mL) is added in methylene chloride (16mL) solution 1.6mmol).Reaction mixture takes off tertiary fourth oxygen at normal temperature
Carbonyl-protection 6 hours.After thin-layer chromatography (TLC) tracks fully reacting, under zero degree ice bath with ammonium hydroxide adjust pH value to 10~
12.Residue is extracted with ethyl acetate, and anhydrous magnesium sulfate is dry.It is dissolved after organic phase concentration with tetrahydrofuran, it is bis- that 3,5- is added
(trifluoromethyl) phenyl isothiocyanate (0.52g, 1.9mmol), reaction are concentrated after 12 hours, are separated with column chromatography, dichloro
Methane/methanol 9: 1 elutes to obtain compound 6d.White solid, yield 60% (0.55g, 0.96mmol).
Wherein, compound 6a~6d spectral data is as shown in the table:
Table 1
Embodiment 3
Catalytic effect experiment :-two picolinamide chiral catalyst 6a-6d of thiocarbamide of the invention is applied in asymmetric reaction
In, such as application of the compound 6d in nitrostyrolene and the michael addition reaction of diethyl malonate asymmetry, process is such as
Under:
Sequentially added into the toluene solution of nitrostyrene derivative (0.1mmol) diethyl malonate (24.0mg,
0.15mmol), compound 6d (5.7mg, 0.01mmol, 10mol%) and trifluoromethanesulfonic acid ketone (1.8mg, 0.005mmol,
5mol%).Reaction mixture reacts at normal temperature, after tracking fully reacting by thin-layer chromatography, is separated using column chromatography, stone
Oily ether/ethyl acetate 9: 1 affords michael addition product.
Reaction equation is as follows:
Catalytic effect is as shown in the table:
Table 2
From upper table 2, it can be seen that ,-two picolinamide chiral catalyst 6d of thiocarbamide of the invention is obtained in asymmetric reaction
Higher yield, reaches as high as 87%, minimum also to have 62%；It is minimum also to have 85% with enantiomeric excess high percentage up to 95%,
It can be seen that enantio-selectivity is higher.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With.It can be applied to various suitable the field of the invention completely.It for those skilled in the art, can be easily
Realize other modification.
Claims (10)
1. a kind of-two picolinamide catalyst of thiocarbamide, which is characterized in that structural formula is as follows:
2.-two picolinamide catalyst of thiocarbamide as described in claim 1, wherein the R is methyl, benzyl, isopropyl or uncle
One of butyl.
3. a kind of preparation method of-two picolinamide catalyst of thiocarbamide characterized by comprising
Step 1: sequentially adding two pyridyl-methanamines, 4- into the dichloromethane solution for (S)-amino acid that tertbutyloxycarbonyl is protected
Dimethylamino pyridine and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, normal-temperature reaction 12~24 after mixing
Hour, the first organic phase is obtained by extraction；Resulting first organic phase is after washing, drying, concentration, through chromatography and elution
Obtain the two picolinamide intermediate of (S)-amino of tertbutyloxycarbonyl protection；
Step 2: the two picolinamide intermediate of (S)-amino that resulting tertbutyloxycarbonyl is protected uses methylene chloride/trifluoro
Acetic acid carries out de- tertbutyloxycarbonyl protection reaction, and after thin-layer chromatography tracks fully reacting, ammonium hydroxide is used under zero degree ice bath
PH to 10~12 is adjusted, then extraction is dried to obtain Second Organic Phase；
Step 3: residue after the concentration of resulting Second Organic Phase is dissolved using tetrahydrofuran, then with the bis- (fluoroforms of 3,5-
Base) phenyl isothiocyanate reaction, it is then concentrated, separates, affording-two picolinamide catalyst of thiocarbamide.
4. the preparation method of-two picolinamide catalyst of thiocarbamide as claimed in claim 3, which is characterized in that the step 1
In, mixed process refers to: stirring 12~24 hours under 20~25 DEG C of normal temperature conditions；
It is extracted using ethyl acetate；
It is washed using saturated salt solution；
Methylene chloride in the methylene chloride/trifluoroacetic acid system: methanol=19: 1.
5. the preparation method of-two picolinamide catalyst of thiocarbamide as claimed in claim 3, which is characterized in that the step 2
In, the protection reaction is carried out under the conditions of 20~25 DEG C, protecting the time of reaction is 6~12 hours；
It is extracted using ethyl acetate；
It is dried using anhydrous magnesium sulfate.
6. the preparation method of-two picolinamide catalyst of thiocarbamide as claimed in claim 3, which is characterized in that the step 3
In, the time of the Second Organic Phase and 3, bis- (trifluoromethyl) the phenyl isothiocyanate reactions of 5- is 12 hours；
Use methylene chloride: methanol=9: 1 eluant, eluent is eluted.
7. the preparation method of-two picolinamide catalyst of thiocarbamide as claimed in claim 3, which is characterized in that the tertiary fourth oxygen
(S)-amino acid, two pyridyl-methanamines, 4- dimethylamino pyridine and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne of carbonyl-protection
The ratio between amount of substance of diimmonium salt hydrochlorate is 1.2: 1: 0.2:1.5.
8. the preparation method of-two picolinamide catalyst of thiocarbamide as claimed in claim 3, which is characterized in that the tertiary fourth oxygen
The two picolinamide intermediate of (S)-amino of carbonyl-protection and 3, the ratio between the amount of bis- (trifluoromethyl) the phenyl isothiocyanate substances of 5-
It is 1: 1.
9. the preparation method of-two picolinamide catalyst of thiocarbamide as claimed in claim 3, which is characterized in that the tertiary fourth oxygen
The structure of (S)-amino acid of carbonyl-protection is as follows:
Wherein R is any one in methyl, benzyl, isopropyl and tert-butyl；
The structure of two pyridyl-methanamine is as follows:
The structure of the two picolinamide intermediate of (S)-amino of the tertbutyloxycarbonyl protection is as follows:
The structure of bis- (trifluoromethyl) phenyl isothiocyanates of 3,5- is as follows:
10. a kind of-two picolinamide catalyst of thiocarbamide as described in claim 1, which is characterized in that as chiral catalyst
Using.
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| CN112724416A (en) * | 2020-12-16 | 2021-04-30 | 北京科技大学 | Bio-based hydrogen bond organic framework material and preparation method and application thereof |
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|---|---|---|---|---|
| CN111790439A (en) * | 2020-07-29 | 2020-10-20 | 南宁师范大学 | Chiral secondary amine diphenylphosphine arylformamide bifunctional catalyst and preparation method and application thereof |
| CN112724416A (en) * | 2020-12-16 | 2021-04-30 | 北京科技大学 | Bio-based hydrogen bond organic framework material and preparation method and application thereof |
| CN112724416B (en) * | 2020-12-16 | 2022-04-01 | 北京科技大学 | Bio-based hydrogen bond organic framework material and preparation method and application thereof |
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