CN114560775B - Preparation method of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine - Google Patents
Preparation method of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine Download PDFInfo
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- CN114560775B CN114560775B CN202210264931.7A CN202210264931A CN114560775B CN 114560775 B CN114560775 B CN 114560775B CN 202210264931 A CN202210264931 A CN 202210264931A CN 114560775 B CN114560775 B CN 114560775B
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- trimethyl
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- indene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- 238000000746 purification Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- YTCIYOXHHQLDEI-SNVBAGLBSA-N inpyrfluxam Chemical compound C([C@H](C=12)C)C(C)(C)C2=CC=CC=1NC(=O)C1=CN(C)N=C1C(F)F YTCIYOXHHQLDEI-SNVBAGLBSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BNYCHCAYYYRJSH-UHFFFAOYSA-N 1h-pyrazole-5-carboxamide Chemical compound NC(=O)C1=CC=NN1 BNYCHCAYYYRJSH-UHFFFAOYSA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000220225 Malus Species 0.000 description 1
- 235000011430 Malus pumila Nutrition 0.000 description 1
- 235000015103 Malus silvestris Nutrition 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B01J35/19—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine, belonging to the technical field of pesticide intermediate synthesis. The invention provides a method for preparing (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine with high purity in high yield, which comprises the following steps: takes 7-fluoro-1, 3-trimethyl-1H-indene-4-amine as raw material, pd-C or Pd/gamma-Al 2 O 3 Is used as a catalyst, and reacts with hydrogen in a solvent to obtain (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine. The invention remarkably improves the yield and purity of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine by optimizing a catalytic system and adding a proper cocatalyst.
Description
Technical Field
The invention belongs to the technical field of pesticide intermediate synthesis, and particularly relates to a preparation method of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine.
Background
Inpyrfluxam is a broad spectrum pyrazole carboxamide fungicide developed by Sumitomo chemical company, japan, and has the structure shown below:
inpyrfluxam is suitable for crops such as cotton, beet, rice, apple, corn, peanut and the like, and can be used for seed treatment.
In CN108777958A, a synthesis process of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine of Inpyrfluxam intermediate of formula (I) is disclosed, the synthetic route is as follows:
the method is characterized in that a compound of the formula (II) is used as a raw material, and is hydrogenated under the catalysis of 10% Pd-C to obtain a crude product with GC purity of 83%, and the crude product with GC purity of 95% is obtained through further crystallization and purification. The crude product yield and purity of the process are low, and the product yield after purification is extremely low, and only 0.225g of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine with 95% GC purity is finally obtained per 1g of 7-fluoro-1, 3-trimethyl-1H-indene-4-amine raw material.
Thus, there is a need for a process for the preparation of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-inden-4-amine in high yields.
Disclosure of Invention
The invention provides a preparation method of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine, which aims at the defects in the prior art and comprises the following steps:
starting from compounds of formula (II) Pd-C or Pd/gamma-Al 2 O 3 Reacting with hydrogen in a solvent to obtain (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine (I) serving as a catalyst;
wherein, when Pd-C is used as a catalyst, the solvent is selected from toluene or xylene; when Pd/gamma-Al is used 2 O 3 In the case of a catalyst, the solvent is selected from xylene, methylene chloride or dimethylacetamide.
Wherein, in the method, the temperature of the reaction is 20-40 ℃.
Preferably, in the above method, the temperature of the reaction is 20 to 25 ℃.
Wherein, in the method, the dosage of the catalyst is 1 to 10 percent of the weight of the compound of the formula (II).
Preferably, in the above process, the catalyst is used in an amount of from 5 to 10% by weight of the compound of formula (II).
Wherein, in the above method, the solvent is added in an amount of 10-100mL per 1g of the compound of formula (II).
Preferably, in the above process, the solvent is used in an amount of 20-40mL of solvent per 1g of compound of formula (II).
Wherein, in the method, a promoter is also added in the reaction, and the promoter is selected from sodium acetate or sodium butyrate.
Wherein, in the method, the addition amount of the cocatalyst is 1-50% of the Pd molar amount in the catalyst.
Preferably, in the above method, the addition amount of the cocatalyst is 5 to 10% of the molar amount of Pd in the catalyst.
In the invention, the Pd-C catalyst is Pd-C catalyst with 10 percent of Pd weight content, pd-gamma-Al 2 O 3 The catalyst is Pd/gamma-Al with the weight content of Pd of 10 percent 2 O 3 A catalyst.
The invention has the beneficial effects that:
according to the invention, a large amount of catalysts are matched with the solvent for screening, and a proper catalytic system is adopted, so that compared with the prior art, the yield and purity of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine are remarkably improved, and a product with GC purity of more than 95% can be directly obtained by adding a proper cocatalyst, so that the product can be directly used for subsequent reactions without further purification, and the method has important industrial application value.
Detailed Description
Specifically, the preparation method of the (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine comprises the following steps:
starting from compounds of formula (II) Pd-C or Pd/gamma-Al 2 O 3 Reacting with hydrogen in a solvent to obtain (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine (I) serving as a catalyst;
wherein, when Pd-C is used as a catalyst, the solvent is selected from toluene or xylene; when Pd/gamma-Al is used 2 O 3 In the case of a catalyst, the solvent is selected from xylene, methylene chloride or dimethylacetamide.
The invention screens a large amount of catalysts and solvents by Pd-C or Pd/gamma-Al 2 O 3 The yield and purity of the (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine are obviously improved by adopting an organic solvent which is matched with the catalyst.
In the method of the invention, the temperature of the reaction is 20-40 ℃; preferably 20-25 ℃.
In the method of the invention, the dosage of the catalyst is 1 to 10 percent of the weight of the compound of the formula (II); preferably 5 to 10%.
In the method of the invention, the solvent is added in an amount of 10-100mL of solvent per 1g of the compound of formula (II); preferably 20-40mL of solvent are added per 1g of compound of formula (II).
In order to further improve the yield and purity of the product under mild reaction conditions, a cocatalyst can be added; experiments show that when the cocatalyst is sodium acetate or sodium butyrate, the effect is particularly remarkable, and the yield and purity of the product can be further improved, so that the method is more beneficial to direct use for subsequent reactions without purification. The amount of promoter used is generally from 1 to 50%, preferably from 5 to 10%, for example 5%, 10% per mole of Pd.
The present invention will be described in further detail by way of examples, which are not intended to limit the scope of the invention.
The catalysts in the examples were purchased from Sean Kaili New Material Co., ltd.
Example 1
Example 1
7-fluoro-1, 3-trimethyl-1H-inden-4-amine (II) was prepared according to the method disclosed in example 1 of CN108777958A, GC purity 95%. The procedure of example 1 was repeated to give 890mg of crude product with a GC purity of 83%.
7-fluoro-1, 3-trimethyl-1H-indene-4-amine (1 g,7.6 mmol) is taken, 20mL of solvent is added, a certain amount of catalyst is added, hydrogen is introduced at room temperature (25 ℃) for reaction for 2 hours, filtration is carried out, the solvent is removed, the product is obtained, and the GC purity is detected.
The specific results are shown in table 1 below:
TABLE 1
As can be seen from table 1, when toluene or xylene is selected as the solvent when 10% pd-C is used as the catalyst, the effect is significantly better than other solvents; when using 10% Pd/gamma-Al 2 O 3 When the catalyst is used, the solvent is selected from dichloromethane or dimethylacetamide, and the effect is obviously better than that of other solvents. The catalyst is screened, meanwhile, a proper reaction solvent is adopted, and after the reaction system is filtered, the solvent is removed to obtain a product, so that the yield is high, more importantly, the purity is basically above 90%, the product can be directly used for the next reaction without purification, and the industrial production is facilitated.
Example 2
According to the method of example 1, 50mg of 10% Pd/gamma-Al is dissolved in dimethylacetamide 2 O 3 (0.05 mol) as catalyst, a certain amount of cocatalyst was additionally added, and the specific results are shown in Table 2 below:
TABLE 2
| Numbering device | Co-catalyst | Cocatalyst usage | Weight of the product | GC purity |
| 21 | Magnesium sulfate | 0.005mol | 925mg | 91％ |
| 22 | Sodium sulfate | 0.005mol | 933mg | 91％ |
| 23 | Ferric chloride | 0.005mol | 923mg | 91％ |
| 24 | Manganese chloride | 0.005mol | 938mg | 91％ |
| 25 | Tin chloride | 0.005mol | 919mg | 91％ |
| 26 | Acetic acid sodium salt | 0.005mol | 971mg | 96％ |
| 27 | Sodium butyrate | 0.005mol | 986mg | 96％ |
As can be seen from Table 2, when sodium acetate or sodium butyrate was added as a promoter, the yield and purity were both significantly improved, and the other promoters were not significantly effective.
Claims (6)
1. A preparation method of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine is characterized in that: the method comprises the following steps:
starting from compounds of formula (II) Pd-C or Pd/gamma-Al 2 O 3 Reacting with hydrogen in a solvent to obtain (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine (I) serving as a catalyst;
wherein, when Pd-C is used as a catalyst, the solvent is selected from toluene or xylene; when Pd/gamma-Al is used 2 O 3 In the case of a catalyst, the solvent is selected from xylene, methylene chloride or dimethylacetamide;
the dosage of the catalyst is 1-10% of the weight of the compound of the formula (II);
a promoter is also added in the reaction, and the promoter is selected from sodium acetate or sodium butyrate;
the addition amount of the cocatalyst is 5% -10% of the Pd molar amount in the catalyst.
2. The method according to claim 1, characterized in that: the temperature of the reaction is 20-40 ℃.
3. The method according to claim 2, characterized in that: the temperature of the reaction is 20-25 ℃.
4. The method according to claim 1, characterized in that: the catalyst is used in an amount of 5 to 10% by weight of the compound of formula (II).
5. The method according to claim 1, characterized in that: the solvent is used in an amount of 10-100mL of solvent per 1g of compound of formula (II).
6. The method according to claim 5, wherein: the solvent is used in an amount of 20-40mL of solvent per 1g of compound of formula (II).
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| CN202210264931.7A CN114560775B (en) | 2022-03-17 | 2022-03-17 | Preparation method of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine |
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| CN202210264931.7A CN114560775B (en) | 2022-03-17 | 2022-03-17 | Preparation method of (R, S) -7-fluoro-1, 3-trimethyl-2, 3-dihydro-1H-indene-4-amine |
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| Publication Number | Publication Date |
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| CN114560775A CN114560775A (en) | 2022-05-31 |
| CN114560775B true CN114560775B (en) | 2023-08-22 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011446A1 (en) * | 2002-07-26 | 2004-02-05 | Bayer Pharmaceuticals Corporation | Indane, dihydrobenzofuran, and tetrahydronaphthalene carboxylic acid derivatives and their use as antidiabetics |
| CN101687051A (en) * | 2007-07-12 | 2010-03-31 | 通用电气医疗集团股份有限公司 | Contrast agents |
| CN107033033A (en) * | 2016-10-14 | 2017-08-11 | 上海吉尔多肽有限公司 | The synthetic method of hydroxytyrosine between a kind of N α fluorenylmethyloxycarbonyls |
| CN108777958A (en) * | 2016-03-17 | 2018-11-09 | Fmc有限公司 | The method that S- enantiomers are converted into its meso form |
| CN113072620A (en) * | 2021-04-26 | 2021-07-06 | 南通大学 | PD-1 targeting peptide with analgesic activity, and synthesis method and application thereof |
-
2022
- 2022-03-17 CN CN202210264931.7A patent/CN114560775B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011446A1 (en) * | 2002-07-26 | 2004-02-05 | Bayer Pharmaceuticals Corporation | Indane, dihydrobenzofuran, and tetrahydronaphthalene carboxylic acid derivatives and their use as antidiabetics |
| CN101687051A (en) * | 2007-07-12 | 2010-03-31 | 通用电气医疗集团股份有限公司 | Contrast agents |
| CN108777958A (en) * | 2016-03-17 | 2018-11-09 | Fmc有限公司 | The method that S- enantiomers are converted into its meso form |
| CN107033033A (en) * | 2016-10-14 | 2017-08-11 | 上海吉尔多肽有限公司 | The synthetic method of hydroxytyrosine between a kind of N α fluorenylmethyloxycarbonyls |
| CN113072620A (en) * | 2021-04-26 | 2021-07-06 | 南通大学 | PD-1 targeting peptide with analgesic activity, and synthesis method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Asymmetric hydrogenation of indene carboxylic acids: stereochemistry of hydrogen addition;Borszeky K等;《Tetrahedron: Asymmetry》;第10卷(第24期);第4781-4789页 * |
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