CN118084665A - Method for synthesizing chiral alcohol by reducing alpha, beta-unsaturated lactone through palladium-catalyzed asymmetric hydrogenation - Google Patents
Method for synthesizing chiral alcohol by reducing alpha, beta-unsaturated lactone through palladium-catalyzed asymmetric hydrogenation Download PDFInfo
- Publication number
- CN118084665A CN118084665A CN202211449263.1A CN202211449263A CN118084665A CN 118084665 A CN118084665 A CN 118084665A CN 202211449263 A CN202211449263 A CN 202211449263A CN 118084665 A CN118084665 A CN 118084665A
- Authority
- CN
- China
- Prior art keywords
- palladium
- reaction
- beta
- asymmetric hydrogenation
- unsaturated lactone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 title claims abstract description 20
- 150000002596 lactones Chemical class 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000003446 ligand Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012696 Pd precursors Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical group OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 6
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- DRZBLHZZDMCPGX-VXKWHMMOSA-N (r)-tert-butyl-[3-[tert-butyl(methyl)phosphanyl]quinoxalin-2-yl]-methylphosphane Chemical compound C1=CC=C2N=C([P@](C)C(C)(C)C)C([P@](C)C(C)(C)C)=NC2=C1 DRZBLHZZDMCPGX-VXKWHMMOSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 1
- 101710159293 Acyl-CoA desaturase 1 Proteins 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 101100041816 Homo sapiens SCD gene Proteins 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 101150097713 SCD1 gene Proteins 0.000 description 1
- 102100028897 Stearoyl-CoA desaturase Human genes 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- POZIHPKRJFLANV-UHFFFAOYSA-N ethyl 2-oxo-1h-quinoline-3-carboxylate Chemical class C1=CC=C2NC(=O)C(C(=O)OCC)=CC2=C1 POZIHPKRJFLANV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- -1 lithium aluminum hydride Chemical compound 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing chiral alcohol by palladium-catalyzed asymmetric hydrogenation reduction of alpha, beta-unsaturated lactone, which takes chiral diphosphine complex of palladium as a catalyst and alpha, beta-unsaturated lactone as a substrate to synthesize chiral alcohol through asymmetric hydrogenation. The method has the advantages of simple and practical operation, commercially available catalyst, mild reaction conditions, low energy consumption and environmental friendliness.
Description
Technical Field
The invention belongs to the field of asymmetric catalytic synthesis, and relates to a method for synthesizing chiral alcohol by reducing alpha, beta-unsaturated lactone through palladium catalytic asymmetric hydrogenation.
Technical Field
The reduction of esters is important in organic synthesis, and common reduction methods include (1) reduction with negative hydrogen reagents such as lithium aluminum hydride, metal borohydride, borane, etc., which are expensive, unsafe to operate, etc., and often require the consumption of equivalent or several times of equivalent alkali for treatment, etc., which can generate a large amount of by-products, cause troublesome post-treatment, and also pollute the environment. (2) Heterogeneous hydrogenation catalytic systems of palladium carbon or platinum carbon are adopted, but the reaction is usually realized under the severe conditions of high temperature and high pressure (200-300 ℃ and more than 100 atm), and the energy consumption of the reaction is high and the byproducts are relatively more. (3) The homogeneous hydrogenation catalytic system using ruthenium, osmium or iridium has the characteristics of high atom economy, simple operation, environmental friendliness and the like, but usually requires the addition of equivalent alkali.
Homogeneous palladium asymmetric hydrogenation catalytic systems can realize the conversion of various functional groups with high efficiency and low energy consumption, but the reduction of ester functional groups has never been realized. The invention adopts a palladium/biphosphine ligand catalytic system, realizes simultaneous reduction of double bonds and ester groups in alpha, beta-unsaturated lactones for the first time, and obtains chiral alcohol products. The method has the advantages of wide substrate range, high yield, high enantioselectivity and the like.
Disclosure of Invention
The invention aims to provide a method for synthesizing chiral alcohol by palladium-catalyzed asymmetric hydrogenation reduction of alpha, beta-unsaturated lactone, which has the advantages of simple and practical operation, easily available raw materials, good enantioselectivity and diastereoselectivity, high yield, green atomic economy, environmental friendliness and the like.
The technical scheme of the invention is as follows:
The invention provides a method for synthesizing chiral alcohol by palladium-catalyzed asymmetric hydrogenation reduction of alpha, beta-unsaturated lactone, which takes chiral diphosphine complex of palladium as a catalyst and alpha, beta-unsaturated lactone as a substrate, and synthesizes chiral alcohol through asymmetric hydrogenation. The reaction formula of the method is as follows:
Or (b)
Wherein:
r is C1-C4 alkyl or benzyl;
r' is C1-C6 alkyl, benzyl, benzene ring, naphthalene ring, thiophene ring or aromatic ring containing substituent, wherein the substituent is methyl, ethyl, methoxy or halogen;
ar is benzene ring, naphthalene ring or aromatic ring containing substituent, wherein the substituent is methyl or ethyl;
the catalyst is a complex of a metal palladium precursor and a chiral diphosphine ligand.
Based on the above technical scheme, preferably, the asymmetric hydrogenation reaction solvent is an organic solvent, and the organic solvent is Trifluoroethanol (TFE) or Hexafluoroisopropanol (HFIP), preferably trifluoroethanol.
Based on the technical scheme, the asymmetric hydrogenation reaction temperature is preferably 50-100 ℃, preferably 60 ℃; the reaction time is 24 to 48 hours, preferably 36 hours; the hydrogen pressure is 300-1000psi, preferably 400-1000psi, more preferably 600psi.
Based on the above technical scheme, preferably, the molar ratio of the alpha, beta-unsaturated lactone, the metal palladium precursor and the chiral diphosphine ligand in the asymmetric hydrogenation reaction is 1:0.1:0.12-1:0.04:0.04, preferably 1:0.05:0.06.
Based on the above technical scheme, preferably, the metal palladium precursor is palladium chloride, palladium acetate or palladium trifluoroacetate, preferably palladium trifluoroacetate.
Based on the above technical scheme, preferably, the chiral diphosphine ligand is (R, R) -Quinoxp or (1 s,1s ', 2R') -DuanPhos.
Based on the above technical scheme, preferably, the concentration of the alpha, beta-unsaturated lactone substrate is 0.067mmol/mL.
Based on the technical scheme, preferably, the preparation method of the catalyst comprises the following steps: under the protection of nitrogen, the metal palladium precursor and the chiral diphosphine ligand are stirred in acetone for 30-60 minutes at room temperature, and then the acetone is removed by vacuum concentration.
Based on the technical scheme, preferably, the specific steps of the asymmetric hydrogenation reaction are as follows:
adding alpha, beta-unsaturated lactone, a catalyst and a solvent into a reaction bottle, putting the reaction bottle into an autoclave, introducing hydrogen for reaction to obtain a hydrogenated product, and purifying to obtain a pure product.
The invention adopts a homogeneous palladium catalytic system to realize asymmetric hydrogenation of alpha, beta-unsaturated lactone, and has high yield, high enantioselectivity (the enantiomeric excess can reach 99%) and high diastereoselectivity (the diastereoisomeric proportion can reach > 20:1) to generate chiral alcohol.
Advantageous effects
1. The raw materials are simple and easy to obtain, the catalyst is commercially available, the preparation is convenient, and the reaction operation is simple, convenient and practical.
2. The reaction activity is high, the raw materials are completely converted, the separation is convenient, and the high-purity product can be obtained.
3. Good stereoselectivity, and can obtain enantiomer with high enantioselectivity.
4. The reaction condition is mild, the energy consumption is low, and the method is environment-friendly and green.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The tetra-substituted olefin synthesis in the examples below is referred to as follows:
1.Hahn-Weinheimer,P.;Borsche,W.Zur Kenntnis der Benzisoxazole.VI.Die Acylierung von Benzisoxazolen nach Friedel-Crafts.Justus Liebigs Annalen der Chemie.1950,570,155-159.
2.Zhao,Q.K.;Wu,X.;Yang,F.;Yan,P.C.;Xie,J.-H.;Zhou,Q.L.Catalytic Asymmetric Hydrogenation of 3-Ethoxycarbonyl Quinolin-2-ones and Coumarins.Org.Lett.2021,23,3593-3598.
3.Yang S.-M.;Tang,Y.;Zhang,R.;Lu,H.;Kuo,G.-H.;Gaul,M.D.;Li,Y.4-Bicyclic Heter-oaryl-Piperidine Derivatives as Potent,Orally Bioavailable Stearoyl-CoA Desaturase-1(SCD1)Inhibitors.Part 1:Urea-Based Analogs.Bioorg.Med.Chem.Lett.2013,23,6773-6776.
Examples 1 to 7
Condition optimization
Palladium trifluoroacetate (0.01 mmol) and chiral ligand L (0.012 mmol) were charged into a reaction flask, 1mL of acetone was added after nitrogen substitution, stirring was performed at room temperature for 1 hour, and then acetone was removed by vacuum concentration to obtain a catalyst. In a glove box, substrate 1a (0.20 mmol), the catalyst prepared in situ and 3ml of organic solvent were placed in a high-pressure reaction vessel, hydrogen was introduced, and reacted at the reaction temperature for a certain period of time. After the reaction is finished, slowly releasing hydrogen, removing the solvent by rotary evaporation, and separating by column chromatography to obtain a pure product.
The organic solvent, the chiral ligand type, and the hydrogen pressure, the reaction temperature and the reaction time were changed, and the specific results are shown in table 1; ee is enantioselectivity.
TABLE 1 optimization of asymmetric hydrogenation reaction conditions for alpha, beta-unsaturated lactones
aReaction conditions:1a(0.20mmol),Pd(OCOCF3)2(5.0mol％),L(6mol％),solvent(3.0mL).bDetermined by NMR and all the products have>20:1dr.cDetermined by HPLC.
Examples 8 to 31
Asymmetric hydrogenation of α, β -unsaturated lactones:
Palladium trifluoroacetate (0.01 mmol) and chiral ligand (R, R) -Quinoxp (0.012 mmol) were placed in a reaction flask, 1mL of acetone was added after nitrogen substitution, and the mixture was stirred at room temperature for 1 hour, and then the acetone was concentrated in vacuo to remove the acetone to obtain a catalyst. In a glove box, substrate 1 (0.20 mmol), the catalyst prepared in situ, and 3 ml of trifluoroethanol were placed in a high pressure reactor, hydrogen (600 psi) was introduced, and reacted at 60℃for 36 hours. After the reaction is finished, slowly releasing hydrogen, removing the solvent by rotary evaporation, and separating by column chromatography to obtain a pure product.
The alpha, beta-unsaturated lactone is 1, and different examples are obtained by changing the type of 1 in the reaction, and the changed types are specifically as follows:
Example 32
Palladium trifluoroacetate (0.002 mmol) and chiral ligand (R, R) -Quinoxp (0.0024 mmol) were placed in a reaction flask, 1mL of acetone was added after nitrogen substitution, and the mixture was stirred at room temperature for 1 hour, and then the acetone was concentrated in vacuo to remove the acetone to obtain a catalyst. In a glove box, substrate 3 (0.20 mmol), the catalyst prepared in situ, and 3 ml of trifluoroethanol were placed in a high pressure reactor, hydrogen (600 psi) was introduced, and reacted at 60℃for 36 hours. After the reaction is finished, slowly releasing hydrogen, removing the solvent by rotary evaporation, and separating by column chromatography to obtain a pure product.
/>
/>
/>
Claims (5)
1. A method for reducing alpha, beta-unsaturated lactone by palladium-catalyzed asymmetric hydrogenation is characterized in that chiral diphosphine complex of palladium is used as a catalyst, alpha, beta-unsaturated lactone is used as a substrate, and chiral alcohol is synthesized by asymmetric hydrogenation;
The reaction formula is as follows:
Wherein:
r is C1-C4 alkyl or benzyl;
r' is C1-C6 alkyl, benzyl, benzene ring, naphthalene ring, thiophene ring or aromatic ring containing substituent, wherein the substituent is methyl, ethyl, methoxy or halogen;
ar is benzene ring, naphthalene ring or aromatic ring containing substituent, wherein the substituent is methyl or ethyl;
the catalyst is a complex of a metal palladium precursor and a chiral diphosphine ligand;
the reaction solvent is trifluoroethanol or hexafluoroisopropanol;
The reaction temperature is 50-100 ℃, the reaction time is 24-48 hours, and the hydrogen pressure is 300-1000psi.
2. The method of claim 1, wherein the metallic palladium precursor is palladium chloride, palladium acetate, or palladium trifluoroacetate; the chiral diphosphine ligand is (R, R) -Quinoxp or (1S, 1S ', 2R') -DuanPhos.
3. The method according to claim 1, wherein the catalyst is prepared by the following steps: under the protection of nitrogen, the metal palladium precursor and the chiral diphosphine ligand are stirred in acetone for 30-60 minutes at room temperature, and then the acetone is removed by vacuum concentration.
4. The method of claim 1, wherein the molar ratio of α, β -unsaturated lactone, metallic palladium precursor to chiral diphosphine ligand is from 1:0.1:0.12 to 1:0.04:0.04.
5. The method according to claim 1, wherein the specific steps of the asymmetric hydrogenation reaction are:
Adding alpha, beta-unsaturated lactone substrate, catalyst and solvent into a reaction bottle, placing the reaction bottle into an autoclave, introducing hydrogen for reaction to obtain hydrogenated product, and purifying to obtain pure product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211449263.1A CN118084665A (en) | 2022-11-18 | 2022-11-18 | Method for synthesizing chiral alcohol by reducing alpha, beta-unsaturated lactone through palladium-catalyzed asymmetric hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211449263.1A CN118084665A (en) | 2022-11-18 | 2022-11-18 | Method for synthesizing chiral alcohol by reducing alpha, beta-unsaturated lactone through palladium-catalyzed asymmetric hydrogenation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118084665A true CN118084665A (en) | 2024-05-28 |
Family
ID=91140852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211449263.1A Pending CN118084665A (en) | 2022-11-18 | 2022-11-18 | Method for synthesizing chiral alcohol by reducing alpha, beta-unsaturated lactone through palladium-catalyzed asymmetric hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118084665A (en) |
-
2022
- 2022-11-18 CN CN202211449263.1A patent/CN118084665A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Asymmetric hydrogenation of α, α'-disubstituted cycloketones through dynamic kinetic resolution: an efficient construction of chiral diols with three contiguous stereocenters. | |
| Xu et al. | Iridium‐Catalyzed Reductive Amination of Levulinic Acid to Pyrrolidinones under H2 in Water | |
| CN114163375B (en) | Synthesis method of 6,6-dimethyl-3-azabicyclo [3.1.0] hexane or derivative thereof | |
| KR20060117369A (en) | Hydrogenation method for producing optically active alcohols or carboxylic acids | |
| Zhong et al. | Catalytic asymmetric synthesis of spirocyclobutyl oxindoles and beyond via [2+ 2] cycloaddition and sequential transformations | |
| CN113999084A (en) | Synthetic preparation method of (S) - (-) -nicotine | |
| CN102030721B (en) | Method for synthesizing chiral benzosultam via palladium-catalytic asymmetric hydrogenation | |
| CN118084665A (en) | Method for synthesizing chiral alcohol by reducing alpha, beta-unsaturated lactone through palladium-catalyzed asymmetric hydrogenation | |
| Zhang et al. | Pd (ii)/Zn co-catalyzed chemo-selective hydrogenation of α-methylene-γ-keto carboxylic acids | |
| CN114605272A (en) | Preparation method of (R) -fluoxetine and derivative thereof | |
| Montagnon et al. | Selective Synthesis of Tetrahydro Oxepines by Cu‐Catalyzed Condensations of Diazomalonates and gem‐Dialkyl Vinyl Oxetanes | |
| CN114560761A (en) | Method for synthesizing 2, 3-disubstituted indanone derivative in aqueous phase at one time | |
| CN110028436B (en) | Preparation method of Vonoprazan key intermediate | |
| CN118084843A (en) | Method for synthesizing chiral dihydrocoumarin through asymmetric hydrogenation of palladium-catalyzed tetra-substituted olefin | |
| CN110790694B (en) | Method for synthesizing chiral indoline by using indole generated in situ by asymmetric hydrogenation under catalysis of palladium | |
| Szőri et al. | The enantioselective hydrogenation of 5, 6-dihydro-2H-pyran-3-carboxylic acid over a cinchona alkaloid-modified palladium catalyst: asymmetric synthesis of a cockroach attractant | |
| CN110396072A (en) | (s) preparation method of -3- hydroxyl tetrahydrofuran | |
| CN111087405A (en) | Method for asymmetrically synthesizing amaryllidaceae alkaloid (+) -gamma-lycorane | |
| CN114031507B (en) | Synthesis method of o-aminobenzyl alcohol compound | |
| CN115286485B (en) | Method for synthesizing secondary alcohol | |
| CN109836373B (en) | Environment-friendly preparation method of vitamin B6 and tail gas recycling method | |
| CN115160162B (en) | Asymmetric hydrogenation method of alpha-amino beta-keto ester | |
| CN110452172B (en) | Synthesis method of benzocaprolactam | |
| EP3415500B1 (en) | Method for preparing methylpyrrolidones | |
| CN113620826B (en) | Preparation method of D-p-hydroxyphenylglycine methyl ester hydrochloride suitable for industrial production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication |