CN113527362A - Method for synthesizing chiral phosphoramidite ligand based on R-2-phenylethylamine - Google Patents
Method for synthesizing chiral phosphoramidite ligand based on R-2-phenylethylamine Download PDFInfo
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- CN113527362A CN113527362A CN202110822766.8A CN202110822766A CN113527362A CN 113527362 A CN113527362 A CN 113527362A CN 202110822766 A CN202110822766 A CN 202110822766A CN 113527362 A CN113527362 A CN 113527362A
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- 239000003446 ligand Substances 0.000 title claims abstract description 37
- 150000008300 phosphoramidites Chemical class 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002466 imines Chemical class 0.000 claims abstract description 20
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- -1 amine hydrochloride Chemical class 0.000 claims abstract description 14
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657154—Cyclic esteramides of oxyacids of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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Abstract
The invention discloses a method for synthesizing a chiral phosphoramidite ligand based on R-2-phenylethylamine. The method comprises the steps of firstly reacting R-2-phenylethylamine with acetophenone to obtain an imine intermediate, and then reacting the imine intermediate with H2Reducing under the catalysis of Pd/C to obtain amine with high dr value, reacting amine with concentrated hydrochloric acid to generate amine hydrochloride, and finally reacting the amine hydrochloride with chiral diphenol and PCl3The chiral phosphoramidite ligand is obtained by the reaction. The method has the advantages of mild reaction path conditions, high yield and high corresponding selectivity, and can synthesize corresponding chiral phosphoramidite ligands by using various chiral diphenols as frameworks.
Description
Technical Field
The invention relates to a method for synthesizing a chiral phosphoramidite ligand based on R-2-phenylethylamine, belonging to the technical field of organic synthetic chemistry.
Background
The core problem of metal-catalyzed asymmetric reactions is how to design and synthesize catalysts with high enantioselectivity and catalytic activity. Chiral ligands are the source of asymmetric induction and control of chiral catalysts, and among them, the chiral phosphorus ligands were the earliest, most widely studied, and successfully used in industrial production. In recent years, the skeleton structure of phosphorus ligands has been more diversified, and the appearance of phosphorus ligands containing heteroatoms such as N, O, S has attracted much attention.
Since 2000, excellent chiral monophosphorus ligands were synthesized, which have achieved good results in many reactions such as asymmetric hydrogenation, and some of them even surpass the diphosphorus ligands which are superior in the conventional concept. For this reason, chiral monophosphorous ligands have attracted renewed attention, and among them, monodentate phosphoramidite ligands are most representative, such as binaphthol skeleton-type ligands and spirocyclic diol skeleton-type ligands. The ligand is very stable in air due to the P-O bond and the P-N bond, and has good catalytic performance.
The study of the synthesis method of chiral phosphoramidite ligand using R-2-phenylethylamine as an amine source is very necessary because it can form an Ir cyclic compound with higher activity with Ir catalyst (Christoph A. Kiener, Chuthian Shu, Christoph Incarvito, and John F. Hartwig. journal of the American Chemical Society,2003,125, (47), 14272-. In 2016, the Benjamin List subject group obtained amines of intermediate dr and ee values by asymmetric reductive condensation (V.N.Wakchare, B.List, Angew.chem.int.Ed.,2016,55, 15775.).
Disclosure of Invention
The invention discloses a method for synthesizing a phosphoramidite ligand based on R-2-phenylethylamine. According to the method, an imine intermediate is efficiently synthesized by utilizing the synergistic effect of anhydrous magnesium sulfate and a 4A molecular sieve, Pd/C is used as a reduction catalyst, amine with a high dr value is obtained through reduction, and finally, a chiral diphenol skeleton and the amine are connected through phosphorus trichloride under the condition of triethylamine to synthesize a commonly used chiral phosphoramidite ligand.
The technical scheme for realizing the purpose of the invention is as follows:
the method for synthesizing the chiral phosphoramidite ligand based on R-2-phenylethylamine comprises the following synthetic route:
(1) the acetophenone and R-2-phenyl phenethylamine are reacted under the promotion of anhydrous magnesium sulfate and a 4A molecular sieve to obtain an imine intermediate 1, and the reaction formula is as follows:
(2) the imine intermediate 1 is reduced by Pd/C catalyst to obtain corresponding amine, and then concentrated hydrochloric acid is used to react with the corresponding amine to generate amine hydrochloride 2, the reaction formula is as follows:
(3) the hydrochloride 2 of amine is combined with a chiral diphenol skeleton under the action of phosphorus trichloride and triethylamine to obtain a commonly used chiral phosphoramidite ligand, and the reaction general formula is as follows:
wherein the content of the first and second substances,
the method for synthesizing the chiral phosphoramidite ligand based on the R-2-phenylethylamine comprises the following specific steps:
step 2, adding a Pd/C catalyst into a methanol solution of a crude product imine intermediate 1 in a hydrogen atmosphere, reacting at room temperature for 2-3 days, filtering with diatomite, collecting filtrate, spin-drying, adding concentrated hydrochloric acid, stirring for reaction, spin-drying a solvent, and recrystallizing the obtained solid with acetone to obtain amine hydrochloride 2;
And 3, under the argon protection atmosphere, sequentially dropwise adding triethylamine and phosphorus trichloride into a dichloromethane solution of amine hydrochloride 2 in an ice bath, stirring for 3-4 hours at room temperature, then dropwise adding a dichloromethane solution of chiral diphenols, reacting overnight at room temperature, washing the system with a saturated sodium chloride solution after the reaction is finished, extracting dichloromethane, drying with anhydrous magnesium sulfate, spin-drying the solvent to obtain a crude product, and finally purifying by column chromatography to obtain the chiral phosphoramidite ligand.
Preferably, in step 1, the concentration of R-2-phenylphenethylamine in toluene is 0.5M.
Preferably, in the step 1, the molar ratio of the R-2-phenyl phenethylamine to the acetophenone to the anhydrous magnesium sulfate is 1:1.5: 1.
Preferably, in step 1, the ratio of the 4A molecular sieve to the R-2-phenylethylamine is 0.1: 1, g: mmol of the active component.
Preferably, in step 2, the concentration of the imine intermediate 1 in methanol is 0.5M.
Preferably, in step 2, the molar amount of Pd/C is 10% of that of the imine intermediate 1.
Preferably, in step 3, the concentration of the hydrochloride 2 of the amine in dichloromethane is 0.5M, and the concentration of the chiral diphenol in dichloromethane is 0.5M.
Preferably, in step 3, the molar ratio of the amine hydrochloride 2 to the triethylamine to the phosphorus trichloride to the chiral diphenol is 1:3.0:1.1: 2.0.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, anhydrous magnesium sulfate and the 4A molecular sieve are skillfully utilized to absorb water in a reaction system, so that the reversible reaction in the step 1 is carried out positively, and an imine intermediate is synthesized quickly and efficiently;
(2) the magnesium sulfate containing the crystal water and the 4A molecular sieve generated in the step 1 can be removed by filtration, the separation operation is simple and convenient, and the separated crude product can be directly used in the step 2, so that the loss is reduced;
(3) the reaction path has mild condition and high yield and corresponding selectivity, and can synthesize corresponding chiral phosphoramidite ligands by using various chiral diphenols as frameworks.
Drawings
FIG. 1 shows the nuclear magnetic H spectrum of the chiral phosphoramidite ligand prepared in the example.
FIG. 2 shows the nuclear magnetic spectrum C of the chiral phosphoramidite ligand prepared in the example.
FIG. 3 shows the nuclear magnetic P spectrum of the chiral phosphoramidite ligand prepared in the example.
FIG. 4 is a racemic liquid chromatogram of the chiral phosphoramidite ligand prepared in the example.
FIG. 5 is a chiral liquid chromatogram of the chiral phosphoramidite ligand prepared in the example.
Detailed Description
The invention is described in more detail below with reference to examples and figures.
Examples
The chiral phosphoramidite ligand synthesized by taking R-binaphthol as a chiral skeleton and corresponding amine as an amine source has the following structure:
And 2, adding a Pd/C (0.1eq) catalyst into a methanol solution of the crude product imine intermediate 1(1.0eq) in a hydrogen atmosphere, reacting at room temperature for 2-3 days, filtering with diatomite, collecting filtrate, spin-drying, adding concentrated hydrochloric acid, stirring for 30 minutes, spin-drying the solvent to obtain an off-white solid, and recrystallizing with acetone to obtain the amine hydrochloride 2.
And 3, under the protection of argon, sequentially dropwise adding triethylamine (3.0eq) and phosphorus trichloride (1.1eq) into a dichloromethane solution of amine hydrochloride 2(1.0eq) in an ice bath, stirring at room temperature for 3-4 hours, then dropwise adding a dichloromethane solution of R-binaphthol (2.0eq) into the solution, reacting at room temperature overnight, washing the system with a saturated sodium chloride solution after the reaction is finished, extracting with dichloromethane, drying with anhydrous magnesium sulfate, spin-drying the solvent to obtain a crude product, and finally performing column chromatography purification to obtain a chiral phosphoramidite ligand, wherein the total yield of the three steps is 62%, and the ee value is more than 99%.
1H NMR(500MHz,Chloroform-d)δ8.07(d,J＝8.7Hz,1H),7.99(d,J＝8.2Hz,1H),7.88(d,J＝8.1Hz,1H),7.80(d,J＝8.9Hz,1H),7.64(d,J＝8.7Hz,1H),7.45(dt,J＝24.6,7.9Hz,4H),7.36–7.16(m,13H),4.49(dq,J＝14.0,7.3Hz,2H),1.76(d,J＝7.1Hz,6H).13C NMR(126MHz,Chloroform-d)δ150.61,150.53,149.82,143.15,132.95,132.83,131.43,130.48,130.41,129.63,128.35,128.16,128.07,128.05,127.82,127.29,127.23,126.73,126.09,125.90,124.83,124.39,124.28,124.24–124.13(m),122.59,122.46,121.23,121.22,54.63,54.54,23.15,23.05.31P NMR(202MHz,Chloroform-d)δ150.52.
Comparative example
The comparative example is basically the same as the example, the only difference is that only anhydrous magnesium sulfate is added in the step 1, and the specific steps are as follows:
And 2, adding a Pd/C (0.1eq) catalyst into a methanol solution of the crude product imine intermediate 1(1.0eq) in a hydrogen atmosphere, reacting at room temperature for 2-3 days, filtering with diatomite, collecting filtrate, spin-drying, adding concentrated hydrochloric acid, stirring for 30 minutes, spin-drying the solvent to obtain an off-white solid, and recrystallizing with acetone to obtain the amine hydrochloride 2.
And 3, under the protection of argon, sequentially dropwise adding triethylamine (3.0eq) and phosphorus trichloride (1.1eq) into a dichloromethane solution of amine hydrochloride 2(1.0eq) in an ice bath, stirring at room temperature for 3-4 hours, then dropwise adding a dichloromethane solution of R-binaphthol (2.0eq) into the solution, reacting at room temperature overnight, washing the system with a saturated sodium chloride solution after the reaction is finished, extracting with dichloromethane, drying with anhydrous magnesium sulfate, spin-drying the solvent to obtain a crude product, and finally performing column chromatography purification to obtain the chiral phosphoramidite ligand, wherein the total yield of the three steps is 43% and the ee value is more than 99%.
Comparing the comparative example and the example, the ee value of the target chiral phosphoramidite ligand is unchanged under the synergistic effect of the anhydrous magnesium sulfate and the 4A molecular sieve, but the yield is improved.
Claims (8)
1. The method for synthesizing the chiral phosphoramidite ligand based on R-2-phenylethylamine is characterized in that the synthetic route is as follows:
(1) the acetophenone and R-2-phenyl phenethylamine are reacted under the promotion of anhydrous magnesium sulfate and a 4A molecular sieve to obtain an imine intermediate 1, and the reaction formula is as follows:
(2) the imine intermediate 1 is reduced by Pd/C catalyst to obtain corresponding amine, and then concentrated hydrochloric acid is used to react with the corresponding amine to generate amine hydrochloride 2, the reaction formula is as follows:
(3) the hydrochloride 2 of amine is combined with a chiral diphenol skeleton under the action of phosphorus trichloride and triethylamine to obtain a chiral phosphoramidite ligand, wherein the reaction general formula is as follows:
wherein the content of the first and second substances,
the method comprises the following specific steps:
step 1, adding R-2-phenyl phenethylamine into a toluene solution of acetophenone at room temperature under the protection of argon, then adding anhydrous magnesium sulfate and a 4A molecular sieve, reacting for 2-3 days at 50 +/-2 ℃, filtering with kieselguhr to remove the magnesium sulfate and the 4A molecular sieve after TLC monitoring reaction is finished, taking filtrate, and spin-drying to obtain a crude product, namely an imine intermediate 1;
Step 2, adding a Pd/C catalyst into a methanol solution of a crude product imine intermediate 1 in a hydrogen atmosphere, reacting at room temperature for 2-3 days, filtering with diatomite, collecting filtrate, spin-drying, adding concentrated hydrochloric acid, stirring for reaction, spin-drying a solvent, and recrystallizing the obtained solid with acetone to obtain amine hydrochloride 2;
and 3, under the argon protection atmosphere, sequentially dropwise adding triethylamine and phosphorus trichloride into a dichloromethane solution of amine hydrochloride 2 in an ice bath, stirring for 3-4 hours at room temperature, then dropwise adding a dichloromethane solution of chiral diphenols, reacting overnight at room temperature, washing the system with a saturated sodium chloride solution after the reaction is finished, extracting dichloromethane, drying with anhydrous magnesium sulfate, spin-drying the solvent to obtain a crude product, and finally purifying by column chromatography to obtain the chiral phosphoramidite ligand.
2. The method of claim 1, wherein in step 1, the concentration of R-2-phenylphenethylamine in toluene is 0.5M.
3. The method as claimed in claim 1, wherein in step 1, the molar ratio of the R-2-phenylphenethylamine, the acetophenone and the anhydrous magnesium sulfate is 1:1.5: 1.
4. The method of claim 1, wherein in step 1, the ratio of 4A molecular sieve to R-2-phenylethylamine is 0.1: 1, g: mmol of the active component.
5. The method of claim 1, wherein in step 2, the concentration of imine intermediate 1 in methanol is 0.5M.
6. The method of claim 1, wherein in step 2, the molar amount of Pd/C is 10% of that of imine intermediate 1.
7. The method of claim 1, wherein in step 3, the concentration of the hydrochloride 2 of the amine in dichloromethane is 0.5M, and the concentration of the chiral diphenol in dichloromethane is 0.5M.
8. The method as claimed in claim 1, wherein in step 3, the mole ratio of the amine hydrochloride 2, the triethylamine, the phosphorus trichloride and the chiral diphenols is 1:3.0:1.1: 2.0.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610355A (en) * | 2015-01-27 | 2015-05-13 | 华东师范大学 | Indole framework based center chirality sulfonamides monophosphine ligand and preparation method |
| CN108659046A (en) * | 2018-05-11 | 2018-10-16 | 浙江大学 | Monophosphorus ligand and its intermediate and preparation method based on tetramethyl spiro indan skeleton and purposes |
| CN109336887A (en) * | 2018-09-07 | 2019-02-15 | 中山大学 | A kind of benzimidazole and chiral heterocycle class compound and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610355A (en) * | 2015-01-27 | 2015-05-13 | 华东师范大学 | Indole framework based center chirality sulfonamides monophosphine ligand and preparation method |
| CN108659046A (en) * | 2018-05-11 | 2018-10-16 | 浙江大学 | Monophosphorus ligand and its intermediate and preparation method based on tetramethyl spiro indan skeleton and purposes |
| CN109336887A (en) * | 2018-09-07 | 2019-02-15 | 中山大学 | A kind of benzimidazole and chiral heterocycle class compound and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| HAI ZHOU等: "Highly Enantioselective Copper-Catalyzed Conjugate Addition of Diethylzinc to Enones Using Chiral Spiro Phosphoramidites as Ligands", 《J. ORG. CHEM.》 * |
| JAMES A. MARSHALL等: "Enantioselective Synthesis of Macrocyclic Propargylic Alcohols by [2,3] Wittig Ring Contraction. Synthesis of (+)-Aristolactone and Cembranoid Precursors", 《J. AM. CHEM. SOC.》 * |
| STEFANIA GUIZZETTI等: "Highly Stereoselective Metal-Free Catalytic Reduction of Imines: An Easy Entry to Enantiomerically Pure Amines and Naturaland Unnatural r-Amino Esters", 《ORG. LETT.》 * |
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