CN111393484A - Preparation of novel ferrocene skeleton-based chiral carbene complex - Google Patents
Preparation of novel ferrocene skeleton-based chiral carbene complex Download PDFInfo
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- CN111393484A CN111393484A CN202010390569.9A CN202010390569A CN111393484A CN 111393484 A CN111393484 A CN 111393484A CN 202010390569 A CN202010390569 A CN 202010390569A CN 111393484 A CN111393484 A CN 111393484A
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- ferrocene
- chiral
- carbene complex
- reaction
- skeleton
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 claims abstract description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 239000011630 iodine Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 238000006138 lithiation reaction Methods 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- WGZWXARAMMXBKD-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) N,N,5-trimethylcyclopenta-1,3-dien-1-amine Chemical compound [Fe++].c1cc[cH-]c1.CN(C)[c-]1cccc1C WGZWXARAMMXBKD-UHFFFAOYSA-N 0.000 claims 2
- JWFDXKOVBQLBBL-UHFFFAOYSA-N 1,1-dibromo-1,2-dichloroethane Chemical group ClCC(Cl)(Br)Br JWFDXKOVBQLBBL-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- -1 ferrocene compound Chemical class 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229920006324 polyoxymethylene Polymers 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 150000001879 copper Chemical class 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 7
- 239000012043 crude product Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- NRAPCRKPJHRWMI-UHFFFAOYSA-N tritylboron Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)([B])C1=CC=CC=C1 NRAPCRKPJHRWMI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
A novel preparation of a ferrocene skeleton-based chiral carbene complex belongs to the field of chemical medicine preparation. The development of coordination chemistry and metal organic chemistry is greatly promoted by azacarbene (N-heterocyclic carbene) and ferrocene due to their own electronic structure and spatial structure. Ferrocene itself has no planar chirality, but when two different substituents are attached to the same cyclopentadiene, ferrocene has planar chirality, so that ferrocene is an excellent framework into which planar chirality can be introduced. At present, the rigidity of the surface chiral carbene complex based on the ferrocene skeleton is not strong, so that the asymmetric catalytic reaction effect is poor. The invention uses phthalamide as raw material, firstly reacts with iodine/bromide of ferrocene with surface chirality in organic solvent in the presence of alkali and catalytic amount of copper salt, and then obtains target product through series reaction and the like. The target product can be used as a chiral ligand, a chiral auxiliary agent or a chiral catalyst for various asymmetric catalytic reactions.
Description
Technical Field
The invention discloses a novel preparation method of a ferrocene skeleton-based chiral carbene complex, belonging to the field of chemical medicine preparation.
Background
N-heterocyclic carbane (NHC) is a highly efficient organic/organometallic catalyst that has been increasingly used in organic chemistry and gradually replaced the role of the corresponding phosphorus ligand, mainly because: 1) the acting force of the M (metal) -C bond is stronger than that of the M-P bond, and the thermal stability is better; 2) the NHC ligand can regulate and control the electronic effect and the space structure of the whole ligand by changing the size of a substituent group connected to a nitrogen atom, so that the effect of regulating and controlling the structure-activity relationship can be achieved. Ferrocene greatly promotes the development of coordination chemistry and metal organic chemistry due to its own electronic structure and spatial structure. Ferrocene itself has no planar chirality, but when two different substituents are attached to the same cyclopentadiene, ferrocene has planar chirality, so that ferrocene is an excellent framework into which planar chirality can be introduced. At present, the rigidity of the surface chiral carbene complex based on the ferrocene skeleton is not strong, so that the asymmetric catalytic reaction effect is poor.
Disclosure of Invention
The invention uses phthalamide as a raw material, and the phthalamide reacts with iodine/bromide of ferrocene with surface chirality in an organic solvent in the presence of alkali, catalytic amount of copper salt and iodide, and then the surface chiral carbene complex based on the ferrocene skeleton can be obtained with high yield through lithiation reaction, reduction reaction and the like. The obtained target product can be used as a chiral ligand, a chiral auxiliary agent or a chiral catalyst for various asymmetric catalytic reactions.
The invention has the advantages that the starting material phthalamide and the derivatives thereof used in the invention can be prepared by conventional functional group transformation, and have structural diversity. In addition, the reaction yield is high, the operation is simple and convenient, and the method is favorable for mass preparation.
Technical scheme
The method adopted by the invention is that the phthalamide and the derivative thereof, the copper salt and the iodine/bromide of the ferrocene are dissolved in the furan/ether organic solvent according to the proportion of 1: 1.2 and react for 12 hours at the temperature of 80 ℃. Then, the target crude product is obtained through methylation reaction, decarbonylation reaction and the like. The crude product is purified by recrystallization.
Detailed Description
In order to fully disclose the preparation method of the ferrocene skeleton-based chiral carbene complex, the invention is further described with reference to the following examples. These examples are intended to be illustrative of the invention and are not intended to be limiting. The scope of the present invention is not limited by these examples. The scope of the invention is set forth in the claims.
Example 1:
preparation of compound 2:
the reaction is carried out at 80 ℃, instruments and equipment used do not need special anhydrous and oxygen-free treatment, 38 mg (0.2mmol) of phthalic diamide, 10 mg (0.25mmol) of sodium amide, 75mg (0.2mmol) of o-dimethylaminomethyl ferrocene iodide and 2m L tetrahydrofuran solvent are added into a reaction system, the reaction mixture is stirred for 24 hours at 80 ℃, the solvent is drained after the reaction is cooled to room temperature, and a crude product 2 is purified by column chromatography (petroleum ether: ethyl acetate is 20: 1) to obtain a target product 78mg, and the yield is 90%.
Preparation of compound 3:
compound 2(86mg, 0.2mmol) and 2ml of an ether solvent were added to the reaction system, t-butyllithium (0.15ml, 0.22mmol, 1.6M) was added at-78 deg.C, and methyl iodide (28mg, 0.2mmol) was further added after 1 hour of reaction to give a methyl-substituted compound. The compound was subjected to reduction reaction and then reacted with paraformaldehyde to give compound 3(56mg, 76%).
Preparation of compound 4:
the resulting compound 3 was reacted without purification with 3(75mg, 0.2mmol) directly with sodium iodide (45mg, 0.3mmol) or trityl boron tetrafluoride (99mg, 0.3mmol) in tetrahydrofuran at 60 ℃ for 12 h. After cooling to room temperature, the solvent was drained and washed with hexane (3 × 2ml) to give the precipitate, the imidazolium salt, in 91mg, 91% yield. And reacting the obtained imidazole salt with sodium hydride in a vacuum wire/glove box for 1-2h to obtain the required carbene 4.
Preparation of compound 5:
due to the poor stability of compound 4, carbenes are often prepared as metal complexes. Can be a): directly using carbene 4 and cuprous chloride (1: 1) in alkaline Cs2CO3Reacting at room temperature for 12h in the presence of the solvent, then draining the solvent, and purifying the crude product by column chromatography (EA: Acetate ═ 20: 1); b) the method comprises the following steps The imidazole salt and sodium hydride are put into a double-necked bottle according to the ratio of 1: 1.5, and 10 times of the imidazole salt and the sodium hydride are addedThe raw material metering amount of solvent THF is stirred for 1-2h at room temperature, equivalent cuprous chloride and 1.5 times equivalent cesium carbonate are added, after 12h of reaction, the solvent is drained, and the crude product is purified by column chromatography to obtain the target product carbene complex 5(0.2mmol equiv., 64mg, 68%).
Claims (5)
1. A novel face chiral carbene complex based on a ferrocene skeleton is characterized in that: the complex has the structural formula:
wherein R is1Is a substituent other than H, R2And R3Is H or an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 24 carbon atoms, and M is a copper group metal atom.
2. The novel ferrocene skeleton-based face chiral carbene complex according to claim 1, characterized in that: in the structural formula of the complex, R1Is dimethylaminomethyl, R2And R3Is a hydrogen atom and M is a copper atom.
3. The preparation method of the novel ferrocene skeleton-based chiral carbene complex, which is described in claim 1, comprises the following three steps:
the first step is as follows: reacting dimethylamino methyl ferrocene serving as a raw material with an iodine simple substance or bromide in an organic solvent to obtain ortho-position iodine/bromide of the dimethylamino methyl ferrocene; the second step is that: the obtained iodide and phthalamide are subjected to coupling reaction in the presence of alkali and CuI to obtain a corresponding chiral ferrocene compound; the third step: and then a final product, namely a novel ferrocene skeleton-based chiral carbene complex is obtained through polyformaldehyde, lithiation reaction, reduction reaction and the like.
4. The preparation method of the novel ferrocene skeleton-based chiral carbene complex, according to claim 3, is characterized in that: the bromide is dichlorodibromoethane; the organic solvent is diethyl ether or tetrahydrofuran; the alkali is amino sodium or sodium hydride, the reaction temperature is 70-80 ℃, the reaction time is 12h, and the dosage of the reaction organic solvent is 10-20 times of the total amount of the reaction raw materials.
5. The application of the novel ferrocene skeleton-based chiral carbene complex is characterized in that: the complex can be used for catalyzing asymmetric reactions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010390569.9A CN111393484A (en) | 2020-05-11 | 2020-05-11 | Preparation of novel ferrocene skeleton-based chiral carbene complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010390569.9A CN111393484A (en) | 2020-05-11 | 2020-05-11 | Preparation of novel ferrocene skeleton-based chiral carbene complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111393484A true CN111393484A (en) | 2020-07-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010390569.9A Pending CN111393484A (en) | 2020-05-11 | 2020-05-11 | Preparation of novel ferrocene skeleton-based chiral carbene complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111393484A (en) |
-
2020
- 2020-05-11 CN CN202010390569.9A patent/CN111393484A/en active Pending
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Application publication date: 20200710 |