CN116082268B - Chiral benzomorpholine compound and preparation method thereof - Google Patents
Chiral benzomorpholine compound and preparation method thereof Download PDFInfo
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- CN116082268B CN116082268B CN202310058087.7A CN202310058087A CN116082268B CN 116082268 B CN116082268 B CN 116082268B CN 202310058087 A CN202310058087 A CN 202310058087A CN 116082268 B CN116082268 B CN 116082268B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- -1 benzomorpholine compound Chemical class 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 150000002503 iridium Chemical class 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- YRLORWPBJZEGBX-UHFFFAOYSA-N 3,4-dihydro-2h-1,4-benzoxazine Chemical group C1=CC=C2NCCOC2=C1 YRLORWPBJZEGBX-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229940078552 o-xylene Drugs 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 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 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229930014626 natural product Natural products 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 230000000975 bioactive effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229960003376 levofloxacin Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/36—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings condensed with one six-membered ring
-
- 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
Abstract
The invention discloses a chiral benzomorpholines compound and a preparation method thereof, and chiral benzomorpholinesThe preparation method of the compound comprises the following steps: a compound, achiral iridium salt, chiral ligand, achiral ferric salt,
Description
Technical Field
The invention belongs to the technical field of synthesis of fine chemical products, and particularly relates to a chiral benzomorpholine compound and a preparation method thereof.
Background
The benzomorpholine skeleton with chiral unit is widely used in natural products and medicine molecular structures, such as levofloxacin and other medicine with wide application. However, the synthesis of chiral structural units still presents great challenges. The development of efficient, economical, green and environment-friendly asymmetric catalytic methods for preparing chiral benzomorpholines is still the focus of research in the fields of synthetic chemistry and pharmaceutical chemistry.
The corresponding chiral amine compound is usually prepared by oxidizing an alcohol compound into a corresponding carbonyl group, dehydrating and condensing to obtain corresponding imine, and then performing asymmetric reduction reaction. The method is long in reaction steps, and needs to use metered oxidant and reducer, so that a large amount of organic waste is generated in the whole process. And is not suitable for the requirements of green and environment-friendly chemical synthesis advocated at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a chiral benzomorpholine compound.
The invention also aims to provide a preparation method of the chiral benzomorpholine compound.
The aim of the invention is achieved by the following technical scheme.
A chiral benzomorpholine compound has a structural formula shown in 1:
wherein R is 1 Is hydrogen, alkyl, halogen or aryl, R 2 Is alkyl or aryl.
The preparation method of the chiral benzomorpholine compound comprises the following steps: a compound, achiral iridium salt, chiral ligand, achiral ferric salt,Mixing a molecular sieve and a solvent, refluxing in a nitrogen environment, and separating by column chromatography to obtain a chiral benzomorpholine compound, wherein the structural formula of the compound is shown as 2:
in the technical scheme, the achiral iridium salt is [ Ir (COD) OMe] 2 Or [ Ir (COD) Cl ]] 2 。
In the technical scheme, the chiral ligand is chiral triarylphosphine type biphosphine ligand.
In the above technical scheme, the chiral triarylphosphine type biphosphine ligand is BINAP type or biphenyl type biphosphine ligand.
In the above technical scheme, the achiral iron salt is Fe (OTf) 3 。
In the above technical scheme, the solvent is o-xylene.
In the technical scheme, the temperature of the reflux is 90-110 ℃, and the time of the reflux is 20-30 hours.
In the technical scheme, the ratio of the compound to the achiral iridium salt to the chiral ligand to the achiral ferric salt is 0.1:0.05:0.01:0.05.
in the above technical scheme, the parts by weight of the substances of the compound and theThe mass portion ratio of the molecular sieve is 0.1 (30-60), the substancesThe unit of the parts by weight is mmol, and the unit of the parts by weight is mg.
In the technical scheme, the ratio of the parts by weight of the compound to the parts by volume of the solvent is 0.1 (1-5), the parts by weight of the compound are in mmol, and the parts by volume are in mL.
In the technical scheme, the eluent used in the column chromatography is a mixture of petroleum ether and ethyl acetate.
In the technical scheme, the ratio of petroleum ether to ethyl acetate is (10-30) in parts by volume: 1.
the invention discloses a chiral benzomorpholine compound and a preparation method thereof, wherein achiral iridium salt and chiral ligand in the preparation method generate chiral iridium salt in situ. The compound reacts under the combined catalysis of chiral iridium salt and achiral ferric salt to obtain chiral benzomorpholine compound. The chiral benzomorpholine skeleton widely exists in natural products and drug molecules, and can be used as a preparation method of natural products and bioactive molecules with the chiral skeleton. The preparation method has the advantages of simple and efficient whole preparation process, easy operation, environmental protection, high repeatability, high yield and the like.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The chiral diphosphine ligand in the following examples has the following structural formula:
example 1
The preparation method of the chiral benzomorpholine compound comprises the following steps: 22.9 mg of the compound represented by 2a (0.1 mmol) and [ Ir (COD) OMe were weighed out] 2 (3.3 mg, 0.05 mmol), chiral bisphosphine ligand (10.3 mmol)Gram, 0.1 mmol), fe (OTf) 3 (0.05 mmol) andmolecular sieves (40 mg) in a 5mL single neck round bottom flask containing a magnetic stirrer, 2mL o-xylene was added, a reflux condenser was connected to the reaction flask, and the reaction was carried out at 100deg.C under nitrogen protection for 24 hours. After the reaction, the system is directly separated by silica gel column chromatography (eluting with petroleum ether/ethyl acetate volume ratio 15:1) to obtain (S) -1a.19 mg, 90% yield, 96% ee (ee refers to enantioselectivity excess) enantioselectivity. White solid. The nuclear magnetic data are: 1 H NMR(400MHz,CDCl 3 ):δ7.47-7.37(m,5H),6.98-6.96(m,1H),6.89-6.84(m,1H),6.78-6.74(m,1H),6.70(d,J＝7.6Hz,1H),5.12(dd,J＝8.4,2.4Hz,1H),3.60(bs,1H),3.52(dd,J＝12.0,2.8Hz,1H),3.39(dd,J＝12.0,8.8Hz,1H). 13 C NMR(75MHz,CDCl 3 ) 144.6,139.0,133.0,128.6,128.3,126.3,121.4,119.0,117.0,115.6,75.9,47.8 specific rotation value: />
Example 2
The preparation method of the chiral benzomorpholine compound comprises the following steps: 30.8 mg of the compound represented by 2b (0.1 mmol) and [ Ir (COD) OMe were weighed out] 2 (3.3 mg, 0.05 mmol), chiral bisphosphine ligand (10.3 mg, 0.1 mmol), fe (OTf) 3 (0.05 mmol) andmolecular sieves (40 mg) in a 5mL single neck round bottom flask containing a magnetic stirrer, 2mL o-xylene was added, a reflux condenser was connected to the reaction flask, and the reaction was carried out at 100deg.C under nitrogen protection for 24 hours. The system directly uses silicon after the reaction is finishedAnd (S) -1b is separated by gel column chromatography (eluting with petroleum ether/ethyl acetate in a volume ratio of 15:1). 19.1 mg, 66% yield, 88% ee (ee refers to enantioselectivity excess) enantioselectivity. Brown solid. The nuclear magnetic data are: 1 H NMR(500MHz,CDCl 3 ):7.43-7.35(m,5H),7.06(d,J＝2.5Hz,1H),6.91(dd,J＝8.5,2.5Hz,1H),6.53(d,J＝8.5Hz,1H),5.07(dd,J＝9.0,2.5Hz,1H),3.92(bs,1H),3.52(dd,J＝12.0,2.5Hz,1H),3.34(dd,J＝12.0,8.5Hz,1H). 13 C NMR(125MHz,CDCl 3 ) Delta 145.4,138.6,132.3,128.8,128.6,126.4,124.3,120.1,116.6,110.0,76.1,47.5 specific rotation value: />
Example 3
The preparation method of the chiral benzomorpholine compound comprises the following steps: 24.3 mg of the compound represented by 2c (0.1 mmol) and [ Ir (COD) OMe were weighed out] 2 (3.3 mg, 0.05 mmol), chiral bisphosphine ligand (10.3 mg, 0.1 mmol), fe (OTf) 3 (0.05 mmol) andmolecular sieves (40 mg) in a 5mL single neck round bottom flask containing a magnetic stirrer, 2mL o-xylene was added, a reflux condenser was connected to the reaction flask, and the reaction was carried out at 100deg.C under nitrogen protection for 24 hours. After the reaction, the system is directly separated by silica gel column chromatography (eluting with petroleum ether/ethyl acetate volume ratio 15:1) to obtain (S) -1c.17.1 mg, 75% yield, 96% ee (ee refers to enantioselectivity excess) enantioselectivity. White solid. The nuclear magnetic data are: 1 H NMR(500MHz,CDCl 3 ):δ7.43-7.33(m,5H),6.70(s,1H),6.66-6.64(m,1H),6.60(d,J＝8.0Hz,1H),4.48(dd,J＝8.5,3.0Hz,1H),4.28(dd,J＝10.5,3.0Hz,1H),4.00(dd,J＝10.5,8.5Hz,1H),2.27(s,3H). 13 C NMR(75MHz,CDCl 3 ) Delta 143.4,139.2,131.2,128.7,128.7,128.2,127.2,121.9,117.1,115.4,71.0,54.3,20.6 specific rotation value：/>
Example 4
The preparation method of the chiral benzomorpholine compound comprises the following steps: 30.8 mg of the compound represented by 2d (0.1 mmol) and [ Ir (COD) OMe were weighed out] 2 (3.3 mg, 0.05 mmol), chiral bisphosphine ligand (10.3 mg, 0.1 mmol), fe (OTf) 3 (0.05 mmol) andmolecular sieves (40 mg) in a 5mL single neck round bottom flask containing a magnetic stirrer, 2mL o-xylene was added, a reflux condenser was connected to the reaction flask, and the reaction was carried out at 100deg.C under nitrogen protection for 24 hours. After the reaction, the system is directly separated by silica gel column chromatography (eluting with petroleum ether/ethyl acetate volume ratio 15:1) to obtain (S) -1d.22.6 mg, 78% yield, 92% ee (ee refers to enantioselectivity excess) enantioselectivity. White solid. The nuclear magnetic data are: 1 H NMR(500MHz,CDCl 3 ):δ7.60-7.59(m,1H),7.50-7.47(m,1H),7.37-7.34(m,1H),7.29-7.25(m,1H),6.92(dd,J＝8.0,1.0Hz,1H),6.83(td,J＝7.5,1.5Hz,1H),6.75-6.71(m,1H),6.68(dd,J＝7.5,1.5Hz,1H),5.07(dd,J＝8.5,2.5Hz,1H),3.91(bs,1H),3.52(dd,J＝12.0,2.5Hz,1H),3.33(dd,J＝11.5,8.5Hz,1H). 13 C NMR(125MHz,CDCl 3 ) Delta 144.3,141.4,132.9,131.5,130.3,129.5,125.0,122.8,121.8,119.2,117.2,115.7,75.3,47.8 specific rotation value:
the foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (6)
1. A preparation method of chiral benzomorpholine compounds is provided, wherein the structural formula of the chiral benzomorpholine compounds is shown as 1:
wherein R is 1 Is hydrogen, alkyl, halogen or aryl, R 2 Is aryl;
the preparation method of the chiral benzomorpholine compound is characterized by comprising the following steps: a compound, achiral iridium salt, chiral ligand, achiral ferric salt,Mixing a molecular sieve and a solvent, refluxing in a nitrogen environment, and separating by column chromatography to obtain a chiral benzomorpholine compound, wherein the structural formula of the compound is shown as 2:
the achiral ferric salt is Fe (OTf) 3 The chiral ligand has the following structural formula:
the achiral iridium salt is [ Ir (COD) OMe] 2 The solvent is o-xylene.
2. The method according to claim 1, wherein the temperature of the reflux is 90 to 110 ℃, and the time of the reflux is 20 to 30 hours.
3. The preparation method according to claim 2, wherein the ratio of the compound, the achiral iridium salt, the chiral ligand and the achiral iron salt is 0.1 in parts by weight of substances: 0.05:0.01:0.05.
4. a production method according to claim 3, wherein the amount of the substance of the compound and theThe ratio of the mass parts of the molecular sieve is 0.1 (30-60), the unit of the mass parts of the substances is mmol, and the unit of the mass parts is mg.
5. The method according to claim 4, wherein the ratio of the parts by weight of the compound to the parts by volume of the solvent is 0.1 (1-5), the parts by weight of the compound are in mmol, and the parts by volume are in mL.
6. The preparation method according to claim 5, wherein the eluent used in the column chromatography is a mixture of petroleum ether and ethyl acetate, and the ratio of petroleum ether to ethyl acetate is (10-30) in parts by volume: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110464727A (en) * | 2019-09-06 | 2019-11-19 | 山东师范大学 | The application of 3,4- dihydro -2H- benzo-[1,4] oxazines class drug or its salt in preparation inhibition iron death drug |
| CN110551037A (en) * | 2018-05-31 | 2019-12-10 | 中国科学院大连化学物理研究所 | Method for catalyzing asymmetric hydrogenation of imine by iridium/chiral diphosphine system |
| CN110862324A (en) * | 2019-11-14 | 2020-03-06 | 西北农林科技大学 | Direct synthesis method of chiral secondary amine compound |
| WO2020127386A1 (en) * | 2018-12-19 | 2020-06-25 | Bp Oil International Limited | Methods for preparing intermediates |
| WO2020127390A1 (en) * | 2018-12-19 | 2020-06-25 | Bp Oil International Limited | Methods for preparing compounds |
| WO2020260417A1 (en) * | 2019-06-26 | 2020-12-30 | Bp Oil International Limited | Methods for preparing benzoxazines |
| WO2020260418A1 (en) * | 2019-06-26 | 2020-12-30 | Bp Oil International Limited | Methods for preparing benzoxazines |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110551037A (en) * | 2018-05-31 | 2019-12-10 | 中国科学院大连化学物理研究所 | Method for catalyzing asymmetric hydrogenation of imine by iridium/chiral diphosphine system |
| WO2020127386A1 (en) * | 2018-12-19 | 2020-06-25 | Bp Oil International Limited | Methods for preparing intermediates |
| WO2020127390A1 (en) * | 2018-12-19 | 2020-06-25 | Bp Oil International Limited | Methods for preparing compounds |
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| WO2020260418A1 (en) * | 2019-06-26 | 2020-12-30 | Bp Oil International Limited | Methods for preparing benzoxazines |
| CN110464727A (en) * | 2019-09-06 | 2019-11-19 | 山东师范大学 | The application of 3,4- dihydro -2H- benzo-[1,4] oxazines class drug or its salt in preparation inhibition iron death drug |
| CN110862324A (en) * | 2019-11-14 | 2020-03-06 | 西北农林科技大学 | Direct synthesis method of chiral secondary amine compound |
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