CN110698506A - Synthesis method of pyrazole-4-boronic acid pinacol ester - Google Patents
Synthesis method of pyrazole-4-boronic acid pinacol ester Download PDFInfo
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- CN110698506A CN110698506A CN201911187190.1A CN201911187190A CN110698506A CN 110698506 A CN110698506 A CN 110698506A CN 201911187190 A CN201911187190 A CN 201911187190A CN 110698506 A CN110698506 A CN 110698506A
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- pyrazole
- pinacol ester
- boronic acid
- acid pinacol
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- TVOJIBGZFYMWDT-UHFFFAOYSA-N 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1h-pyrazole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CNN=C1 TVOJIBGZFYMWDT-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- IPISOFJLWYBCAV-UHFFFAOYSA-N tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole-1-carboxylate Chemical compound C1=NN(C(=O)OC(C)(C)C)C=C1B1OC(C)(C)C(C)(C)O1 IPISOFJLWYBCAV-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical group [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- SNRCKKQHDUIRIY-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloromethane;dichloropalladium;iron(2+) Chemical compound [Fe+2].ClCCl.Cl[Pd]Cl.C1=C[CH-]C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.C1=C[CH-]C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 SNRCKKQHDUIRIY-UHFFFAOYSA-L 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- -1 alkali metal salt Chemical class 0.000 claims 1
- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 abstract 2
- 238000007086 side reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- KEZNMOUMHOZFRA-UHFFFAOYSA-N 1h-pyrazol-4-ylboronic acid Chemical compound OB(O)C=1C=NNC=1 KEZNMOUMHOZFRA-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- IQEFCRDQVLIADR-UHFFFAOYSA-N tert-butyl 4-bromopyrazole-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1C=C(Br)C=N1 IQEFCRDQVLIADR-UHFFFAOYSA-N 0.000 description 1
- WRCRIGRVTPLDDD-UHFFFAOYSA-N tert-butyl 4-iodopyrazole-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1C=C(I)C=N1 WRCRIGRVTPLDDD-UHFFFAOYSA-N 0.000 description 1
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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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthesis method of pyrazole-4-boronic acid pinacol ester, which reduces the side reaction in the reaction process by adding trimethylbenzene as a stable solvent during the reaction.
Description
Technical Field
The invention relates to the field of chemical industry, and in particular relates to a synthetic method of pyrazole-4-boronic acid pinacol ester.
Background
4-pyrazole boronic acid pinacol ester is an important anticancer drug intermediate, but the existing synthetic method is complex and high in cost, and both synthesis and purification are difficult. Therefore, a new synthesis method is needed to solve the above problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and the invention is a method which is simple and cheap to operate, is easy to purify and amplify industrial production, and makes up the technical problems of difficult synthesis and purification of the 4-pyrazole boronic acid pinacol ester and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a synthesis method of pyrazole-4-boronic acid pinacol ester comprises the following steps:
reacting 1-Boc-4-halogenopyrazole and pinacol diboron in an alkali metal weak acid salt solution at 25-110 ℃ under the action of a palladium catalyst to obtain 1-Boc-4-pyrazole pinacol borate;
heating the 1-Boc-4-pyrazole pinacol borate to a molten state until no gas is discharged, cooling to room temperature, adding petroleum ether, stirring, pulping, filtering, and drying to obtain a pure pyrazole-4-boronic acid pinacol ester.
In a further improvement, the halogen in the 1-Boc-4-halogenopyrazole is iodine or bromine.
In a further improvement, the weak alkali metal acid salt is one or any mixture of potassium carbonate, sodium bicarbonate, potassium acetate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate and potassium hydrogen phosphate.
In a further improvement, the palladium catalyst is [1,1 '-bis (diphenylphosphino) ferrocene ] dichloropalladium or [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium dichloromethane complex.
In a further improvement, the solvent of the alkali metal weak acid salt solution is one or any mixture of ethanol, isopropanol, dioxane, methanol, toluene and water.
In a further improvement, the concentration of the alkali metal weak acid salt solution is 0.5 mol/L.
In a further improvement, the molar ratio of the 1-Boc-4-halopyrazole to the pinacol ester diborate to the palladium catalyst to the weak acid salt of an alkali metal is 1: 0.01:1.
In a further improvement, in the second step, the 1-Boc-4-pyrazole boronic acid pinacol ester is heated to 140-180 ℃ and is in a molten state.
The principle of the invention is as follows:
wherein X represents a halogen atom of bromine or iodine, Pd (dppf) Cl2Represents the catalyst [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride or [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride dichloromethane complex, alkali for base and heat for additionAnd (4) heating.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of 1-Boc-4-pyrazole boronic acid pinacol ester of example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of pinacol ester 4-pyrazoleboronic acid of example 3.
Detailed Description
Examples 1,
Adding 200 ml of 1-Boc-4-bromopyrazole (24.7 g, 0.1mol), pinacol ester diborate (25.4 g, 0.1mol) and a catalyst [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (0.74 g, 0.001mol), potassium acetate (19.6 g, 0.2mol) into a reaction bottle, removing oxygen under reduced pressure, heating to reflux under nitrogen protection, reacting for 16 hours under heat preservation, monitoring the completion of the reaction of raw materials by using a point plate, filtering, evaporating ethanol from filtrate under reduced pressure, extracting residues by using petroleum ether, and purifying to obtain 24.2 g of 1-Boc-4-pyrazolboronic acid pinacol ester, wherein the yield is 82.3%.
FIG. 1 is a NMR spectrum of 1-Boc-4-pyrazoleboronic acid pinacol ester obtained in this example;
1H-NMR(400MHz,CDCl3)δ:1.33(12H,s)1.65(9H,s)，7.93(1H,s)，8.39(1H,s)。
examples 2,
Adding 1-Boc-4-iodopyrazole (29.4 g, 0.1mol), pinacol ester diborate (25.4 g, 0.1mol) and a catalyst [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (0.82 g, 0.001mol), sodium acetate (13.6 g, 0.1mol) and 200 ml of isopropanol into a reaction bottle, removing oxygen under reduced pressure, heating to reflux under nitrogen protection, carrying out heat preservation reaction for 16 hours, monitoring the completion of raw material reaction by using a point plate, filtering, evaporating ethanol from filtrate under reduced pressure, extracting residue with petroleum ether, and purifying to obtain 25.2 g of 1-Boc-4-pyrazoleboronic pinacol ester, wherein the yield is 85.7%.
Example 3
24.2 g of 1-Boc-4-pyrazole boronic acid pinacol ester obtained in example 1 is put into a reaction bottle, heated to melt, continuously stirred and heated to 180 ℃ until no obvious gas is released (BOC is removed), the heating is stopped, the solution is cooled to room temperature, petroleum ether is added, the solution is stirred for half an hour, and the product 4-pyrazole boronic acid pinacol ester is obtained by suction filtration, wherein the yield is 80.2%.
FIG. 2 is the NMR spectrum of the product, 4-pyrazole boronic acid pinacol ester, obtained in this example;
1H-NMR(400MHz,CDCl3)δ:7.91(2H,s)5.78(1H,brs)，1.33(12H,s)。
the above examples are merely preferred examples and are not intended to limit the embodiments of the present invention.
Claims (8)
1. A synthesis method of pyrazole-4-boronic acid pinacol ester is characterized by comprising the following steps:
reacting 1-Boc-4-halogenopyrazole and pinacol diboron in an alkali metal weak acid salt solution at 25-110 ℃ under the action of a palladium catalyst to obtain 1-Boc-4-pyrazole pinacol borate;
heating the 1-Boc-4-pyrazole pinacol borate to a molten state until no gas is discharged, cooling to room temperature, adding petroleum ether, stirring, pulping, filtering, and drying to obtain a pure pyrazole-4-boronic acid pinacol ester.
2. The method of synthesizing pyrazole-4-boronic acid pinacol ester of claim 1, wherein the halogen in the 1-Boc-4-halopyrazole is iodine or bromine.
3. The method for synthesizing pyrazole-4-boronic acid pinacol ester according to claim 1, wherein the weak alkali metal salt is one or any mixture of potassium carbonate, sodium bicarbonate, potassium acetate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate and potassium hydrogen phosphate.
4. The method for synthesizing pyrazole-4-boronic acid pinacol ester according to claim 1, wherein the palladium catalyst is [1,1 '-bis (diphenylphosphino) ferrocene ] dichloropalladium or [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium dichloromethane complex.
5. The method for synthesizing pyrazole-4-boronic acid pinacol ester according to claim 1, wherein the solvent of the alkali metal weak acid salt solution is one or any mixture of ethanol, isopropanol, dioxane, methanol, toluene and water.
6. The method for synthesizing pyrazole-4-boronic acid pinacol ester according to claim 1, wherein the concentration of the alkali metal weak acid salt solution is 0.5 mol/L.
7. The method of synthesizing pyrazole-4-boronic acid pinacol ester of claim 1, wherein the molar ratio of the 1-Boc-4-halopyrazole, the pinacol ester of diboronic acid, the palladium catalyst, and the weak acid salt of an alkali metal is 1: 0.005-0.1:1-10.
8. The method for synthesizing pyrazole-4-boronic acid pinacol ester according to claim 1, wherein in the second step, the 1-Boc-4-pyrazole-boronic acid pinacol ester is heated to 140-180 ℃ in a molten state.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329615A (en) * | 1998-11-06 | 2002-01-02 | 联邦科学和工业研究组织 | Hydroboronation process |
| WO2014193647A2 (en) * | 2013-05-26 | 2014-12-04 | Calitor Sciences, Llc | Alkenyl compounds and methods of use |
| CN106188116A (en) * | 2016-07-14 | 2016-12-07 | 沧州普瑞东方科技有限公司 | A kind of method of synthesizing pyrazole 4 boric acid pinacol ester |
| CN108997309A (en) * | 2018-07-17 | 2018-12-14 | 中国科学技术大学苏州研究院 | A kind of preparation method of pyrazoles -4- aryl derivatives |
-
2019
- 2019-11-27 CN CN201911187190.1A patent/CN110698506A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329615A (en) * | 1998-11-06 | 2002-01-02 | 联邦科学和工业研究组织 | Hydroboronation process |
| WO2014193647A2 (en) * | 2013-05-26 | 2014-12-04 | Calitor Sciences, Llc | Alkenyl compounds and methods of use |
| CN106188116A (en) * | 2016-07-14 | 2016-12-07 | 沧州普瑞东方科技有限公司 | A kind of method of synthesizing pyrazole 4 boric acid pinacol ester |
| CN108997309A (en) * | 2018-07-17 | 2018-12-14 | 中国科学技术大学苏州研究院 | A kind of preparation method of pyrazoles -4- aryl derivatives |
Non-Patent Citations (1)
| Title |
|---|
| 王佳: "沸水促进的N-Boc保护基脱除反应和联萘酚骨架的手性磷酸的合成及应用研究", 《中国优秀博硕士学位论文全文数据库》 * |
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