CN109400646A - 一种新型Buchwald-type单膦配体及其制备方法 - Google Patents
一种新型Buchwald-type单膦配体及其制备方法 Download PDFInfo
- Publication number
- CN109400646A CN109400646A CN201811652453.7A CN201811652453A CN109400646A CN 109400646 A CN109400646 A CN 109400646A CN 201811652453 A CN201811652453 A CN 201811652453A CN 109400646 A CN109400646 A CN 109400646A
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- Prior art keywords
- alkyl
- hydrogen
- halogen radical
- trifluoromethyl
- alkoxy
- 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
- 239000003446 ligand Substances 0.000 title claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 25
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 19
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 125000004185 ester group Chemical group 0.000 claims abstract description 16
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 7
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims abstract description 7
- 125000005493 quinolyl group Chemical group 0.000 claims abstract description 7
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 7
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- -1 N-Boc-L- Terleu Chemical compound 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 229940000635 beta-alanine Drugs 0.000 claims description 4
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-aminopropionic acid Natural products NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 4
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001350 alkyl halides Chemical class 0.000 claims description 3
- 238000006254 arylation reaction Methods 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- ZYJPUMXJBDHSIF-NSHDSACASA-N (2s)-2-[(2-methylpropan-2-yl)oxycarbonylamino]-3-phenylpropanoic acid Chemical compound CC(C)(C)OC(=O)N[C@H](C(O)=O)CC1=CC=CC=C1 ZYJPUMXJBDHSIF-NSHDSACASA-N 0.000 claims description 2
- QVHJQCGUWFKTSE-YFKPBYRVSA-N (2s)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound OC(=O)[C@H](C)NC(=O)OC(C)(C)C QVHJQCGUWFKTSE-YFKPBYRVSA-N 0.000 claims description 2
- QJCNLJWUIOIMMF-YUMQZZPRSA-N (2s,3s)-3-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]pentanoic acid Chemical compound CC[C@H](C)[C@@H](C(O)=O)NC(=O)OC(C)(C)C QJCNLJWUIOIMMF-YUMQZZPRSA-N 0.000 claims description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 2
- DCYGAPKNVCQNOE-UHFFFAOYSA-N 2,2,2-triphenylacetic acid Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)O)C1=CC=CC=C1 DCYGAPKNVCQNOE-UHFFFAOYSA-N 0.000 claims description 2
- FFFIRKXTFQCCKJ-UHFFFAOYSA-N 2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1 FFFIRKXTFQCCKJ-UHFFFAOYSA-N 0.000 claims description 2
- AOTQGWFNFTVXNQ-UHFFFAOYSA-N 2-(1-adamantyl)acetic acid Chemical compound C1C(C2)CC3CC2CC1(CC(=O)O)C3 AOTQGWFNFTVXNQ-UHFFFAOYSA-N 0.000 claims description 2
- VRPJIFMKZZEXLR-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxycarbonylamino]acetic acid Chemical compound CC(C)(C)OC(=O)NCC(O)=O VRPJIFMKZZEXLR-UHFFFAOYSA-N 0.000 claims description 2
- MFNXWZGIFWJHMI-UHFFFAOYSA-N 2-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C)(C)C(O)=O MFNXWZGIFWJHMI-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 2
- XRKIHUXCUIFHAS-UHFFFAOYSA-N [4-(3-methoxy-3-oxopropyl)phenyl]boronic acid Chemical compound COC(=O)CCC1=CC=C(B(O)O)C=C1 XRKIHUXCUIFHAS-UHFFFAOYSA-N 0.000 claims description 2
- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 2
- 239000004474 valine Substances 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 3
- SZXBQTSZISFIAO-ZETCQYMHSA-N (2s)-3-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]butanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC(=O)OC(C)(C)C SZXBQTSZISFIAO-ZETCQYMHSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- DVQWNQBEUKXONL-UHFFFAOYSA-N 1-iodo-2-methoxybenzene Chemical compound COC1=CC=CC=C1I DVQWNQBEUKXONL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000007832 transition metal-catalyzed coupling reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000006206 glycosylation reaction Methods 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
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
- C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/60—Quinoline or hydrogenated quinoline ring systems
-
- 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
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
- C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了结构通式（III）所示的化合物，其中R1选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基；R2选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基、苯氧基、C2～C6的酯基；选自苯基、萘基、噻吩基、喹啉基、吲哚基，R3选自氢、C1～C6的烷基、C1～C6的烷氧基、氰基、卤素基、三氟甲磺酰基、C2～C6的酯基、二甲氨基。与现有技术相比，本发明合成过程中不需要通过复杂的反应流程来构建C‑C键，使这种新型Buchwald‑type单膦配体的制备方法更为简单，反应过程中产生的三废少，环境污染少，适合工业化生产。
Description
技术领域
本发明涉及一种新型Buchwald-type单膦配体及其制备方法。
背景技术
单膦配体广泛应用于过渡金属催化偶联反应当中，对于提高反应产率、区域选择性和对映选择性有着极为关键的促进作用。随着过渡金属催化偶联反应的快速发展，新型Buchwald-type单膦配体的研发越来越受到人们的关注。
新型Buchwald-type单膦配体的合成在一些文献中已有报道，主要涉及钯、镍、铑、铱等金属催化引入最核心的芳基取代基，但其合成方法具有较大的局限性：催化成本高、反应需要高温环境、不能够大量制备等弊端。
文献(Tetrahedron 2001, 57, 2589)中以镍盐催化Kumada偶联的方法合成了系列芳基修饰的单膦配体。该合成路线中使用的芳基格式试剂具有易变质不易存储等问题，且该方法底物适用范围有限。文献(Beilstein J. Org. Chem.2011, 7, 1278)中以强碱正丁基锂与原料先发生一步锂卤交换，然后经过亲核取代合成系列烷基修饰的单膦配体。该方法操作工艺复杂，正丁基锂危险性高，不适合工业化生产。文献(Angew. Chem. Int. Ed.2017, 56, 7233.)以一价铑为催化剂，通过单膦配体化合物和溴代芳烃的交叉偶联直接得到芳基修饰的单膦配体，该路线虽然实现了单膦配体的直接修饰，但是体系存在反应温度较高，且不能够大量制备等问题。
现有技术中的单膦配体的制备方法具有对反应条件要求高、安全风险大、操作复杂、步骤繁琐、成本高、三废多、不适合工业化生产、总收率不高等缺点。
发明内容
有鉴于此，本发明的目的是提供一种新型Buchwald-type单膦配体及其制备方法，以克服现有的单膦配体的制备过程复杂、生产成本高，操作工艺复杂，收率低的问题，并开发出多种新型单膦配体。
本发明实现过程如下：
结构通式（III）所示的化合物，
其中， R1选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基；
R2选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基、苯氧基、C2～C6的酯基；
选自苯基、萘基、噻吩基、喹啉基、吲哚基，R3选自氢、C1～C6的烷基、C1～C6的烷氧基、氰基、卤素基、三氟甲磺酰基、C2～C6的酯基、二甲氨基。
一种优选的方式，当R1选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基；
R2选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基、C2～C6的酯基；
选自苯基，R3选自氢、C1～C6的烷基、C1～C6的烷氧基、氰基、卤素基、三氟甲磺酰基、C2～C6的酯基、二甲氨基。
另一种优选的方式，当R1选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基；
R2选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基、C2～C6的酯基；
选自萘基、噻吩基、喹啉基、吲哚基，R3选自氢。
结构通式（III）所示的化合物的制备方法：以结构式 I 和结构式 II 所示化合物为原料，在配体和碱存在下，在有机溶剂中加入钌催化剂实现结构式 I所示化合物邻位芳基化反应得到结构式 III 所示的芳基化修饰的Buchwald-type单膦配体，其反应路线如下式所示：
其中， R1选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基；
R2选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基、苯氧基、C2～C6的酯基；
选自苯基、萘基、噻吩基、喹啉基、吲哚基，R3选自氢、C1～C6的烷基、C1～C6的烷氧基、氰基、卤素基、三氟甲磺酰基、C2～C6的酯基、二甲氨基。
所述配体选自1-金刚烷甲酸、1-金刚烷乙酸、三苯基乙酸、三甲基乙酸、2, 4, 6-三甲基苯甲酸、丙二酸、2, 2,-二甲基丙二酸、4-三氟甲基苯甲酸、N-Boc-L-叔亮氨酸、N-Boc-L-异亮氨酸、N-Ac-L-异亮氨酸、N-Boc-L-苯丙氨酸、N-Ac-L-苯丙氨酸、N-Boc-L-缬氨酸、N-Ac-L-缬氨酸、N-Boc-L-甘氨酸、N-Ac-L-甘氨酸、N-Boc-L-丙氨酸、N-Ac-L-丙氨酸、N-Boc-2-甲基丙氨酸、N-Ac-β-丙氨酸，其用量为结构式 I 化合物摩尔当量的5%～30%。
所述碱选自碳酸钠、碳酸钾、碳酸铯、醋酸钠、醋酸钾、醋酸铯，其用量为结构式 I化合物摩尔当量的1～3倍。
所述钌催化剂选自三苯基膦、羰基、1,5-环辛二烯、五甲基环戊二烯、4-甲基异丙基苯基配位的钌金属盐中的任意一种，其用量为结构式 I 化合物摩尔当量的1%～10%。
所述有机溶剂选自芳烃、醇类、卤代烷、醚类的任意一种或者多种混合。所述芳烃选自苯、甲苯、二甲苯、三氟甲苯和氯苯中的任意一种；所述醇类选自甲醇、乙醇、丙醇、叔丁醇、叔戊醇；所述卤代烷包括二氯甲烷、三氯甲烷和1, 2-二氯乙烷中的任意一种；所述醚类包括四氢呋喃、甲基叔丁基醚、苯甲醚、乙二醇二甲醚和二氧六环中的任意一种。
上述结构式 II 化合物用量为结构式 I 化合物摩尔当量的1～3倍。
具体地说，上述制备方法是结构式 I 化合物在有机溶剂中加入钌催化剂，配体以及碱，在温度80～140℃的条件下与碘代芳烃或杂环碘代芳烃反应得到系列芳基化修饰的新型单膦配体。合成过程中不需要引入官能团即可使整个反应顺利进行，不需要控制很高的温度即可进行反应，因此对设备的要求很低，且合成步骤只需要一步即可完成，操作过程简单，反应过程中产生的三废少，所需要的结构式 I 化合物廉价易得，实现了新型单膦配体的合成工艺操作方便简单、原材料容易获得、降低了成本和对设备的要求、易于实现工业大规模生产的效果。
基于上述阐述，本发明技术方案与现有技术相比，其有益效果在于：(1)合成过程中不需要通过复杂的反应流程来构建C-C键，使这种新型Buchwald-type单膦配体的制备方法更为简单。(2)本申请反应过程中所需要的原材料容易获得，且合成过程中对设备的要求低，降低了生产成本。(3)本申请的在反应过程中产生的三废少，环境污染少，适合工业化生产。
具体实施方式
实施例1
(4''-methoxy-[1,1':2',1''-terphenyl]-2-yl)diphenylphosphane的制备
在反应釜中加入1.353g 2-二苯基膦-联苯，1.404g 2-碘苯甲醚，122.5mg 对伞花烃二氯化钌二聚体，78.7mg N-Ac-β-丙氨酸，1.536g 醋酸铯及2 mL甲苯，控制反应温度在120℃反应18小时后冷却至室温，硅藻土抽滤、减压蒸馏后柱层色谱分离得1.76g 产物，收率为95%。1H NMR (400 MHz, CDCl3) δ7.38-7.36 (m, 2H), 7.27 (d, J = 4.8 Hz, 3H),7.23-7.11 (m, 10H), 7.08 (td, J = 6.0 Hz, 0.8 Hz, 1H), 6.97-6.90 (m, 4H),6.74 (t, J = 5.6 Hz, 1H), 6.69 (d, J = 14.4 Hz, 1H), 3.58 (s, 3H). 13C NMR(100 MHz, CDCl3) δ 156.6, 148.5 (d, J = 32.6 Hz), 141.4 (d, J = 6.6 Hz),138.8 (d, J = 13.7 Hz), 137.8, 136.2 (d, J = 12.2 Hz), 134.1, 134.0, 133.9,133.3 (d, J = 18.3 Hz), 132.4 (d, J = 3.6 Hz), 131.1 (d, J = 3.6 Hz), 130.8(d, J = 5.9 Hz), 130.7, 130.6, 128.5, 128.4 (d, J = 2.6 Hz), 128.4, 128.2 (d,J = 5.6 Hz), 128.0, 128.0, 127.4, 127.1, 126.5, 119.9, 110.3, 55.2. 31P NMR(162 MHz, CDCl3) δ -14.3。
实施例2
2''-(diphenylphosphanyl)-N,N-dimethyl-[1,1':2',1''-terphenyl]-4-amine的制备
制备方法类似实施例1，分离得1.37g 产物，收率为75%。1H NMR (400 MHz, CDCl3) δ7.42-7.35 (m, 2H), 7.26-7.11 (m, 12H), 7.04 (d, J = 7.2 Hz, 3H), 7.00 (d, J =2.0 Hz, 1H), 6.83 (t, J = 4.6 Hz, 2H), 6.52 (d, J = 6.8 Hz, 2H), 2.90 (s,6H). 13C NMR (100 MHz, CDCl3) δ 149.0 (d, J = 32.7 Hz), 141.2 (d, J = 1.7 Hz),140.2 (d, J = 6.8 Hz), 138.8 (d, J = 13.6 Hz), 138.1 (d, J = 13.6 Hz), 136.5(d, J = 12.2 Hz), 134.8 (d, J = 2.2 Hz), 133.9, 133.7, 133.3 (d, J = 18.7Hz), 131.4 (d, J = 3.2 Hz), 131.2 (d, J = 6.1 Hz), 131.0 (d, J = 0.9 Hz),129.8, 128.6, 128.4, 128.3, 128.1, 128.1, 127.9, 127.8, 127.2, 125.7, 112.1,40.7. 31P NMR (162 MHz, CDCl3) δ -14.4。
实施例3
methyl 2-(diphenylphosphanyl)-2''-methoxy-[1,1':2',1''-terphenyl]-4'-carboxylate的制备
制备方法类似实施例1，分离得1.49g 产物，收率为74%。1H NMR (400 MHz, CDCl3) δ8.05 (s, 1H), 7.84 (d, J = 6.4 Hz, 1H), 7.29-7.27 (m, 3H), 7.24-7.11 (m,10H), 7.00 (d, J = 6.4 Hz, 1H), 6.97 (d, J = 5.6 Hz, 1H), 6.88 (t, J = 5.6Hz, 2H), 6.77 (t, J = 6.0 Hz, 1H), 6.70 (d, J = 6.4 Hz, 1H), 3.89 (s, 3H),3.57 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 167.2, 156.5, 147.5 (d, J = 32.4 Hz),146.2 (d, J = 6.3 Hz), 138.3, 138.2 (d, J = 1.1 Hz), 138.2, 137.6 (d, J =13.2 Hz), 134.0 (d, J = 20.3 Hz), 134.0, 133.2 (d, J = 18.2 Hz), 132.2 (d, J= 3.9 Hz), 132.0, 131.2 (d, J = 3.6 Hz), 130.4 (d, J = 6.0 Hz), 129.6, 129.2,128.8, 128.7, 128.5 (d, J = 7.0 Hz), 128.3 (d, J = 5.7 Hz), 128.1, 127.9,127.6, 127.5, 120.0, 110.3, 55.2, 52.1. 31P NMR (162 MHz, CDCl3) δ -14.3。
实施例4
(5-chloro-2''-methoxy-5'-methyl-[1,1':2',1''-terphenyl]-2-yl)diphenylphosphane的制备
在反应釜中加入1.161g 化合物 I，1.053g 2-碘苯甲醚，92.0mg 对伞花烃二氯化钌二聚体，59.1mg N-Ac-β-丙氨酸，1.152g 醋酸铯及2 mL甲苯，控制反应温度在120℃反应18小时后冷却至室温，硅藻土抽滤、减压蒸馏后柱层色谱分离得1.36g 产物，收率为88%。1H NMR(400 MHz, CDCl3) δ 7.29-7.25 (m, 4H), 7.23-7.13 (m, 9H), 7.04 (dd, J = 8.0Hz, 2.0 Hz, 1H), 6.89-6.77 (m, 4H), 6.70 (d, J = 8.4 Hz, 1H), 6.59 (s, 1H),3.61 (s, 3H), 2.14 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 156.5, 149.9 (d, J =33.2 Hz), 139.8 (d, J = 6.4 Hz), 138.1 (d, J = 13.4 Hz), 136.1, 135.4 (d, J =13.6 Hz), 134.8 (d, J = 4.9 Hz), 134.2 (d, J = 20.7 Hz), 133.9, 133.1 (d, J =28.2 Hz), 132.2 (d, J = 4.0 Hz), 131.5 (d, J = 3.2 Hz), 130.6 (d, J = 5.7Hz), 130.4, 130.2, 128.8, 128.6, 128.6, 128.5, 128.4, 128.3, 128.3, 128.0,127.2, 120.0, 110.2, 55.1, 21.1. 31P NMR (162 MHz, CDCl3) δ -14.9。
实施例5
发明人通过改变反应原料，可以获得一系列Buchwald-type单膦配体衍生物，具体列表如下：
从以上实施例以及测定的数据可以看出，采用本申请的方式制备新型单膦配体方法操作方便简单，所需要的原材料容易获得，降低了生产成本，且在合成过程中对设备的要求低，适合工业化生产。
以上仅是本发明的优选实施方式，应当指出的是，上述优选实施方式不应视为对本发明的限制，本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说，在不脱离本发明的精神和范围内，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.结构通式（III）所示的化合物，
其中， R1选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基；
R2选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基、苯氧基、C2～C6的酯基；
选自苯基、萘基、噻吩基、喹啉基、吲哚基，R3选自氢、C1～C6的烷基、C1～C6的烷氧基、氰基、卤素基、三氟甲磺酰基、C2～C6的酯基、二甲氨基。
2.根据权利要求1所述的化合物，其特征在于：R1选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基；R2选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基、C2～C6的酯基；
选自苯基，R3选自氢、C1～C6的烷基、C1～C6的烷氧基、氰基、卤素基、三氟甲磺酰基、C2～C6的酯基、二甲氨基。
3.根据权利要求1所述的化合物，其特征在于：R1选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基；R2选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基、C2～C6的酯基；
选自萘基、噻吩基、喹啉基、吲哚基，R3选自氢。
4.权利要求1所述化合物的制备方法，其特征在于：以结构式 I 和结构式 II 所示化合物为原料，在配体和碱存在下，在有机溶剂中加入钌催化剂实现结构式 I所示化合物邻位芳基化反应得到结构式 III 所示的芳基化修饰的Buchwald-type单膦配体，其反应路线如下式所示：
其中， R1选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基；
R2选自氢、C1～C6的烷基、C1～C6的烷氧基、三氟甲基、卤素基、苯氧基、C2～C6的酯基；
选自苯基、萘基、噻吩基、喹啉基、吲哚基，R3选自氢、C1～C6的烷基、C1～C6的烷氧基、氰基、卤素基、三氟甲磺酰基、C2～C6的酯基、二甲氨基。
5.根据权利要求4所述化合物的制备方法，其特征在于：所述配体选自1-金刚烷甲酸、1-金刚烷乙酸、三苯基乙酸、三甲基乙酸、2, 4, 6-三甲基苯甲酸、丙二酸、2, 2,-二甲基丙二酸、4-三氟甲基苯甲酸、N-Boc-L-叔亮氨酸、N-Boc-L-异亮氨酸、N-Ac-L-异亮氨酸、N-Boc-L-苯丙氨酸、N-Ac-L-苯丙氨酸、N-Boc-L-缬氨酸、N-Ac-L-缬氨酸、N-Boc-L-甘氨酸、N-Ac-L-甘氨酸、N-Boc-L-丙氨酸、N-Ac-L-丙氨酸、N-Boc-2-甲基丙氨酸、N-Ac-β-丙氨酸，其用量为结构式 I 化合物摩尔当量的5%～30%。
6.根据权利要求4所述化合物的制备方法，其特征在于：所述碱选自碳酸钠、碳酸钾、碳酸铯、醋酸钠、醋酸钾、醋酸铯，其用量为结构式 I 化合物摩尔当量的1～3倍。
7.根据权利要求4所述化合物的制备方法，其特征在于：所述钌催化剂选自三苯基膦、羰基、1,5-环辛二烯、五甲基环戊二烯、4-甲基异丙基苯基配位的钌金属盐中的任意一种，其用量为结构式 I 化合物摩尔当量的1%～10%。
8.根据权利要求4所述化合物的制备方法，其特征在于：所述有机溶剂选自芳烃、醇类、卤代烷、醚类的任意一种或者多种混合。
9.根据权利要求8所述化合物的制备方法，其特征在于：所述芳烃选自苯、甲苯、二甲苯、三氟甲苯和氯苯中的任意一种；所述醇类选自甲醇、乙醇、丙醇、叔丁醇、叔戊醇；所述卤代烷包括二氯甲烷、三氯甲烷和1, 2-二氯乙烷中的任意一种；所述醚类包括四氢呋喃、甲基叔丁基醚、苯甲醚、乙二醇二甲醚和二氧六环中的任意一种。
10.根据权利要求4所述化合物的制备方法，其特征在于：结构式 II 化合物用量为结构式 I 化合物摩尔当量的1～3倍。
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| CN112250709A (zh) * | 2020-10-22 | 2021-01-22 | 湖北大学 | 一种邻位芳基取代的叔膦化合物的合成方法 |
| CN113666961A (zh) * | 2020-05-15 | 2021-11-19 | 湖北大学 | 一种间位取代联芳基型叔膦配体的制备方法 |
| CN114632552A (zh) * | 2022-05-19 | 2022-06-17 | 苏州欣诺科生物科技有限公司 | Buchwald预催化剂及其制备方法与应用 |
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| CN108383873A (zh) * | 2018-02-26 | 2018-08-10 | 华中师范大学 | 1-(8-芳基萘基)膦配体及其制备方法以及膦金配合物和应用 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113666961A (zh) * | 2020-05-15 | 2021-11-19 | 湖北大学 | 一种间位取代联芳基型叔膦配体的制备方法 |
| CN113666961B (zh) * | 2020-05-15 | 2023-05-16 | 湖北大学 | 一种间位取代联芳基型叔膦配体的制备方法 |
| CN112250709A (zh) * | 2020-10-22 | 2021-01-22 | 湖北大学 | 一种邻位芳基取代的叔膦化合物的合成方法 |
| CN114632552A (zh) * | 2022-05-19 | 2022-06-17 | 苏州欣诺科生物科技有限公司 | Buchwald预催化剂及其制备方法与应用 |
| CN114632552B (zh) * | 2022-05-19 | 2022-08-02 | 苏州欣诺科生物科技有限公司 | Buchwald预催化剂及其制备方法与应用 |
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