CN114163465A - 一种烯基硼酸酯化合物的合成方法 - Google Patents
一种烯基硼酸酯化合物的合成方法 Download PDFInfo
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- CN114163465A CN114163465A CN202111594319.8A CN202111594319A CN114163465A CN 114163465 A CN114163465 A CN 114163465A CN 202111594319 A CN202111594319 A CN 202111594319A CN 114163465 A CN114163465 A CN 114163465A
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- palladium
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- catalyst
- compound
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Links
- -1 alkenyl borate compound Chemical class 0.000 title claims abstract description 22
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 7
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 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
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 claims description 2
- SCWWDULYYDFWQV-UHFFFAOYSA-N (2-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1O SCWWDULYYDFWQV-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [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 2
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 claims description 2
- YNUJADNRNHJXDT-UHFFFAOYSA-N palladium;pentane-2,4-dione Chemical compound [Pd].CC(=O)CC(C)=O.CC(=O)CC(C)=O YNUJADNRNHJXDT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 35
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 150000001345 alkine derivatives Chemical class 0.000 description 9
- 238000004607 11B NMR spectroscopy Methods 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000003818 flash chromatography Methods 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
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- 239000002184 metal Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000012230 colorless oil Substances 0.000 description 5
- 238000006197 hydroboration reaction Methods 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- SMTJVGKZVGURTO-UHFFFAOYSA-N B(O)(O)OB(O)O.OCC(C)(CO)C Chemical compound B(O)(O)OB(O)O.OCC(C)(CO)C SMTJVGKZVGURTO-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003921 oil Substances 0.000 description 3
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 3
- 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 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- 238000006555 catalytic reaction Methods 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
- MXFYYFVVIIWKFE-UHFFFAOYSA-N dicyclohexyl-[2-[2,6-di(propan-2-yloxy)phenyl]phenyl]phosphane Chemical compound CC(C)OC1=CC=CC(OC(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 MXFYYFVVIIWKFE-UHFFFAOYSA-N 0.000 description 2
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- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RENYIDZOAFFNHC-UHFFFAOYSA-N 1-ethynyl-3-methylbenzene Chemical group CC1=CC=CC(C#C)=C1 RENYIDZOAFFNHC-UHFFFAOYSA-N 0.000 description 1
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical group FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 description 1
- GAZZTEJDUGESGQ-UHFFFAOYSA-N 1-ethynyl-4-nitrobenzene Chemical group [O-][N+](=O)C1=CC=C(C#C)C=C1 GAZZTEJDUGESGQ-UHFFFAOYSA-N 0.000 description 1
- BPBNKCIVWFCMJY-UHFFFAOYSA-N 1-ethynyl-4-phenylbenzene Chemical group C1=CC(C#C)=CC=C1C1=CC=CC=C1 BPBNKCIVWFCMJY-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical group NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 1
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- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
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- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 description 1
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- HHRKFGMMAHZWIM-UHFFFAOYSA-N ethenoxyboronic acid Chemical class OB(O)OC=C HHRKFGMMAHZWIM-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- JPGRSTBIEYGVNO-UHFFFAOYSA-N methyl 4-ethynylbenzoate Chemical group COC(=O)C1=CC=C(C#C)C=C1 JPGRSTBIEYGVNO-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- VUYVXCJTTQJVKJ-UHFFFAOYSA-L palladium(2+);tricyclohexylphosphane;dichloride Chemical compound Cl[Pd]Cl.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 VUYVXCJTTQJVKJ-UHFFFAOYSA-L 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
Abstract
本发明公开了一种烯基硼酸酯化合物的合成方法,是以苯乙炔类化合物为原料,在催化剂、硼试剂以及碱存在下,对苯乙炔烃进行选择性的C‑H键硼化反应,高选择性的得到反式烯烃硼酸酯化合物。本发明具有高效、反应条件温和、操作方便、反应时间比较短、副产物较少等优点,并且适合于大规模生产。
Description
技术领域
本发明涉及一种烯基硼酸酯化合物的合成方法,通过对苯乙炔类化合物进行选择性的 C-H键的硼化来合成反式烯烃硼酸酯化合物,属于有机合成领域。
背景技术
烯基硼酸酯是有机合成中高度通用的构建单元,因为它们在构建C-C键和C-杂原子键方面具有广泛的应用,常见于药物设计、合成生物活性分子和功能材料中。
炔烃的硼氢化是合成这些硼酸酯化合物的直接方法。但是,由铜催化炔烃与二硼酸频哪醇或其他过程反应,通常会产生β-乙烯基(频哪醇)硼。其他类型的乙烯基硼酸酯的制备方法,如β-乙烯基(新戊基乙醇酸根)硼的制备方法相对有限,一般需要多步转化。由于缺乏β乙烯基(新戊基乙醇酸根)硼的制备方法,很少对其进行研究。因此,本研究开发的通过低负载钯催化从炔烃直接制备烯基硼酸酯的方法具有重要意义。
参考文献:
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发明内容
本发明针对现有合成路线的缺点,提供了一种烯基硼酸酯化合物的合成方法,使用低负载的钯含量即可催化炔烃的硼氢化反应,且不需要高温环境,具有原料易得、工艺简单、条件温和、产率比较高、底物范围广、副产物比较少等优点。
本发明烯基硼酸酯化合物的合成方法,是以苯乙炔类化合物为原料,在催化剂、碱以及硼试剂的存在下进行反应,分离提纯后得到烯基硼酸酯化合物。
具体是将苯乙炔类化合物在75℃、氩气保护条件下溶于溶剂中,在催化剂、碱以及硼试剂的存在下进行反应,反应结束后分离提纯得到目标产物。
所述苯乙炔类化合物的结构式为:
其中:R为Cl、Ph、F、噻吩基团或萘基团。
本发明合成方法的反应温度为60-150℃,优选为75℃,反应时间为2-10h。
所述催化剂为氯钯酸钠、双(二亚苄基丙酮)钯、四(三苯基膦)钯、(1,3-双二苯基磷丙烷)钯、二(乙酰丙酮)钯、氯化钯、三氟乙酸钯、双三苯基膦二氯化钯、醋酸钯、二氯二(三环己基磷)钯、[1,1’-双(二苯基磷基)二茂铁]二氯化钯中的至少一种,催化剂的添加量为100ppm-1倍当量(以苯乙炔烃计)。
所述碱为叔丁基醇钾、叔丁基醇锂、叔丁基醇钠、乙酸钾、氢氧化钠、1,8-二氮杂二环十一碳-7-烯、吡啶、甲醇锂、甲醇钠、碳酸铯、碳酸钾中的至少一种,添加量为1-3倍当量(以苯乙炔烃计)。
所述硼试剂为联硼酸频那醇酯、频那醇硼烷、双联邻苯二酚硼酸酯、双(新戊基乙二醇) 二硼中的至少一种,硼试剂的添加量为1-4倍当量(以苯乙炔烃计)。
所述溶剂为乙腈、二氯甲烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、1,4-二氧六环、甲醇、甲苯、丙酮、二甲亚砜、二乙二醇二甲醚、乙酸乙酯或四氢呋喃。
所述分离提纯是向反应液中加入水,用乙酸乙酯萃取,无水硫酸钠干燥,最后利用旋蒸除去溶剂,通过柱层析分离纯化,柱层析分离纯化时的洗脱液为石油醚:乙酸乙酯=20:1~100:1,v/v,即可得到目标产物。
本发明反应过程如下:
本发明的有益效果体现在:
1、本发明的合成方法条件温和反应时间比较短,操作简便安全,有害金属含量低。
2、本发明的合成方法底物适用性广,产率比较高,副产物比较少,能兼容多种官能团,适用于多种取代基的烯基硼酸酯。
具体实施方式
为进一步阐述本发明的特征和优点,下面结合具体的实施例对本发明的技术方案进行描述。但下列实施例仅为了进一步说明本发明,而不是限制本发明。
实施例1:
向将联硼酸新戊二醇酯(0.30mmol,1.5equiv)、4-二甲氨基吡啶(0.60mmol,3.0equiv) 放入装有搅拌子的透明Schlenk管中,管子抽真空,然后鼓入氩气,重复3-4次。在氩气氛围下添加联苯乙炔(1a)(0.20mmol,1.0equiv)、Pd(PCy3)2Cl2(400ppm)和溶剂(乙醇,3mL),将反应混合物在70℃下搅拌10小时;反应结束后冷却至室温,用水淬灭并用乙酸乙酯萃取,合并有机层,经硫酸钠干燥,然后真空浓缩,产物通过硅胶快速柱色谱法纯化(石油醚/乙酸乙酯=20:1)得无色油(2a)(44mg,75%)。该化合物的核磁数据为:1H NMR(600MHz,CDCl3) δ7.59(d,J=8.1Hz,2H),7.56(d,J=2.6Hz,3H),7.43(t,J=7.7Hz,2H),7.37(d,J=18.3Hz, 1H),7.33(t,J=7.4Hz,1H),6.14(d,J=18.3Hz,1H),3.71(s,4H),1.01(s,6H).13C NMR(151 MHz,CDCl3)δ146.69,141.33,140.76,136.91,128.86,127.53,127.46,127.31,127.06,72.40, 31.88,21.83.11B NMR(193MHz,CDCl3)δ25.31.
实施例2:
表1低浓度金属催化的炔烃氢化硼化
针对上述反应,我们以4-乙炔基-1,1'-联苯(1)和联硼酸新戊二醇酯(2)为模型底物,邻二甲苯为溶剂,醋酸钾为碱,通过筛选适宜的400ppm浓度的金属催化剂来实现炔烃的氢化硼化反应。开始进行廉价金属的尝试,400ppm(0.04mol%)的氯化镍,或者其与多种膦配体组合(PPh3,PCy3,Xantphos)也能提供较低产率的目标产物,但副产物较多。400ppm(0.04 mol%)的氯化亚铜与菲罗啉配体(1,10-Ph,NC)组合不能提供目标产物,400ppm(0.04mol%) 的氯化亚铜与膦配体组合(PPh3,PCy3,Sphos,Xphos,5mol%)能提供较低产率的目标产物,但反应比较杂。令人兴奋的是,400ppm的Pd(PCy3)2Cl2可以提供60%的目标产物,并且副产物少。与前几种转化相比,此种转化ppm浓度廉价金属也可以催化,但与钯催化剂相比副反应较多。
实施例3:
表2炔烃氢化硼化的碱的优化
Entry | Base | Yield(%)<sup>b</sup> |
1 | CH<sub>3</sub>COOK | 60 |
2 | CH<sub>3</sub>COONa | 50 |
3 | Na<sub>2</sub>CO<sub>3</sub> | 25 |
4 | K<sub>2</sub>CO<sub>3</sub> | 30 |
5 | Cs<sub>2</sub>CO<sub>3</sub> | 15 |
6 | KBF<sub>4</sub> | trace |
7 | KOH | 33 |
8 | NaOH | trace |
9 | DMAP | 65 |
10 | DABCO | 10 |
11 | TEA | 22 |
12 | DBU | 55 |
筛选出适宜的催化剂后,对碱进行了筛选。三个当量的醋酸钠可以提供的50%的目标产物。碳酸钠、碳酸钾、碳酸铯能提供较低产率的目标产物(25%,30%,15%),氢氧化钾可以提供33%的目标产物,氢氧化钠也不能提供目标产物。有机碱也进行了考察,三乙胺能提供22%的目标产物,1,8-二氮杂双环[5.4.0]十一碳-7-烯可以提供的55%的目标产物。三乙烯二胺可以提供10%的目标产物,4-二甲氨基吡啶的效果最好,可以提供65%的目标产物。
实施例4:
表3炔烃氢化硼化的溶剂优化
Entry | Slovent | Yield(%)<sup>b</sup> |
1 | o-xylene | 65 |
2 | toluene | 60 |
3 | cyclohexane | 25 |
4 | DCE | 0 |
5 | MeCN | 18 |
6 | EA | 5 |
7 | EtOH(95%) | 75 |
筛选出适宜的催化剂、碱,接着对溶剂也进行了筛选。邻二甲苯和甲苯可以分别提供65%和60%的目标产物,环己烷,乙腈和乙酸乙酯可以提供较低产率的目标产物(25%,18%,5%),1,2-二氯乙烷不能提供目标产物,乙醇是此反应的最佳溶剂,在最优条件下可以提供75%的目标产物。
实施例5:
表4低浓度钯催化的炔烃氢化硼化
Entry | Catalyst(400ppm) | Yield(%)<sup>b</sup> |
1 | Pd(OAc)<sub>2</sub> | 24 |
2 | PdCl<sub>2</sub> | 20 |
3 | Pd<sub>2</sub>(dba)<sub>3</sub> | 41 |
4 | Pd(PPh<sub>3</sub>)<sub>4</sub> | 23 |
5 | Pd(dppf)Cl<sub>2</sub> | 15 |
6 | Pd(OAc)<sub>2</sub>/PPh<sub>3</sub> | 40 |
7 | Pd(OAc)<sub>2</sub>/Xantphos | 10 |
8 | Pd(OAc)<sub>2</sub>/Binap | 30 |
9 | Pd(OAc)<sub>2</sub>/Dave-phos | 36 |
10 | Pd(OAc)<sub>2</sub>/<sup>t</sup>BuXphos | 30 |
11 | Pd(OAc)<sub>2</sub>/Ruphos | 35 |
12 | Pd(OAc)<sub>2</sub>/PCy<sub>3</sub> | 52 |
13 | Pd(PCy<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub> | 75 |
在上文研究基础上,我们又进一步考察了多种商品化的钯,在这种低浓度金属催化反应上的表现。400ppm的醋酸钯,氯化钯,三二亚苄基丙酮二钯可以提供较低产率的目标产物 (24%,20%,41%)。四(三苯基膦)钯可以提供23%的目标产物,1,1'-双二苯基膦二茂铁二氯化钯能提供15%的目标产物。在400ppm的醋酸钯为前催化剂的条件下,多种膦配体的作用也进行了考察(5mol%的配体),PPh3可以提供40%的目标产物,Dave-phos可以提供36%的目标产物,Ruphos,PCy3可以分别提供35%和52%的目标产物。Xantphos,Binap,tBuXphos能提供较低产率目标产物(10%,30%,30%)。Pd(OAc)2/PCy3能提供52%的目标产物,经过筛选Pd(PCy3)2Cl2的效果最好,75%的目标产物。
实施例6:
用苯乙炔(1b)代替联苯乙炔(1a),其他同实施例1。产物通过硅胶快速柱色谱法纯化(石油醚/乙酸乙酯=20:1)得无色油(2b)(26mg,60%)。该化合物的核磁数据为:1H NMR(600MHz,CDCl3)δ7.49(d,J=7.0Hz,2H),7.34(d,J=7.5Hz,1H),7.33–7.31(m,2H),7.27(d, J=7.3Hz,1H),6.11(d,J=18.3Hz,1H),3.70(s,4H),1.00(s,6H).13C NMR(151MHz,CDCl3)δ 147.22(s),137.89(s),128.60(s),127.08(s),111.81(s),72.16(s),31.94(s),21.96(s).11B NMR (193MHz,CDCl3)δ25.43(s).
实施例7:
用3-甲基苯乙炔(1c)代替联苯乙炔(1a),其他同实施例1。产物通过硅胶快速柱色谱法纯化(石油醚/乙酸乙酯=20:1)得无色油(2c)(28mg,61%)该化合物的核磁数据为:1HNMR(600MHz,CD3COCD3)δ7.32(s,1H),7.29(d,J=7.7Hz,1H),7.24(d,J=18.3Hz,1H), 7.21(t,J=7.6Hz,1H),7.09(d,J=7.5Hz,1H),6.04(d,J=18.2Hz,1H),3.66(s,4H),2.30(s,3H),0.95(s,2H).13C NMR(151MHz,CD3COCD3)δ147.01,138.05,137.90,129.30,128.52,127.53,124.10,71.68,31.54,21.07,20.51.11B NMR(128MHz,CD3COCD3)δ25.31
实施例8:
用4-氨基苯乙炔(1d)代替联苯乙炔(1a),其他同实施例1。产物通过硅胶快速柱色谱法纯化(石油醚/乙酸乙酯=20:1)得无色油(2d)(21mg,45%)。该化合物的核磁数据为:1H NMR(600MHz,CD3COCD3)δ7.22(d,J=8.4Hz,2H),7.15(d,J=18.2Hz,1H),6.61(d,J=8.5Hz,2H),5.72(d,J=18.2Hz,1H),4.83(s,2H),3.63(s,4H),0.94(s,6H).13C NMR(151MHz, CD3COCD3)δ149.42,147.53,128.24,126.82,114.13,71.62,31.54,21.11.11BNMR(193MHz, CD3COCD3)δ25.48.
实施例9:
用4-氟苯乙炔(1e)代替联苯乙炔(1a),其他同实施例1。产物通过硅胶快速柱色谱法纯化(石油醚/乙酸乙酯=20:1)得无色油(2e)(30.5mg,65%)。该化合物的核磁数据为:1H NMR(400MHz,CD3COCD3)δ7.55(m,2H),7.25(d,J=18.3Hz,1H),7.09(m,2H),5.99(d, J=18.3Hz,1H),3.67(s,4H),0.95(s,6H).13C NMR(101MHz,CD3COCD3)δ169.38,166.93,150.64,139.66,134.06,120.48,76.89,36.75,26.25.11B NMR(128MHz,CD3COCD3)δ30.48.
实施例10:
用4-甲氧羰基基苯乙炔(1f)代替联苯乙炔(1a),其他同实施例1。产物通过硅胶快速柱色谱法纯化(石油醚/乙酸乙酯=20:1)得无色油(2f)(27.5mg,50%)。该化合物的核磁数据为:1H NMR(600MHz,CD3COCD3)δ7.96(d,J=8.4Hz,2H),7.63(d,J=8.3Hz,2H),7.31(d,J=18.3Hz,1H),6.21(d,J=18.3Hz,1H),3.85(s,3H),3.68(s,4H),0.96(s,6H).13C NMR(151 MHz,CD3COCD3)δ166.08,145.48,142.23,130.02,129.72,126.92,71.73,51.48,31.54, 21.02.11B NMR(193MHz,CD3COCD3)δ25.23.
实施例11:
用4-氰基苯乙炔(1g)代替联苯乙炔(1a),其他同实施例1。产物通过硅胶快速柱色谱法纯化(石油醚/乙酸乙酯=20:1)得无色油(2g)(30.5mg,63%)。该化合物的核磁数据为:1H NMR(400MHz,CD3COCD3)δ7.74–7.67(m,4H),7.28(d,J=18.2Hz,1H),6.25(d,J=18.3Hz,1H),3.67(s,4H),0.95(s,6H).13C NMR(101MHz,CD3COCD3)δ132.49,132.01,129.10,128.41,127.56,118.53,71.77,31.58,21.06.11B NMR(128MHz,CD3COCD3)δ25.02.
实施例12:
用4-硝基苯乙炔(1h)代替联苯乙炔(1a),其他同实施例1。产物通过硅胶快速柱色谱法纯化(石油醚/乙酸乙酯=20:1)得无色油(2h)(18.5mg,35%)。该化合物的核磁数据为:1H NMR(400MHz,CD3COCD3)δ7.84–7.61(m,4H),7.29(d,J=18.3Hz,1H),6.24(d,J=18.3Hz),3.69(s,4H),0.96(s,6H).13C NMR(101MHz,CD3COCD3)δ144.85,142.18,132.54,127.60,118.48,111.66,71.70,31.55,20.97.11B NMR(128MHz,CD3COCD3)δ25.12。
Claims (9)
2.根据权利要求1所述的合成方法,其特征在于:
具体是将苯乙炔类化合物在氩气保护条件下溶于溶剂中,在催化剂、碱以及硼试剂的存在下进行反应,反应结束后分离提纯得到目标产物。
3.根据权利要求2所述的合成方法,其特征在于:
所述催化剂为氯钯酸钠、双(二亚苄基丙酮)钯、四(三苯基膦)钯、(1,3-双二苯基磷丙烷)钯、二(乙酰丙酮)钯、氯化钯、三氟乙酸钯、双三苯基膦二氯化钯、醋酸钯、二氯二(三环己基磷)钯、[1,1’-双(二苯基磷基)二茂铁]二氯化钯中的至少一种,催化剂的添加量为100ppm-1倍当量。
4.根据权利要求2所述的合成方法,其特征在于:
所述碱为叔丁基醇钾、叔丁基醇锂、叔丁基醇钠、4-二甲氨基吡啶、乙酸钾、氢氧化钠、1,8-二氮杂二环十一碳-7-烯、吡啶、甲醇锂、甲醇钠、碳酸铯、碳酸钾中的至少一种,添加量为1-3倍当量。
5.根据权利要求2所述的合成方法,其特征在于:
所述硼试剂为联硼酸频那醇酯、频那醇硼烷、双联邻苯二酚硼酸酯、双(新戊基乙二醇)二硼中的至少一种,硼试剂的添加量为1-4倍当量。
6.根据权利要求2所述的合成方法,其特征在于:
所述溶剂为乙腈、二氯甲烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、1,4-二氧六环、甲醇、甲苯、丙酮、二甲亚砜、二乙二醇二甲醚、乙酸乙酯或四氢呋喃。
7.根据权利要求2所述的合成方法,其特征在于:
反应温度为60-150℃,反应时间为2-10h。
8.根据权利要求2所述的合成方法,其特征在于:
所述分离提纯是向反应液中加入水,用乙酸乙酯萃取,无水硫酸钠干燥,最后利用旋蒸除去溶剂,通过柱层析分离纯化,即可得到目标产物。
9.根据权利要求8所述的合成方法,其特征在于:
柱层析分离纯化时的洗脱液为石油醚:乙酸乙酯=20:1~100:1,v/v。
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