CN117551139A - 一种含有三蝶烯三齿结构的金属钯化合物及其应用 - Google Patents
一种含有三蝶烯三齿结构的金属钯化合物及其应用 Download PDFInfo
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- CN117551139A CN117551139A CN202311496195.9A CN202311496195A CN117551139A CN 117551139 A CN117551139 A CN 117551139A CN 202311496195 A CN202311496195 A CN 202311496195A CN 117551139 A CN117551139 A CN 117551139A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 150000002941 palladium compounds Chemical class 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000006411 Negishi coupling reaction Methods 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 3
- 238000007341 Heck reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 32
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000001514 detection method Methods 0.000 abstract 1
- 238000006053 organic reaction Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 238000012360 testing method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000543 intermediate Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000008901 benefit Effects 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000004949 mass spectrometry Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 2
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 2
- VIMMECPCYZXUCI-MIMFYIINSA-N (4s,6r)-6-[(1e)-4,4-bis(4-fluorophenyl)-3-(1-methyltetrazol-5-yl)buta-1,3-dienyl]-4-hydroxyoxan-2-one Chemical compound CN1N=NN=C1C(\C=C\[C@@H]1OC(=O)C[C@@H](O)C1)=C(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 VIMMECPCYZXUCI-MIMFYIINSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PSWDQTMAUUQILQ-UHFFFAOYSA-N 2-[(6-methoxy-4-methylquinazolin-2-yl)amino]-5,6-dimethyl-1h-pyrimidin-4-one Chemical compound N1=C(C)C2=CC(OC)=CC=C2N=C1NC1=NC(=O)C(C)=C(C)N1 PSWDQTMAUUQILQ-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- 238000007125 Buchwald synthesis reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229940125907 SJ995973 Drugs 0.000 description 1
- VFHDCDDYMMQCBF-UHFFFAOYSA-M [Cl-].[Zn+]C1=CC=CC=C1 Chemical compound [Cl-].[Zn+]C1=CC=CC=C1 VFHDCDDYMMQCBF-UHFFFAOYSA-M 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AKJFBIZAEPTXIL-UHFFFAOYSA-N chloro(dicyclohexyl)phosphane Chemical compound C1CCCCC1P(Cl)C1CCCCC1 AKJFBIZAEPTXIL-UHFFFAOYSA-N 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 229940125796 compound 3d Drugs 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MCRSZLVSRGTMIH-UHFFFAOYSA-N ditert-butyl(chloro)phosphane Chemical compound CC(C)(C)P(Cl)C(C)(C)C MCRSZLVSRGTMIH-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XZMHJYWMCRQSSI-UHFFFAOYSA-N n-[5-[2-(3-acetylanilino)-1,3-thiazol-4-yl]-4-methyl-1,3-thiazol-2-yl]benzamide Chemical compound CC(=O)C1=CC=CC(NC=2SC=C(N=2)C2=C(N=C(NC(=O)C=3C=CC=CC=3)S2)C)=C1 XZMHJYWMCRQSSI-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- RWWYLEGWBNMMLJ-YSOARWBDSA-N remdesivir Chemical compound NC1=NC=NN2C1=CC=C2[C@]1([C@@H]([C@@H]([C@H](O1)CO[P@](=O)(OC1=CC=CC=C1)N[C@H](C(=O)OCC(CC)CC)C)O)O)C#N RWWYLEGWBNMMLJ-YSOARWBDSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4238—Negishi-type, i.e. RY + R'ZnZ, in which R, R' is optionally substituted alkyl, alkenyl, alkynyl, aryl, Y is the leaving group and Z is halide or R'
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4255—Stille-type, i.e. RY + R'3SnR'', in which R is alkenyl, aryl, R' is alkyl and R'' is alkenyl or aryl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
-
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Abstract
本发明涉及一种含有三蝶烯三齿结构的金属钯化合物及其应用,化合物的结构式为I所示,
Description
技术领域
本发明属于有机合成技术领域,涉及一种含有三蝶烯三齿结构的金属钯化合物及其应用。
背景技术
金属催化剂具有丰富的反应性,在有机合成中起着十分重要的作用,成为各类有机化学反应中如氢化、偶联、环加成等反应中应用最广泛的催化剂。在过去的几十年里,由于其具有反应条件温和、底物的适用范围较广、副产物无毒害以及产物易于处理等优点,使得金属催化剂被广泛地应用于实验室研究、制药业已经精细化工领域,用来合成很多种类型的有机化合物。
以Suzuki反应为例,Suzuki反应是最常用的构筑芳香环偶联反应之一,其中最为常用的就是金属钯催化剂,该类型的催化体系得到了非常广泛的研究,由于钯金属催化剂对于空气和热有着相对较高的稳定性,且在催化反应中易于回收利用,反应有着较高的活性,而且其中一些比较成熟的体系可以在比较温和的条件下催化活化和非活化氯苯的和苯硼酸的偶联,因此成为现代有机合成最重要的手段之一,被应用到很多有机分子合成领域。
尽管金属催化剂的研究已经有了很大的进展,但是其在工业上的应用仍然存在着很多的问题和缺陷。由于其价格昂贵,对于许多配体和催化剂体系而言,存在着结构复杂、制备条件苛刻、容易失活及反应后难以回收利用等问题因此高稳定性、高活性、底物适用范围广、可回收利用性、造价低廉、有很高的TON和TOF的金属催化剂依然是很重要的研究内容。
发明内容
本发明的目的在于克服现有技术的不足之处,提供一种具有高稳定性、高活性、底物适用范围广的一种含有三蝶烯三齿结构的金属钯化合物及其应用,该类化合物合成步骤简单,收率高,成本较低,作为催化剂使用时适用于各类不同的金属催化反应,有较高的推广应用价值。
为实现上述目的,本发明是通过以下技术方案实现的:
一种含有三蝶烯三齿结构的金属钯化合物,其结构如式I所示,
所述式I中,R1、R2、R3、R4各自独立的选自-H、-D、-T、-Cl、-Br、-F、-CN、-CD3、-CF3、-OCF3、碳原子数为1-15的取代或未取代的烷基、碳原子为1-15的取代或未取代的烷氧基、碳原子数为2-15的直链取代或未取代的烯烃基、氟代的碳原子数为1-15的取代或未取代的烷基、氟代的碳原子数为1-15的取代或未取代的烷氧基、氟代的碳原子数为2-15的直链取代或未取代烯烃基、碳原子数为5-20的取代或未取代的芳基、碳原子数为5-20的取代或未取代的杂芳基、碳原子数为5-20的取代或未取代的稠环芳基或碳原子数为5-20的取代或未取代的杂稠环芳基中的任意一种;
X表示Cl、Br、I。
上述的含有三蝶烯三齿结构的金属钯化合物应用于催化剂中。
进一步的,所述催化剂应用于包括但不限于Suzuki反应、Buchwald-Hartwig反应、Heck反应、Still反应或Negishi反应中。
本发明的有益效果是:
本专利提供的含有三蝶烯三齿结构的金属钯化合物,制备简便,收率高,作为催化剂使用时适用于多种底物,催化剂使用量可大幅降低,对于各类金属催化的反应均有较好的催化效果。对于研究催化反应的进展与应用,降低生产成本,扩展底物适用范围具有重要的应用价值。
具体实施方式
以下结合具体实施例对本发明的技术方案进行详细的说明,以下的实施例仅是示例性的,仅能用来解释和说明本发明的技术方案,而不能解释为是对本发明技术方案的限制。
实施例1化合物1的制备
步骤1:化合物1a的制备
向500mL两口瓶内,加入2.1g(10.0mmol)化合物1b,3.0g(10.0mmol)化合物1c,1.2g(30.0mmol)氢氧化钠,100mL的乙二醇二甲醚,回流搅拌反应10h,降至室温加入30mL1N的盐酸,搅拌10min,抽滤,滤饼30mL水洗3次,得到淡黄色固体2.7g,收率93%。
质谱(ESI):m/z 285.09(M+)。
步骤2:化合物1的制备
向500mL两口瓶内,加入2.9g(10.0mmol)化合物1a,2.1g(12.0mmol)氯化钯,4.9g(22.0mmol)二苯基氯化磷,0.8g(30.0mmol)醋酸钠,100mL的甲苯,回流搅拌反应2h,抽干溶剂,氧化铝柱层析,二氯甲烷淋洗得到化合物1的淡黄色固体7.2g,收率91%。
元素分析C44H31ClO2P2Pd,理论值:C,66.43;H,3.93;P,7.79。实测值:C,66.33;H,3.98;P,7.77。
质谱(ESI):m/z 793.04(M+)。
实施例2化合物2的制备
步骤1:化合物2a的制备
向500mL两口瓶内,加入2.6g(10.0mmol)化合物2b,3.0g(10.0mmol)化合物1c,1.2g(30.0mmol)氢氧化钠,100mL的乙二醇二甲醚,回流搅拌反应10h,降至室温加入30mL1N的盐酸,搅拌10min,抽滤,滤饼30mL水洗3次,得到白色固体3.0g,收率88%。
质谱(ESI):m/z 335.11(M+)。
步骤2:化合物2的制备
向500mL两口瓶内,加入3.4g(10.0mmol)化合物2a,3.2g(12.0mmol)溴化钯,4.0g(22.0mmol)二叔丁基氯化磷,0.8g(30.0mmol)醋酸钠,100mL的甲苯,回流搅拌反应2h,抽干溶剂,氧化铝柱层析,二氯甲烷淋洗得到化合物2的淡黄色固体7.6g,收率94%。
元素分析C40H49BrO2P2Pd,理论值:C,59.31;H,6.10;P,7.65。实测值:C,59.73;H,5.98;P,7.77。
质谱(ESI):m/z807.13(M+)。
实施例3化合物3的合成
步骤1:化合物3a的制备
向500mL两口瓶内,加入2.1g(10.0mmol)化合物3b,0.6g(10.0mmol)硝基甲烷,1.8g(10.0mmol)醋酸铜,100mL的N,N-二甲基甲酰胺,回流搅拌反应4h,降至室温加入20mL水和20mL乙酸乙酯,搅拌10min,分液,水相20mL乙酸乙酯萃取3次,有机相合并,抽干溶剂得到白色固体2.2g,收率94%。
质谱(ESI):m/z234.05(M+)。
步骤2:化合物3d的制备
向500mL两口瓶内,加入2.4g(10.0mmol)化合物3a,3.3g(10.0mmol)化合物3c,1.2g(30.0mmol)氢氧化钠,100mL的乙二醇二甲醚,回流搅拌反应10h,降至室温加入30mL1N的盐酸,搅拌10min,抽滤,滤饼30mL水洗3次,得到白色固体3.0g,收率87%。
质谱(ESI):m/z 339.13(M+)。
步骤3:化合物3的制备
向500mL两口瓶内,加入3.4g(10.0mmol)化合物3d,4.3g(12.0mmol)碘化钯,5.1g(22.0mmol)二环己基氯化磷,0.8g(30.0mmol)醋酸钠,100mL的甲苯,回流搅拌反应2h,抽干溶剂,氧化铝柱层析,二氯甲烷淋洗得到化合物3的淡黄色固体8.2g,收率85%。
元素分析C47H58INO2P2Pd,理论值:C,58.54;H,6.06;N,1.45;P,6.42。实测值:C,58.71;H,6.16;N,1.05;P,6.32。
质谱(ESI):m/z 962.19(M+)。
实施例4化合物4的合成
步骤1:化合物4a的制备
向500mL两口瓶内,加入2.1g(10.0mmol)化合物1b,3.5g(10.0mmol)化合物4b,1.2g(30.0mmol)氢氧化钠,100mL的乙二醇二甲醚,回流搅拌反应10h,降至室温加入30mL1N的盐酸,搅拌10min,抽滤,滤饼30mL水洗3次,得到白色固体3.2g,收率96%。
质谱(ESI):m/z 335.11(M+)。
步骤2:化合物2的制备
向500mL两口瓶内,加入3.4g(10.0mmol)化合物4a,2.1g(12.0mmol)氯化钯,6.1g(22.0mmol)化合物4c,0.8g(30.0mmol)醋酸钠,100mL的甲苯,回流搅拌反应2h,抽干溶剂,氧化铝柱层析,二氯甲烷淋洗得到化合物4的淡黄色固体8.6g,收率90%。
元素分析C56H49ClO2P2Pd,理论值:C,70.22;H,5.16;P,6.47。实测值:C71.93;H,5.18;P,6.77。
质谱(ESI):m/z955.18(M+)。
实施例5Suzuki偶联反应催化比较
在装有磁子的Schlenk管中依次加入1.5mmol苯硼酸、1.1mmol的叔丁醇钾和0.01%mmol的催化剂(化合物1、2、3、4、ref-1),然后加入1.0mmol的对甲氧基溴苯、1mL异丙醇,80℃下搅拌2h。然后用二氯甲烷溶解后拌入氧化铝,柱层析(淋洗液二氯甲烷/石油醚=2∶1),得到无色的产品,称重后计算产率。
其中化合物1、2、3、4为实施例1至4合成的化合物,化合物ref-1为商用对比催化剂,反应通式如下:
其反应结果如下表1所示:
表1、Suzuki反应对比试验结果
试验编号 | 采用催化剂 | 收率(%) |
1 | 1 | 89 |
2 | 2 | 89 |
3 | 3 | 91 |
4 | 4 | 94 |
5 | ref-1 | 62 |
由上可知,本发明专利方法制得的含有三蝶烯三齿结构的金属钯化合物(实施例1-4,试验编号1-4)在应用中和对比例ref-1(实验编号5)相比,由于含有三蝶烯大位阻基团能够稳定催化循环中的中间体,同时三齿形成的环状结构,阻碍了对活性中心的进攻,使活性中间体自身的反应性降低,对活性中间体起到了非常好的稳定性效果,因此实现了较高的催化活性,仅用万分之一的用量就能以非常高的收率实现Suzuki催化反应,而在工业生产中,催化剂的用量对于原材料的成本控制,后处理的难易程度均存在非常大的影响,在成本控制上有着巨大的优势,这是对比例所不能达到的。
实施例6 Hartwig-Buchwald偶联反应催化比较
在装有磁子的Schlenk管中依次加入1.0mmol对甲氧基溴苯、1.1mmol的叔丁醇钾和0.01%mmol的催化剂(1、2、3、4、ref-2),然后加入1.2mmol的二苯胺、1mL甲苯,100℃下搅拌2h。然后用二氯甲烷溶解后拌入氧化铝,柱层析(淋洗液二氯甲烷/石油醚=2∶1),得到无色的产品,称重后计算产率。
其中化合物1、2、3、4为实施例1至4合成的化合物,化合物ref-2为商用对比催化剂,反应通式如下:
其反应结果如下表2所示:
表2、Hartwig-Buchwald反应对比试验结果
试验编号 | 采用催化剂 | 收率(%) |
6 | 1 | 89 |
7 | 2 | 88 |
8 | 3 | 84 |
9 | 4 | 91 |
10 | ref-2 | 48 |
由上可知,本发明专利方法制得的含有三蝶烯三齿结构的金属钯化合物(实施例1-4,试验编号6-9)在应用中和对比例ref-2(实验编号10)相比,由于含有三蝶烯大位阻基团能够稳定催化循环中的中间体,同时三齿形成的环状结构,阻碍了对活性中心的进攻,使活性中间体自身的反应性降低,对活性中间体起到了非常好的稳定性效果,因此实现了较高的催化活性,仅用万分之一的用量就能以非常高的收率实现Hartwig-Buchwald催化反应,而在工业生产中,催化剂的用量对于原材料的成本控制,后处理的难易程度均存在非常大的影响,在成本控制上有着巨大的优势,这是对比例所不能达到的。
实施例7Heck偶联反应催化比较
在装有磁子的Schlenk管中依次加入1.0mmol对溴苯甲酸、1.2mmol的碳酸钾和0.01%mmol的催化剂(化合物1、2、3、4、ref-3),然后加入1.2mmol的丙烯酸、1mL二甲苯,120℃下搅拌2h。然后用二氯甲烷溶解后拌入氧化铝,柱层析(淋洗液二氯甲烷/石油醚=4∶1),得到无色的产品,称重后计算产率。
其中化合物1、2、3、4为实施例1至4合成的化合物,化合物ref-3为商用对比催化剂,反应通式如下:
其反应结果如下表3所示:
表3、Heck反应对比试验结果
试验编号 | 采用催化剂 | 收率(%) |
11 | 1 | 88 |
12 | 2 | 80 |
13 | 3 | 84 |
14 | 4 | 85 |
15 | ref-3 | 70 |
由上可知,本发明专利方法制得的含有三蝶烯三齿结构的金属钯化合物(实施例1-4,试验编号11-14)在应用中和对比例ref-3(实验编号15)相比,由于含有三蝶烯大位阻基团能够稳定催化循环中的中间体,同时三齿形成的环状结构,阻碍了对活性中心的进攻,使活性中间体自身的反应性降低,对活性中间体起到了非常好的稳定性效果,因此实现了较高的催化活性,仅用万分之一的用量就能以非常高的收率实现Heck催化反应,而在工业生产中,催化剂的用量对于原材料的成本控制,后处理的难易程度均存在非常大的影响,在成本控制上有着巨大的优势,这是对比例所不能达到的。
实施例8 Still反应催化比较
在装有磁子的Schlenk管中依次加入1.0mmol对甲氧基溴苯、1.2mmol的氟化钾和0.01%mmol的催化剂(化合物1、2、3、4、ref-4),然后加入1.2mmol的三丁基苯基烯、1mL二氧六环,100℃下搅拌6h。然后用二氯甲烷溶解后拌入氧化铝,柱层析(淋洗液二氯甲烷/石油醚=4∶1),得到无色的产品,称重后计算产率。
其中化合物1、2、3、4为实施例1至4合成的化合物,化合物ref-4为商用对比催化剂,反应通式如下:
其反应结果如下表4所示:
表4、Still反应对比试验结果
试验编号 | 采用催化剂 | 收率 |
16 | 1 | 91 |
17 | 2 | 87 |
18 | 3 | 90 |
19 | 4 | 81 |
20 | ref-4 | 62 |
由上可知,本发明专利方法制得的含有三蝶烯三齿结构的金属钯化合物(实施例1-4,试验编号16-19)在应用中和对比例ref-4(实验编号20)相比,由于含有三蝶烯大位阻基团能够稳定催化循环中的中间体,同时三齿形成的环状结构,阻碍了对活性中心的进攻,使活性中间体自身的反应性降低,对活性中间体起到了非常好的稳定性效果,因此实现了较高的催化活性,仅用万分之一的用量就能以非常高的收率实现Still催化反应,而在工业生产中,催化剂的用量对于原材料的成本控制,后处理的难易程度均存在非常大的影响,在成本控制上有着巨大的优势,这是对比例所不能达到的。
实施例9 Negishi反应催化比较
在装有磁子的Schlenk管中依次加入1.0mmol对甲氧基溴苯、1.2mmol的碳酸钾和0.01%mmol的催化剂(化合物1、2、3、4、ref-5),然后加入1.2mmol的苯基氯化锌、1mL四氢呋喃,60℃下搅拌6h。然后用二氯甲烷溶解后拌入氧化铝,柱层析(淋洗液二氯甲烷/石油醚=4∶1),得到无色的产品,称重后计算产率。
其中化合物1、2、3、4为实施例1至4合成的化合物,化合物ref-5为商用对比催化剂,反应通式如下:
其反应结果如下表5所示:
表5、Negishi反应对比试验结果
试验编号 | 采用催化剂 | 收率(%) |
21 | 1 | 81 |
22 | 2 | 79 |
23 | 3 | 72 |
24 | 4 | 84 |
25 | Ref-5 | 73 |
由上可知,本发明专利方法制得的含有三蝶烯三齿结构的金属钯化合物(实施例1-4,试验编号21-24)在应用中和对比例ref-5(实验编号25)相比,由于含有三蝶烯大位阻基团能够稳定催化循环中的中间体,同时三齿形成的环状结构,阻碍了对活性中心的进攻,使活性中间体自身的反应性降低,对活性中间体起到了非常好的稳定性效果,因此实现了较高的催化活性,仅用万分之一的用量就能以非常高的收率实现Negishi催化反应,而在工业生产中,催化剂的用量对于原材料的成本控制,后处理的难易程度均存在非常大的影响,在成本控制上有着巨大的优势,这是对比例所不能达到的。。
综上可知,本发明专利所制得的含有三蝶烯三齿结构的金属钯化合物与常规的催化剂相比,有着更好的催化效果,对于各种不同取代基的反应底物也有着很好的普遍适用性,在催化剂用量上也有着显著的优势,仅需万分之一的用量就可以保证催化反映的进行,能普遍适用于各类金属催化的反应。合成方法简便,收率较高,有较高的推广应用价值,这是常规的金属催化剂所不能实现的,这样的效果是本领域技术人员所不能预料到的。
尽管结合优选实施例对本发明进行了说明,但本发明并不局限于上述实施例,应当理解,在本发明构思的引导下,本领域技术人员可进行各种修改和改进,所附权利要求概括了本发明的范围。
Claims (3)
1.一种含有三蝶烯三齿结构的金属钯化合物,其特征在于,其结构如式I所示,
所述式I中,R1、R2、R3、R4各自独立的选自-H、-D、-T、-Cl、-Br、-F、-CN、-CD3、-CF3、-OCF3、碳原子数为1-15的取代或未取代的烷基、碳原子为1-15的取代或未取代的烷氧基、碳原子数为2-15的直链取代或未取代的烯烃基、氟代的碳原子数为1-15的取代或未取代的烷基、氟代的碳原子数为1-15的取代或未取代的烷氧基、氟代的碳原子数为2-15的直链取代或未取代烯烃基、碳原子数为5-20的取代或未取代的芳基、碳原子数为5-20的取代或未取代的杂芳基、碳原子数为5-20的取代或未取代的稠环芳基或碳原子数为5-20的取代或未取代的杂稠环芳基中的任意一种;
X表示Cl、Br、I。
2.一种含有三蝶烯三齿结构的金属钯化合物的应用,其特征在于,上述权利要求1中的含有三蝶烯三齿结构的金属钯化合物应用于催化剂中。
3.根据权利要求2所述的含有三蝶烯三齿结构的金属钯化合物在催化剂的应用,其特征在于,所述催化剂应用于包括但不限于Suzuki反应、Buchwald-Hartwig反应、Heck反应、Still反应或Negishi反应中。
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