CN104744519B - 含吡啶甲基的扩环氮杂环卡宾钯化合物 - Google Patents
含吡啶甲基的扩环氮杂环卡宾钯化合物 Download PDFInfo
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- CN104744519B CN104744519B CN201510107498.6A CN201510107498A CN104744519B CN 104744519 B CN104744519 B CN 104744519B CN 201510107498 A CN201510107498 A CN 201510107498A CN 104744519 B CN104744519 B CN 104744519B
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- 238000006049 ring expansion reaction Methods 0.000 title claims abstract description 28
- 150000002941 palladium compounds Chemical class 0.000 title claims abstract description 27
- 238000005859 coupling reaction Methods 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- -1 halogenated aryl hydrocarbon Chemical class 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000003863 metallic catalyst Substances 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 19
- 239000000706 filtrate Substances 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- FVGPUOVYTQHXAU-UHFFFAOYSA-N 1,2,3,4-tetrahydropyrimidin-1-ium bromide Chemical compound [Br-].[NH2+]1CNCC=C1 FVGPUOVYTQHXAU-UHFFFAOYSA-N 0.000 description 12
- DKYBVKMIZODYKL-UHFFFAOYSA-N 1,3-diazinane Chemical class C1CNCNC1 DKYBVKMIZODYKL-UHFFFAOYSA-N 0.000 description 12
- NPOMSUOUAZCMBL-UHFFFAOYSA-N dichloromethane;ethoxyethane Chemical compound ClCCl.CCOCC NPOMSUOUAZCMBL-UHFFFAOYSA-N 0.000 description 12
- 238000007445 Chromatographic isolation Methods 0.000 description 11
- 238000011097 chromatography purification Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical class NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229910002666 PdCl2 Inorganic materials 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 125000002524 organometallic group Chemical group 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical class O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QWFHFNGMCPMOCD-UHFFFAOYSA-N 6-bromopyridine-2-carbaldehyde Chemical compound BrC1=CC=CC(C=O)=N1 QWFHFNGMCPMOCD-UHFFFAOYSA-N 0.000 description 3
- 0 CC*N(*)C=CN(*)CN Chemical compound CC*N(*)C=CN(*)CN 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZQVLPMNLLKGGIU-UHFFFAOYSA-N 5-bromopyridine-2-carbaldehyde Chemical compound BrC1=CC=C(C=O)N=C1 ZQVLPMNLLKGGIU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 210000000080 chela (arthropods) Anatomy 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- OTPDWCMLUKMQNO-UHFFFAOYSA-N 1,2,3,4-tetrahydropyrimidine Chemical compound C1NCC=CN1 OTPDWCMLUKMQNO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 150000001538 azepines Chemical class 0.000 description 1
- 125000002785 azepinyl group Chemical group 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
-
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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- C07—ORGANIC CHEMISTRY
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/08—Radicals containing only hydrogen and carbon atoms
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- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/033—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to carbocyclic rings
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- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- 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
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
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Abstract
本发明属于有机化合物领域,涉及钳形扩环氮杂环卡宾钯化合物。该化合物具有如下结构:
Description
技术领域
本发明属于有机化合物领域,涉及钳形扩环氮杂环卡宾钯化合物及其在催化C-N偶联反应中的应用。
背景技术
氮杂环卡宾(N-Heterocyclic Carbenes,NHCs)及其金属化合物多用于金属有机化学、配位化学、均相催化、材料化学以及药物化学研究领域。目前研究多集中在五元氮杂环卡宾(五元-NHCs)及其金属化合物,包括咪唑衍生的经典型咪唑-2-卡宾金属化合物、咪唑啉-2-卡宾金属化合物(A-D)和Crabtree教授课题组首次报道的以咪唑-4-卡宾为代表的非经典型卡宾金属化合物(E-F)。
咪唑衍生的五元-NHCs-金属化合物
三齿的钳形氮杂环卡宾配体,即配体中的卡宾碳、Ν上所连取代基中具有配位功能的杂原子,与同一金属中心配位,形成具有环状结构的配合物。此外,氮杂环卡宾配体本身还具有较强的σ-配位能力,因而三齿的钳形五元氮杂环卡宾金属化合物通常情况下对空气、水分以及热的稳定性增强,有利于其制备和应用,在均相催化方面取得了非常广泛的应用。例如,三齿配位的PCP、NCN、CCC、CNC钳形五元-氮杂环卡宾钯化合物被广泛应用于Heck、Suzuki等C-C偶联反应(参考文献(a)Liao,C.–Y.;Chan,K.–T.;Zeng,J.–Y.;Hu,C.–H.;Tu,C.–Y.;Lee,H.M.Organometallics 2007,26,1692.(b)Hahn,F.E.;Jahnke,M.C.;Pape,T.Organometallics 2006,25,5927.(c)Lee,H.M.;Zeng,J.Y.;Hu,C.–H.;Lee,M.–T.Inorg.Chem.2004,43,6822.(d)Tsoureas,N.;Danopoulos,A.A.;Tulloch,A.A.D.;Light,M.E.Organometallics 2003,22,4750.(e)Herrmann,W.A.;V.P.W.;C.W.K.;Grosche,M.;Reisinger,C.–P.;Weskamp,T.J.Organomet.Chem.2001,617-618,616.(f)Yang,C.;Lee,H.M.;Nolan,S.P.Org.Lett.2001,3,1511.)。
钳形NHC-Pd化合物催化的C-C偶联反应
杂环上原子数目大于五的NHCs被称为扩环氮杂环卡宾(Ring-Expanded NHCs,RE-NHCs),与五元-NHCs相比,六元-、七元-等RE-NHCs表现出相当不同的性质,尤其是显著增强的碱性/亲核性和空间效应,因而相应金属化合物的结构特征、催化活性和选择性也明显不同。由于扩环氮杂环卡宾的σ-供电子能力增强,N-Ccarbene-N键角变大,R-N-Ccarbene键角变小,促使N上取代基更加靠近金属中心,使位阻效应增大,从而提高催化剂的活性和稳定性。已报道的扩环氮杂环卡宾金属化合物的结构如下所示(参考文献(a)Collins,L.R.;Rookes,T.M.;Mahon,M.F.;Riddlestone,I.M.;Whittlesey,M.K.Organometallics 2014,33,5882.(b)Dunsford,J.J.;Cavell,K.J.;Kariuki,B.M.Organometallics 2012,31,4118.(c)Park,J.K.;Lackey,H.H.;Ondrusek,B.A.;McQuade,D.T.J.Am.Chem.Soc.2011,133,2410.(d)Armstrong,R.;Ecott,C.;Mas-Marzá,E.;Page,M.J.;Mahon,M.F.;Whittlesey,M.K.Organometallics 2010,29,991.(e)Scarborough,C.C.;Grady,M.J.W.;Guzei,I.A.;Gandhi,B.A.;Bunel,E.E.;Stahl,S.S.Angew.Chem.,Int.Ed.2005,44,5269.
文献报道的部分六元-、七元-、等RE-NHCs-金属化合物
目前,在RE-NHCs及其金属化合物的合成及性能的文献报道中,氮杂环卡宾中的卡宾碳与金属配位,形成单齿配位的简单络合物,催化效果不太理想。探索新的钳形扩环氮杂环卡宾金属催化剂,有利于钯催化的C-N偶联反应芳胺类化合物的合成。目前三齿配位的钳形扩环氮杂环卡宾金属化合物未见报道。
发明内容
本发明的目的在于提供催化效果好的三齿配位钳形扩环氮杂环卡宾钯化合物。
本发明所述的钳形扩环氮杂环卡宾钯化合物具有以下通式:
R同时相同或不同;X同时相同或不同。
优选结构如下化合物:
上述化合物合成路线如下:
本发明所述的钳形的扩环氮杂环卡宾钯化合物的合成方法通过如下步骤实现:
(1)1,3-丙二胺衍生物与2-吡啶甲醛衍生物以1:2摩尔比,在甲醇中,依次经脱水、还原得双取代1,3-丙二胺衍生物;进一步与等摩尔量的甲醛水溶液在甲醇中发生关环反应,生成六氢嘧啶衍生物;
(2)六氢嘧啶衍生物与NBS以1:1摩尔比,在乙二醇二甲醚反应脱氢,生成四氢嘧啶溴鎓盐衍生物后,与1.5摩尔量的六氟磷酸铵在乙醇中发生阴离子交换,生成四氢嘧啶六氟磷酸鎓盐;
(3)四氢嘧啶六氟磷酸鎓盐与氯化钯以1:0.5-2摩尔比、在有机溶剂中、在碱存在下,在50~200℃温度下、反应5~25小时,减压除去溶剂后,过柱分离得到钳形的扩环氮杂环卡宾钯化合物。
本发明所述的1,3丙二胺衍生物为1,3-丙二胺、2,2-二甲基-1,3-丙二胺;所述的2-吡啶甲醛衍生物为2-吡啶甲醛,5-溴-2-吡啶甲醛、6-溴-2-吡啶甲醛。
本发明所述的有机溶剂为四氢呋喃、甲苯、1,4-二氧六环、吡啶、N,N-二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、乙二醇二甲醚、二甲基亚砜。
本发明所述的碱为双(三甲基硅烷基)氨基钠、双(三甲基硅烷基)氨基钾、叔丁醇钠、叔丁醇钾、叔戊醇钠、叔戊醇钾。
本发明合成的钳形扩环氮杂环卡宾钯化合物具有独特的结构特点,在微波辐射下对溴苯、杂环卤代芳烃与胺的C-N偶联反应表现出高效的催化性能,芳胺常见于药物分子及天然产物中,也是许多新型功能材料的重要结构单元。钯催化的C-N偶联反应是合成芳胺类化合物的一种重要方法。本发明化合物为C-N偶联反应提供一类新型的金属催化剂,用于催化C-N偶联反应时,反应时间短,催化剂用量少、使用廉价易得的碱、反应溶剂无需处理、操作简单、催化产率高。
催化C-N偶联反应采用以下步骤:将本发明钳形扩环氮杂环卡宾钯化合物催化剂、碱、卤代芳烃、胺加入到溶剂中,在微波辐射下于50~100℃反应10~40分钟后,降至室温,减压除去溶剂,柱色谱分离得到纯品。
具体实施方式
以下结合较佳实例,对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
实施例1
在100mL圆底烧瓶中,将吡啶-2-甲醛(30mmol,3.21g)和1,3-丙二胺(15mmol,1.11g)在30mL甲醇中混合,室温反应5.0小时后,冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g),慢慢升温至70℃反应5小时,冷却至室温,旋干反应液。再用50mL CH2Cl2溶解、过滤,滤液旋干,得残留黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后,向其中加入等摩尔量甲醛水溶液,室温搅拌3小时后,减压除去溶剂,柱层析分离纯化得1,3-二(2-吡啶甲基)六氢嘧啶(3.50g,产率87%)。
在100mL圆底烧瓶中,将1,3-二(2-吡啶甲基)六氢嘧啶(5mmol,1.34g)溶于30mL乙二醇二甲醚(DME),向其中加入N-溴代丁二酰亚胺(NBS,5mmol,0.89g),室温搅拌3小时后,抽滤,将淡黄色滤饼经二氯甲烷-***重结晶,得1,3-二(2-吡啶甲基)四氢嘧啶溴鎓盐纯品。将1,3-二(2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后,旋干溶剂,残留物用二氯甲烷-***重结晶,得四氢嘧啶六氟磷酸鎓盐纯品(1.75g,产率85%)。
在Schlenk瓶中加入1,3-二(2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol,0.82g)和PdCl2(2mmol,0.35g),氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL),油浴140℃搅拌12h。反应结束后,将反应液冷却至室温,过滤,滤液经柱层析分离纯化(梯度洗脱,展开剂:正己烷/二氯甲烷=1/10~1/20),得钳形扩环氮杂环卡宾钯化合物(I)。无色固体(0.64g,58%).1H NMR(400MHz,DMSO-d6):δ9.00-8.98(m,2H,Py-H),8.22-8.18(m,2H,Py-H),7.88(d,J=7.1Hz,2H,Py-H),7.67-7.63(m,2H,Py-H),5.30(d,J=15.1Hz,2H,picolyl-CH2),4.80(d,J=15.3Hz,2H,picolyl-CH2),3.58-3.48(m,4H,pyrimidine-CH2),1.92(t,J=5.8Hz,2H,pyrimidine-CH2)ppm.13C NMR(100MHz,DMSO-d6):δ174.9,154.8,154.0,141.4,125.6,125.2,61.6,47.5,20.8ppm.Anal Cacld for C16H18ClF6N4PPd(551.99):C,34.74;H,3.28;N,10.13.Found:C,34.56;H,3.02;N,9.89.
实施例2
将吡啶-2-甲醛(30mmol,3.21g)和2,2-二甲基-1,3-丙二胺(15mmol,1.53g)在30mL甲醇中混合,室温反应7.0小时后,冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g),慢慢升温至70℃反应5小时。停止反应,冷却至室温,旋干反应液。再用50mL CH2Cl2溶解、过滤,滤液旋干,得黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后,再向其中加入等摩尔量甲醛水溶液,室温搅拌3小时后,减压除去溶剂,柱层析分离纯化得3,3-二甲基-1,3-二(2-吡啶甲基)六氢嘧啶(3.96g,产率89%)。
将3,3-二甲基-1,3-二(2-吡啶甲基)六氢嘧啶(5mmol,1.48g)溶于30mLDME,再向其中加入NBS(5mmol,0.89g),室温搅拌3小时后,抽滤得淡黄色粉末,经二氯甲烷-***重结晶得3,3-二甲基-1,3-二(2-吡啶甲基)四氢嘧啶溴鎓盐。将3,3-二甲基-1,3-二(2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后蒸干,再用CH2Cl2溶解、过滤,将滤液旋蒸,残留物用二氯甲烷-***重结晶得3,3-二甲基-1,3-二(2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐纯品(1.89g,产率86%)。
在Schlenk瓶中加入3,3-二甲基-1,3-二(2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol,0.88g)和PdCl2(2mmol,0.35g),氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL),油浴140℃搅拌12h。反应结束后,将反应液冷却至室温,过滤,滤液经柱层析分离纯化(梯度洗脱,展开剂:正己烷/二氯甲烷=1/10~1/20),得钳形扩环氮杂环卡宾钯化合物(II)。淡黄色固体(0.70g,60%).1H NMR(400MHz,DMSO-d6):δ9.01(d,J=4.9Hz,2H,Py-H),8.23-8.19(m,2H,Py-H),7.86(d,J=7.4Hz,2H,Py-H),7.68-7.65(m,2H,Py-H),5.38(d,J=15.1Hz,2H,picolyl-CH2),4.77(d,J=15.2Hz,2H,picolyl-CH2),3.28(d,J=3.2Hz,4H,pyrimidine-CH2),0.79(s,6H,CH3)ppm;13C NMR(100MHz,DMSO-d6):δ174.0,154.9,154.0,141.5,125.5,125.2,61.6,58.7,28.1,23.5ppm;Anal Cacld forC18H22ClF6N4PPd(580.02):C,37.20;H,3.82;N,9.64;Found:C,36.93;H,3.87;N,9.49.
实施例3
将5-溴吡啶-2-甲醛(30mmol,5.58g)和1,3-丙二胺(15mmol,1.11g)在30mL甲醇中混合,室温反应5.0小时后,冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g),慢慢升温至70℃反应5小时。停止反应,冷却至室温,旋干反应液。再用50mL CH2Cl2溶解、过滤,滤液旋干,得黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后,再向其中加入等摩尔量甲醛水溶液,室温搅拌3小时后,减压除去溶剂,柱层析分离纯化得1,3-二(5-溴-2-吡啶甲基)六氢嘧啶(5.30g,产率83%)。
将1,3-二(5-溴-2-吡啶甲基)六氢嘧啶(5mmol,2.13g)溶于30mL DME,再向其中加入NBS(5mmol,0.89g),室温搅拌3小时后,抽滤得淡黄色粉末,经二氯甲烷-***重结晶得1,3-二(5-溴-2-吡啶甲基)四氢嘧啶溴鎓盐。将1,3-二(5-溴2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后蒸干,再用CH2Cl2溶解、过滤,将滤液旋蒸,残留物用二氯甲烷-***重结晶得1,3-二(5-溴2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐纯品(2.42g,产率85%)。
在Schlenk瓶中加入1,3-二(5-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol,1.14g)和PdCl2(2mmol,0.35g),氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL),油浴140℃搅拌12h。反应结束后,将反应液冷却至室温,过滤,滤液经柱层析分离纯化(梯度洗脱,展开剂:正己烷/二氯甲烷=1/10~1/20),得钳形扩环氮杂环卡宾钯化合物(III)。浅黄色固体(0.75g,53%).1H NMR(400MHz,DMSO-d6):δ9.10-9.08(s,2H,Py-H),8.32-8.28(d,J=7.1Hz,,2H,Py-H),7.98(d,J=7.1Hz,2H,Py-H),5.35(d,J=15.1Hz,2H,picolyl-CH2),4.86(d,J=15.2Hz,2H,picolyl-CH2),3.63-3.54(m,4H,pyrimidine-CH2),1.97(t,J=5.8Hz,2H,pyrimidine-CH2)ppm.13C NMR(100MHz,DMSO-d6):δ174.8,154.3,153.6,141.0,125.1,124.7,61.5,47.3,20.6ppm.Anal Cacld for C16H16Br2ClF6N4PPd(707.81):C,27.03;H,2.27;N,7.88.Found:C,27.28;H,2.09;N,7.70.
实施例4
将5-溴吡啶-2-甲醛(30mmol,5.58g)和2,2-二甲基-1,3-丙二胺(15mmol,1.53g)在30mL甲醇中混合,室温反应7.0小时后,冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g),慢慢升温至70℃反应5小时。停止反应,冷却至室温,旋干反应液。再用50mL CH2Cl2溶解、过滤,滤液旋干,得黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后,再向其中加入等摩尔量甲醛水溶液,室温搅拌3小时后,减压除去溶剂,柱层析分离纯化得3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)六氢嘧啶(5.52g,产率81%)。
将3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)六氢嘧啶(5mmol,2.27g)溶于30mLDME,再向其中加入NBS(5mmol,0.89g),室温搅拌3小时后,抽滤得淡黄色粉末,经二氯甲烷-***重结晶得3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)四氢嘧啶溴鎓盐。将3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后蒸干,再用CH2Cl2溶解、过滤,将滤液旋蒸,残留物用二氯甲烷-***重结晶得3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐纯品(2.51g,产率84%)。
在Schlenk瓶中加入3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol,1.20g)和PdCl2(2mmol,0.35g),氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL),油浴140℃搅拌12h。反应结束后,将反应液冷却至室温,过滤,滤液经柱层析分离纯化(梯度洗脱,展开剂:正己烷/二氯甲烷=1/10~1/20),得钳形扩环氮杂环卡宾钯化合物(IV)。浅黄色固体(0.81g,55%).1H NMR(400MHz,DMSO-d6):δ9.11(s,2H,Py-H),8.32-8.29(d,J=7.5Hz,,2H,Py-H),7.96(d,J=7.5Hz,2H,Py-H),5.43(d,J=15.2Hz,2H,picolyl-CH2),4.82(d,J=15.2Hz,2H,picolyl-CH2),3.32(d,J=3.2Hz,4H,pyrimidine-CH2),0.84(s,6H,CH3)ppm;13C NMR(100MHz,DMSO-d6):δ174.1,154.4,153.5,141.0,125.1,124.7,61.4,58.5,27.9,23.3ppm;Anal Cacld for C18H20Br2ClF6N4PPd(735.84):C,29.25;H,2.73;N,7.58;Found:C,29.10;H,2.87;N,7.40.
实施例5
将6-溴吡啶-2-甲醛(30mmol,5.58g)和1,3-丙二胺(15mmol,1.11g)在30mL甲醇中混合,室温反应5.0小时后,冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g),慢慢升温至70℃反应5小时。停止反应,冷却至室温,旋干反应液。再用50mL CH2Cl2溶解、过滤,滤液旋干,得黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后,再向其中加入等摩尔量甲醛水溶液,室温搅拌3小时后,减压除去溶剂,柱层析分离纯化得1,3-二(6-溴-2-吡啶甲基)六氢嘧啶(5.25g,产率82%)。
将1,3-二(6-溴-2-吡啶甲基)六氢嘧啶(5mmol,2.13g)溶于30mL DME,再向其中加入NBS(5mmol,0.89g),室温搅拌3小时后,抽滤得淡黄色粉末,经二氯甲烷-***重结晶得1,3-二(6-溴-2-吡啶甲基)四氢嘧啶溴鎓盐。将1,3-二(6-溴2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后蒸干,再用CH2Cl2溶解、过滤,将滤液旋蒸,残留物用二氯甲烷-***重结晶得1,3-二(6-溴2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐纯品(2.36g,产率83%)。
在Schlenk瓶中加入1,3-二(6-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol,1.14g)和PdCl2(2mmol,0.35g),氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL),油浴140℃搅拌12h。反应结束后,将反应液冷却至室温,过滤,滤液经柱层析分离纯化(梯度洗脱,展开剂:正己烷/二氯甲烷=1/10~1/20),得钳形扩环氮杂环卡宾钯化合物(V)。浅黄色固体(0.78g,55%).1H NMR(400MHz,DMSO-d6):δ8.27-8.23(m,2H,Py-H),7.93(d,J=7.2Hz,2H,Py-H),7.72-7.68(m,2H,Py-H),5.33(d,J=15.2Hz,2H,picolyl-CH2),4.83(d,J=15.3Hz,2H,picolyl-CH2),3.62-3.53(m,4H,pyrimidine-CH2),1.95(t,J=5.8Hz,2H,pyrimidine-CH2)ppm.13C NMR(100MHz,DMSO-d6):δ175.0,155.3,154.4,141.9,126.0,125.6,61.9,47.8,21.0ppm.Anal Cacld for C16H16Br2ClF6N4PPd(707.81):C,27.03;H,2.27;N,7.88.Found:C,27.30;H,2.08;N,7.65.
实施例6
将6-溴吡啶-2-甲醛(30mmol,5.58g)和2,2-二甲基-1,3-丙二胺(15mmol,1.53g)在30mL甲醇中混合,室温反应7.0小时后,冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g),慢慢升温至70℃反应5小时。停止反应,冷却至室温,旋干反应液。再用50mL CH2Cl2溶解、过滤,滤液旋干,得黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后,再向其中加入等摩尔量甲醛水溶液,室温搅拌3小时后,减压除去溶剂,柱层析分离纯化得3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)六氢嘧啶(5.23g,产率77%)。
将3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)六氢嘧啶(5mmol,2.27g)溶于30mLDME,再向其中加入NBS(5mmol,0.89g),室温搅拌3小时后,抽滤得淡黄色粉末,经二氯甲烷-***重结晶得3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)四氢嘧啶溴鎓盐。将3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后蒸干,再用CH2Cl2溶解、过滤,将滤液旋蒸,残留物用二氯甲烷-***重结晶得3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐纯品(2.60g,产率87%)。
在Schlenk瓶中加入3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol,1.20g)和PdCl2(2mmol,0.35g),氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL),油浴140℃搅拌12h。反应结束后,将反应液冷却至室温,过滤,滤液经柱层析分离纯化(梯度洗脱,展开剂:正己烷/二氯甲烷=1/10~1/20),得钳形扩环氮杂环卡宾钯化合物(VI)。浅黄色固体(0.75g,51%).1H NMR(400MHz,DMSO-d6):δ8.28-8.24(m,2H,Py-H),7.90(d,J=7.3Hz,2H,Py-H),7.73-7.70(m,2H,Py-H),5.40(d,J=15.1Hz,2H,picolyl-CH2),4.81(d,J=15.2Hz,2H,picolyl-CH2),3.30(d,J=3.1Hz,4H,pyrimidine-CH2),0.80(s,6H,CH3)ppm;13C NMR(100MHz,DMSO-d6):δ174.1,155.4,154.5,141.9,125.9,125.7,62.0,59.0,28.3,23.8ppm;Anal Cacld for C18H20Br2ClF6N4PPd(735.84):C,29.25;H,2.73;N,7.58;Found:C,28.99;H,2.80;N,7.43.
实施例7
其它步骤同上。
在Schlenk瓶中加入1,3-二(2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol,0.82g)和PdCl2(2mmol,0.35g),氩气保护下加入NaN(SiMe3)2(2.1mmol)和甲苯(8mL),油浴120℃搅拌20h。反应结束后,将反应液冷却至室温,过滤,滤液经柱层析分离纯化(梯度洗脱,展开剂:正己烷/二氯甲烷=1/10~1/20),得钳形扩环氮杂环卡宾钯化合物(I)。数据见实施实例1。
实施例8:
其它步骤同上。
在Schlenk瓶中加入1,3-二(2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol,0.82g)和PdCl2(2mmol,0.35g),氩气保护下加入KN(SiMe3)2(2.1mmol)和吡啶(6mL),油浴140℃搅拌12h。反应结束后,将反应液冷却至室温,过滤,滤液经柱层析分离纯化(梯度洗脱,展开剂:正己烷/二氯甲烷=1/10~1/20),得钳形扩环氮杂环卡宾钯化合物(I)。数据见实施例1。
应用例:
部分C-N偶联催化反应实例:
将卤代芳烃(1.0mmol)、胺(3.0mmol)、碱(2.0mmol)、本发明钳形扩环氮杂环卡宾钯化合物催化剂(0.01mmol)加入到溶剂中,微波辐射下于50~100℃反应10~40分钟后,降至室温,减压除去溶剂,柱色谱分离得到纯品。
部分催化反应结果如下表:
以上数据显示了所合成的钳形扩环氮杂环卡宾钯化合物对C-N偶联反应具有很好的催化效果。而C-N偶联反应在有机合成、药物研发以及功能性材料开发等具有重要的地位,本发明合成的钳形扩环氮杂环卡宾钯化合物具有很好的应用前景。
Claims (1)
1.结构式如下的含吡啶甲基的扩环氮杂环卡宾钯化合物在催化C-N偶联反应中的应用,其特征在于,通过如下步骤实现:
,
将含吡啶甲基的扩环氮杂环卡宾钯化合物催化剂、碱、卤代芳烃、胺加入到溶剂中,在微波辐射下于50~100℃反应10~40分钟后,降至室温,减压除去溶剂,柱色谱分离得到芳胺。
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