CN112876516B - N-(4-吲哚基)氮杂环卡宾钯络合物及应用 - Google Patents
N-(4-吲哚基)氮杂环卡宾钯络合物及应用 Download PDFInfo
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- CN112876516B CN112876516B CN202110167141.2A CN202110167141A CN112876516B CN 112876516 B CN112876516 B CN 112876516B CN 202110167141 A CN202110167141 A CN 202110167141A CN 112876516 B CN112876516 B CN 112876516B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 36
- -1 4-indolyl Chemical group 0.000 title claims description 58
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 title claims description 17
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 abstract description 8
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 abstract description 7
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 5
- SZXWBDRHZNYHHX-UHFFFAOYSA-N [N]C1=CC=CC2=C1C=CN2 Chemical compound [N]C1=CC=CC2=C1C=CN2 SZXWBDRHZNYHHX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 43
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 22
- 239000002994 raw material Substances 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000010898 silica gel chromatography Methods 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 12
- 239000003446 ligand Substances 0.000 description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 101150003085 Pdcl gene Proteins 0.000 description 10
- 238000010790 dilution Methods 0.000 description 10
- 239000012895 dilution Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- PWRBCZZQRRPXAB-UHFFFAOYSA-N 3-chloropyridine Chemical compound ClC1=CC=CN=C1 PWRBCZZQRRPXAB-UHFFFAOYSA-N 0.000 description 9
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006464 oxidative addition reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SWGQITQOBPXVRC-UHFFFAOYSA-N methyl 2-bromobenzoate Chemical compound COC(=O)C1=CC=CC=C1Br SWGQITQOBPXVRC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 238000010651 palladium-catalyzed cross coupling reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- PRLDILURXJMICQ-UHFFFAOYSA-N 4-[(4-aminophenyl)methoxymethyl]aniline Chemical compound C1=CC(N)=CC=C1COCC1=CC=C(N)C=C1 PRLDILURXJMICQ-UHFFFAOYSA-N 0.000 description 1
- JZLFHSJOLKQDKU-UHFFFAOYSA-O C1=CNC2=CC=CC([N+]3=CNC=C3)=C12 Chemical class C1=CNC2=CC=CC([N+]3=CNC=C3)=C12 JZLFHSJOLKQDKU-UHFFFAOYSA-O 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 238000006411 Negishi coupling reaction Methods 0.000 description 1
- 101100060071 Schizosaccharomyces pombe (strain 972 / ATCC 24843) cis4 gene Proteins 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229940052810 complex b Drugs 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
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- 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
- B01J31/22—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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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
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- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- 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
- C07C213/08—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 not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- 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
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- 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
- B01J2231/4227—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 with Y= Cl
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Abstract
本发明公开了一类化学结构通式如下式所示的N‑(4‑吲哚基)氮杂环卡宾钯络合物；
本发明提供的钯络合物可用于催化Suzuki‑Miyaura偶联、Buchwald–Hartwig反应等交叉偶联反应。
Description
技术领域
本发明属于化学合成与金属有机催化技术领域，涉及一类N-(4-吲哚基)氮杂环卡宾钯络合物，此类络合物可用于催化Suzuki-Miyaura偶联、Buchwald–Hartwig反应等交叉偶联反应。
背景技术
金属催化的交叉偶联反应在制药、农业化学和材料科学等合成应用领域中起着重要作用。近年来，氮杂环卡宾(NHC)配体逐步应用于钯催化交叉偶联，显示出良好的催化效果，引发了人们对NHC-Pd络合物的关注。
常见的钯催化交叉偶联反应包括Suzuki-Miyaura偶联、Heck反应、Negishi反应、Sonogashira反应、Buchwald-Hartwig反应等。以钯催化的Suzuki-Miyaura偶联为例，其催化机理过程可分为三个基元步骤，即氧化加成、转金属和还原消除。第一步氧化加成(OA)是零价金属钯(Pd0)对碳卤键的插入，产生二价钯(PdII)络合物，受碳卤键的强弱和周边基团体积所影响；第二步将碳亲核试剂配位到缺电子的金属钯中心，由富电子的亲核试剂促进；最后一步还原消除(RE)是两个碳配体间成键形成产物，同时金属钯由PdII恢复到Pd0，通常由体积较大的基团或配体所促进。内侧带有大体积取代基的NHC配体能使金属钯周围的空间位阻效应显著增大，缩短两个碳配体间的距离，有利于还原消除步骤，同时抑制β-氢消除。此外，此类大体积NHC配体也能减少钯原子的配体数，从而增强氧化加成步骤的活性。
目前钯催化的各类交叉偶联反应已被广泛应用。然而，在这一领域仍然存在着相当多的挑战。例如，钯催化剂在催化过程中易析出钯单质，不仅使催化剂的寿命缩短、催化性降低，也使产物纯化困难。此外，对于大位阻反应，催化效率也往往较低。因此，如何提高催化剂的稳定性和催化效率是非常关键的问题。
发明内容
本发明目的在于提供一类N-(4-吲哚基)氮杂环卡宾钯络合物，该类化合物的化学结构通式如下：
式中：R选自
C1-C25的饱和或芳香的取代基；
Y选自H、Cl；
R1、R2、R3、R4、R5、R6、R7、R8、R9选自氢、C1-C15的饱和或芳香的取代基。
R5还可以通过C3-C8的饱和碳链与R6相连。
R为C1-C25的饱和或芳香的取代基，C1-C25的饱和或芳香的取代基为含碳环、含直链或支侧链的取代基；C1-C25的饱和或芳香的取代基选自甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、异戊基、环戊基、己基、异己基、环己基、庚基、环己甲基、辛基、壬基、癸基、苄基、二苯基甲基、苯基、邻甲苯基、间甲苯基、对甲苯基、联苯基、萘基、蒽基、芘基、并四苯基、2,3-二甲基苯基、2,4-二甲基苯基、2,5-二甲基苯基、2,6-二甲基苯基、2,6-二乙基苯基、2,6-二正丙基苯基、2,6-二异丙基苯基、2,6-二正丁基苯基、2,6-二仲丁基苯基、2,6-二(3-戊基)苯基、2,4,6-三甲基苯基。
R1、R2、R3、R4、R5、R6、R7、R8或R9为C1-C15的饱和或芳香的取代基，C1-C15的饱和或芳香的取代基为含碳环、含直链或支侧链的取代基；C1-C15的饱和或芳香的取代基选自甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、戊基、3-戊基、环戊基、己基、环己基、庚基、环己基甲基、辛基、壬基、癸基、苄基、苯基。
本发明基于交叉偶联反应的特点，设计了N-(4-吲哚基)氮杂环卡宾与金属钯络合的NHC-Pd催化剂，由于这类催化剂的NHC配体具有较大的空间体积和内侧位阻，有利于促进交叉偶联反应的进行。
此类催化剂的合成制备分为两个步骤：
第一步先以苯胺类化合物为原料分别合成对应的N-(4-吲哚基)咪唑盐和咪唑啉盐(即氮杂环卡宾前体NHC-HX)，参考“Yan,H.；Liu,Z.X.；Tan,K.；Tan,K.；Ji,R.G.；Ye,Y.X.；Yan,T.B.；Shen,Y.H.Synthesis and evaluation of indole-substituted N-heterocyclic carbeneligands.Tetrahedron Lett.2020,61,152450”中的方法制得；
第二歩以合成得到的NHC-HX在碱性条件下与金属钯盐进行络合，合成相应的NHC-Pd络合物；
本发明另一目的是将上述N-(4-吲哚基)氮杂环卡宾钯络合物作为催化剂应用在交叉偶联反应中。
本发明的优点和技术效果：
1、本发明使用的含有吲哚侧链的NHC配体具有较强的配位能力和空间位阻效应，有助于提高钯络合物的稳定性；
2、本发明使用的含有吲哚侧链的NHC配体两侧可引入不同位阻的基团，可实现对配体结构的微调和优化；
3、本发明通过调节侧链取代基得到内侧位阻大和电子云密度高的氮杂环卡宾钯络合物，更有利于催化交叉偶联反应。
附图说明
图1为X-单晶衍射鉴定的络合物d晶体结构；
图2为X-单晶衍射鉴定的络合物i晶体结构。
具体实施方式
以下对本发明技术方案的具体实施方式详细描述，但并不构成对本发明保护范围的限定。本发明实施例中所使用的试剂均为市售的化学纯试剂，下述实施例中原料N-(4-吲哚基)氮杂环卡宾前体咪唑盐或咪唑啉盐按照文献中方法制备(H.Yan et al.,Tetrahedron Lett.2020,61,152450)。
实施例1：N-(4-吲哚基)氮杂环卡宾钯络合物a的制备
以3-(2-乙基-1,3,5,7-四甲基-1H-吲哚-4-基)-1-(2,6-二异丙基苯基)-4,5-二氢-1H-咪唑-3-氯化物(41mg)为原料，向干燥的厚壁耐压瓶中依次加入磁力搅拌子、PdCl2(17mg)、原料(41mg)、K2CO3(61mg)和吡啶(1mL)，氩气置换后旋上瓶塞，在80℃下搅拌过夜，反应完全后，冷却至室温；向反应体系中加入DCM稀释，硅藻土过滤，DCM洗涤，滤液浓缩后，用硅胶柱层析法进行纯化，得到的产物a为淡黄色固体(34mg,56.2％)；
1H NMR(600MHz,CDCl3)δ8.40(d,J＝5.1Hz,2H),7.40(t,J＝7.6Hz,1H),7.33(t,J＝7.7Hz,1H),7.31–7.25(m,1H),7.20–7.19(m,1H),7.01–6.93(m,2H),6.73(s,1H),4.04–4.00(m,4H),3.90–3.87(m,1H),3.83(s,3H),3.35–3.31(m,1H),2.73–2.64(m,5H),2.62(s,3H),2.48(s,3H),1.53–1.52(d,J＝6.6Hz,3H),1.46–1.45(d,J＝6.6Hz,3H),1.22–1.20(d,J＝6.9Hz,3H),1.18–1.16(d,J＝6.9Hz,3H),1.09(t,J＝7.5Hz,3H).
13C NMR(150MHz,CDCl3)δ184.9,151.5,147.9,147.6,140.3,137.3,135.4,135.2,129.4,128.9,126.7,126.6,126.3,124.5,123.9,121.5,105.7,53.9,32.6,29.0,28.4,27.0,24.7,24.1,20.8,18.7,17.9,14.3,10.8.
HRMS(ESI)m/z:[M+H]+calcd forC29H40N3430.3218,found 430.3217.
实施例2：N-(4-吲哚基)氮杂环卡宾钯络合物b的制备
以3-(2-乙基-1,3,5,7-四甲基-1H-吲哚-4-基)-1-间甲苯基-4,5-二氢-1H-咪唑-3-氯化物(61mg)为原料，向干燥的厚壁耐压瓶中依次加入磁力搅拌子、PdCl2(28mg)、原料(61mg)、K2CO3(99mg)、3-氯吡啶(1mL)，氩气置换后旋上瓶塞，在110℃下搅拌过夜；反应完全后，冷却至室温，向反应体系中加入DCM稀释，硅藻土过滤，DCM洗涤。滤液浓缩后，用硅胶柱层析法进行纯化，得到的产物b为淡黄色固体(42mg,43％)；
1H NMR(600MHz,CDCl3)δ8.41(d,J＝2.3Hz,1H),8.32(dd,J＝5.6,1.2Hz,1H),7.42(ddd,J＝8.2,2.2,1.4Hz,1H),7.00–6.90(m,3H),6.73(s,1H),4.22–4.01(m,3H),3.95–3.91(m,1H),3.85(s,3H),2.74–2.67(m,4H),2.67–2.60(m,4H),2.56(s,3H),2.49(s,3H),2.47(s,3H),2.26(s,3H),1.10–1.07(t,J＝7.6Hz,3H).
13C NMR(150MHz,CDCl3)δ182.8,150.5,149.6,140.4,138.5,137.6,137.4,136.9,135.3,131.8,129.7,128.2,126.9,126.7,126.3,124.2,121.6,110.1,105.6,53.8,51.0,32.7,21.3,20.8,19.5,18.6,17.9,14.3,11.0.
HRMS(ESI)m/z:[M+H]+calcd for C26H34N3 388.2745,found 388.2747.
实施例3：N-(4-吲哚基)氮杂环卡宾钯络合物c的制备
以3-(2-乙基-1,3,5,7-四甲基-1H-吲哚-4-基)-1-(2,6-二异丙基苯基)-4,5-二氢-1H-咪唑-3-氯化物(58mg)为原料，向干燥的厚壁耐压瓶中依次加入磁力搅拌子、PdCl2(24mg)、原料(58mg)、K2CO3(86mg)、3-氯吡啶(1mL)，氩气置换后旋上瓶塞，在110℃下搅拌过夜。反应完全后，冷却至室温，向反应体系中加入DCM稀释，硅藻土过滤，DCM洗涤；滤液浓缩后，用硅胶柱层析法进行纯化，得到的产物c为淡黄色固体(44mg,49％)；
1H NMR(600MHz,CDCl3)δ8.46(d,J＝2.1Hz,1H),8.38(d,J＝5.5Hz,1H),7.42(d,J＝8.3Hz,1H),7.34(t,J＝7.7Hz,1H),7.27(d,J＝7.6Hz,1H),7.20(d,J＝1.0Hz,1H),6.93(dd,J＝8.1,5.7Hz,1H),6.73(s,1H),4.03(dt,J＝8.6,4.4Hz,4H),3.87(d,J＝6.6Hz,1H),3.84(s,3H),3.32(dt,J＝13.3,6.6Hz,1H),2.74–2.70(m,1H),2.68(s,3H),2.64(dd,J＝15.2,7.7Hz,1H),2.60(s,3H),2.48(s,3H),1.52(d,J＝6.6Hz,3H),1.46(d,J＝6.5Hz,3H),1.21(d,J＝6.8Hz,3H),1.17(d,J＝6.9Hz,3H),1.09(t,J＝7.5Hz,3H).
13C NMR(150MHz,CDCl3)δ183.7,150.5,149.5,147.9,147.5,140.3,137.4,135.3,131.9,129.5,128.7,126.8,126.6,126.3,124.6,124.3,121.6,105.7,53.9,32.6,29.0,28.4,27.0,24.7,24.1,20.8,18.7,17.9,14.3,10.8.
HRMS(ESI)m/z:[M+H]+calcd for C29H40N3430.3217,found 430.3217.
实施例4：N-(4-吲哚基)氮杂环卡宾钯络合物d的制备
以3-(1,9二甲基-5,6,7,8-四氢化-1H-咔唑-4-基)-1-(2,6-二异丙基苯基)-1H-咪唑-3-高氯酸盐(72mg)为原料，向干燥的厚壁耐压瓶中依次加入磁力搅拌子、PdCl2(26mg)、原料(72mg)、K2CO3(94mg)、3-氯吡啶(1mL)，氩气置换后旋上瓶塞，在110℃下搅拌过夜。反应完全后，冷却至室温，向反应体系中加入DCM稀释，硅藻土过滤，DCM洗涤。滤液浓缩后，用硅胶柱层析法进行纯化，得到的产物d为淡黄色固体(57mg,57.9％)。
1H NMR(600MHz,CDCl3)δ8.54(d,J＝2.0Hz,1H),8.46(dd,J＝5.6,1.3Hz,1H),7.64(d,J＝7.6Hz,1H),7.46(ddd,J＝11.2,6.1,4.5Hz,2H),7.31–7.29(m,2H),7.20(d,J＝1.9Hz,1H),6.98–6.96(m,2H),6.92(dd,J＝7.6,0.7Hz,1H),3.84(s,3H),3.24(dt,J＝13.6,6.8Hz,1H),3.00(dt,J＝13.5,6.7Hz,1H),2.76(s,3H),2.63(dt,J＝15.0,4.9Hz,2H),2.20(ddd,J＝14.6,7.7,5.3Hz,1H),1.94–1.90(m,1H),1.71(ddd,J＝15.4,10.2,6.3Hz,2H),1.60–1.53(m,2H),1.37(d,J＝6.6Hz,3H),1.33(d,J＝6.7Hz,3H),1.06(d,J＝6.9Hz,3H),0.98(d,J＝6.9Hz,3H).
13C NMR(150MHz,CDCl3)δ151.3,150.5,149.6,147.3,147.1,137.7,137.5,136.7,134.9,132.0,130.4,129.3,125.4,124.9,124.4,124.0,123.2,122.0,120.4,108.5,32.3,28.7,28.4,26.9,26.2,23.3,23.1,23.0,22.9,22.0,20.6.
HRMS(ESI)m/z:[M+H]+calcd for C29H37N3426.2903,found 426.2904.
X-射线单晶衍射鉴定的d晶体结构见图1。
实施例5：N-(4-吲哚基)氮杂环卡宾钯络合物e的制备
以3-(2-乙基-1,3,5,7-四甲基-1H-吲哚-4-基)-1-(2,6-二异丙基苯基)-1H-咪唑-3-高氯酸盐(58mg)为原料，向干燥的厚壁耐压瓶中依次加入磁力搅拌子、PdCl2(21mg)、原料(58mg)、K2CO3(76mg)、3-氯吡啶(1mL)，氩气置换后旋上瓶塞，在110℃下搅拌过夜。反应完全后，冷却至室温，向反应体系中加入DCM稀释，硅藻土过滤，DCM洗涤。滤液浓缩后，用硅胶柱层析法进行纯化，得到的产物e为淡黄色固体(41mg,52.1％)；
1H NMR(600MHz,CDCl3)δ8.50(d,J＝2.1Hz,1H),8.41(dd,J＝5.5,1.2Hz,1H),7.45–7.41(m,2H),7.33–7.30(m,1H),7.26(d,J＝7.7Hz,1H),7.11(d,J＝1.8Hz,1H),7.06(d,J＝1.8Hz,1H),6.95(dd,J＝8.0,5.7Hz,1H),6.77(s,1H),3.87(s,3H),3.53(dt,J＝13.4,6.7Hz,1H),2.79(dd,J＝13.4,6.7Hz,1H),2.73(s,3H),2.70–2.66(m,1H),2.61(dd,J＝15.1,7.5Hz,1H),2.38(s,3H),1.91(s,3H),1.44(d,J＝6.6Hz,3H),1.37(d,J＝6.6Hz,3H),1.11(d,J＝6.8Hz,3H),1.07(t,J＝7.5Hz,3H),0.99(d,J＝6.9Hz,3H).
13C NMR(150MHz,CDCl3)δ152.4,150.6,149.6,147.0,146.6,140.6,137.4,135.1,131.9,130.3,127.8,126.5,126.3,125.8,125.4,125.1,124.3,123.9,122.1,105.6,32.7,29.0,28.4,27.0,26.1,23.4,23.1,20.8,18.5,17.8,14.3,10.1.
HRMS(ESI)m/z:[M+H]+calcd for C29H38N3 428.3061,found 428.306.
实施例6：N-(4-吲哚基)氮杂环卡宾钯络合物f的制备
以3-(2-乙基-1,3,5,7-四甲基-1H-吲哚-4-基)-1-间甲苯基-1H-咪唑-3-高氯酸盐(61mg)为原料，向干燥的厚壁耐压瓶中依次加入磁力搅拌子、PdCl2(24mg)、原料(61mg)、K2CO3(87mg)、3-氯吡啶(1mL)，氩气置换后旋上瓶塞，在110℃下搅拌过夜；反应完全后，冷却至室温，向反应体系中加入DCM稀释，硅藻土过滤，DCM洗涤。滤液浓缩后，用硅胶柱层析法进行纯化，得到的产物f为淡黄色固体(44mg,52％)；
1H NMR(600MHz,CDCl3)δ8.49(d,J＝2.2Hz,1H),8.40(dd,J＝5.6,1.2Hz,1H),7.43(ddd,J＝8.2,2.2,1.3Hz,1H),7.13(d,J＝1.9Hz,1H),7.01(s,1H),6.99(d,J＝1.9Hz,1H),6.97(s,1H),6.94(dd,J＝8.1,5.6Hz,1H),6.76(s,1H),3.87(s,3H),2.73(s,3H),2.68(dd,J＝15.1,7.6Hz,1H),2.60(dd,J＝15.1,7.6Hz,1H),2.42(s,3H),2.34(s,3H),2.31(s,3H),2.25(s,3H),1.89(s,3H),1.07(t,J＝7.5Hz,3H).
13C NMR(150MHz,CDCl3)δ151.2,150.6,149.7,140.6,139.2,137.4,136.7,136.1,135.4,135.1,131.8,129.4,127.7,126.7,126.2,125.8,124.2,123.5,122.1,105.7,32.7,21.4,20.8,19.4,18.3,17.8,14.3,10.1.
HRMS(ESI)m/z:[M+H]+calcd for C26H32N3 386.2591,found 386.2591.
实施例7：N-(4-吲哚基)氮杂环卡宾钯络合物g的制备
以1,3-双(2-乙基-1,3,5,7-四甲基-1H-吲哚-4-基)-1H-咪唑-3-氯化物(49mg)为原料，向干燥的厚壁耐压瓶中依次加入磁力搅拌子、PdCl2(19mg)、原料(49mg)、K2CO3(67mg)、3-氯吡啶(1mL)，氩气置换后旋上瓶塞，在110℃下搅拌过夜。反应完全后，冷却至室温，向反应体系中加入DCM稀释，硅藻土过滤，DCM洗涤。滤液浓缩后，用硅胶柱层析法进行纯化，得到的产物g为淡黄色固体(trans/cis4:1,32mg,43.7％)；
1H NMR(600MHz,CDCl3)δ8.59–8.58(m,1H),(8.50–8.48,8.42–8.41)(m,1H),7.47(ddd,J＝8.2,2.3,1.4Hz,1H),(7.20,7.18)(ds,2H),6.98(dd,J＝8.1,5.6Hz,1H),(6.85,6.81)(ds,2H),(3.96,3.94)(ds,6H),2.80(d,J＝2.5Hz,6H),2.76–2.66(m,4H),(2.5,2.33)(ds,6H),(2.16,1.99)(ds,6H),1.16–1.13(m,6H).
13C NMR(150MHz,CDCl3)δ151.4,150.8,149.9,140.5,137.3,135.3,135.1,131.7,128.1,127.6,126.3,126.0,125.6,125.3,124.1,121.9,105.8,32.7,20.8,18.5,17.8,14.3,10.9,10.3.
HRMS(ESI)m/z:[M+H]+calcd for C31H39N4 467.3166,found 467.3169.
实施例8：N-(4-吲哚基)氮杂环卡宾钯络合物h的制备
以3-(2-丙基-3-已基-1,5,7-三甲基-1H-吲哚-4-基)-1-(2,6-二异丙基苯基)-1H-咪唑-3-高氯酸盐(58mg)为原料，向干燥的厚壁耐压瓶中依次加入磁力搅拌子、PdCl2(20mg)、原料(58mg)、K2CO3(72mg)、3-氯吡啶(1mL)，氩气置换后旋上瓶塞，在110℃下搅拌过夜。反应完全后，冷却至室温，向反应体系中加入DCM稀释，硅藻土过滤，DCM洗涤。滤液浓缩后，用硅胶柱层析法进行纯化，得到的产物h为淡黄色固体(66mg,62.3％)；
1H NMR(600MHz,CDCl3)δ8.53(d,J＝2.2Hz,1H),8.47–8.44(m,1H),7.50(t,J＝7.7Hz,2H),7.38–7.36(m,1H),7.34(d,J＝7.7Hz,1H),7.26–7.25(m,1H),7.13(d,J＝1.7Hz,1H),7.00(dd,J＝8.1,5.6Hz,1H),6.83(s,1H),3.93(s,3H),3.50(dt,J＝13.5,6.7Hz,1H),2.99(dt,J＝13.4,6.7Hz,1H),2.80(s,3H),2.65(ddd,J＝14.7,10.7,5.5Hz,2H),2.47(dd,J＝15.4,7.7Hz,1H),2.39(s,3H),2.24(dd,J＝15.3,7.6Hz,1H),1.61–1.57(m,2H),1.50(d,J＝6.6Hz,3H),1.46(d,J＝6.6Hz,3H),1.16(d,J＝6.9Hz,3H),1.11(d,J＝6.9Hz,3H),1.03(t,J＝7.3Hz,3H),0.94(t,J＝7.6Hz,3H).
13C NMR(150MHz,CDCl3)δ152.5,150.7,149.7,147.0,146.6,139.6,137.4,135.2,131.8,130.4,127.6,126.8,126.2,125.1,124.7,124.3,123.9,122.2,113.5,32.9,28.9,28.6,26.8,26.3,23.6,23.4,23.0,20.9,18.5,17.8,14.4.
HRMS(ESI)m/z:[M+H]+calcd for C31 H42 N3 456.3375,found 456.3373.
实施例9：N-(4-吲哚基)氮杂环卡宾钯络合物i的制备
以3-(2-乙基-1,3,5,7-四甲基-1H-吲哚-4-基)-1-间甲苯基-1H-咪唑-3-高氯酸盐(64mg)为原料，向干燥的厚壁耐压瓶中依次加入磁力搅拌子、PdCl2(24mg)、原料(64mg)、K2CO3(86mg)、3-氯吡啶(1mL)，氩气置换后旋上瓶塞，在110℃下搅拌过夜。反应完全后，冷却至室温，向反应体系中加入DCM稀释，硅藻土过滤，DCM洗涤。滤液浓缩后，用硅胶柱层析法进行纯化，得到的产物i为淡黄色固体(47mg,53.6％)；
1H NMR(600MHz,CDCl3)δ8.52(d,J＝2.2Hz,1H),8.43(dd,J＝5.6,1.3Hz,1H),7.48(ddd,J＝8.2,2.3,1.4Hz,1H),7.27(d,J＝1.9Hz,1H),7.07(s,1H),7.05–7.03(m,2H),6.99(dd,J＝8.2,5.6Hz,1H),6.83(s,1H),3.93(s,3H),2.80(s,3H),2.69–2.59(m,2H),2.49(s,3H),2.47–2.43(m,1H),2.37(d,J＝5.4Hz,6H),2.34(s,3H),2.19(dd,J＝15.3,7.6Hz,1H),1.62–1.56(m,2H),1.02(t,J＝7.3Hz,3H),0.93(t,J＝7.6Hz,3H).
13C NMR(150MHz,CDCl3)δ151.5,150.6,149.7,139.6,139.2,137.4,136.6,136.2,135.3,131.8,129.4,127.4,126.9,126.1,125.5,124.7,124.2,123.4,122.2,113.6,32.9,26.9,23.6,21.4,20.8,19.3,18.6,18.3,17.9,14.4.
HRMS(ESI)m/z:[M+H]+calcd for C28H36N3 414.2906,found 414.2904.
X-射线单晶衍射鉴定的i晶体结构见图2。
实施例10：N-(4-吲哚基)氮杂环卡宾钯络合物j的制备
以1,3-双(2-丙基-3-已基-1,5,7-三甲基-1H-吲哚-4-基)-1H-咪唑-3-氯化物(65mg)为原料，向干燥的厚壁耐压瓶中依次加入磁力搅拌子、PdCl2(22mg)、原料(65mg)、K2CO3(80mg)、3-氯吡啶(1mL)，氩气置换后旋上瓶塞，在110℃下搅拌过夜。反应完全后，冷却至室温，向反应体系中加入DCM稀释，硅藻土过滤，DCM洗涤。滤液浓缩后，用硅胶柱层析法进行纯化，得到的产物j为淡黄色固体(trans/cis 7:3,38mg,40.8％)；
1H NMR(600MHz,CDCl3)δ(8.52–8.51,8.34–8.35)(m,1H),8.44–8.40(m,1H),7.45–7.41(m,1H),(7.28,7.25)(ds,2H),6.97–6.92(m,1H),(6.84,6.80)(ds,2H),(3.94,3.92)(ds,6H),(2.79,2.29)(ds,6H),2.68–2.60(m,4H),(2.56–2.53,2.47–2.44)(m,2H),(2.52–2.51,2.15–2.12)(m,2H),(2.50,2.29)(ds,6H),1.61–1.57(m,4H),1.04–0.96(m,12H).
13C NMR(150MHz,CDCl3)δ151.8,150.8,149.8,139.5,139.3,137.1,135.4,135.2,131.6,127.8,126.7,126.3,124.9,124.6,124.3,124.1,122.1,113.8,32.9,29.8,26.9,23.6,20.9,18.8,18.5,18.3,18.1,17.9,14.4.
HRMS(ESI)m/z:[M+H]+calcd for C35H47N4523.3802,found 523.3795.
上述实施例制得的N-(4-吲哚基)氮杂环卡宾钯络合物的Suzuki-Miyaura偶联反应催化活性测试
实施例11：溴苯与苯硼酸Suzuki-Miyaura偶联反应的测试
向装有磁力搅拌子的干燥反应管中依次加入N-(4-吲哚基)氮杂环卡宾钯络合物(2mol％)、苯硼酸(1.2mmol)和K2CO3(3mmol)，氩气置换后加入溴苯(1mmol)和1,4-二氧六环(2mL)。将反应混合物在80℃下加热12h，硅藻土过滤，乙酸乙酯冲洗，滤液用水洗涤，乙酸乙酯萃取水相(4mL)，萃取2次，有机层合并，无水Na2SO4干燥，过滤、浓缩后经硅胶柱层析纯化(PE:EA＝20:1)得到相应的产物。
催化活性评价结果如表1，以Organ等发展的Pd-PEPPSI-IPr作为参照催化剂。
表1.N-(4-吲哚基)NHC-Pd络合物催化溴苯与苯硼酸偶联反应
实施例12：2-溴苯甲酸甲酯与苯硼酸Suzuki-Miyaura偶联反应的测试
在装有磁力搅拌子的干燥反应管中依次加入N-(4-吲哚基)氮杂环卡宾钯络合物(2mol％)、苯硼酸(1.2mmol)和K2CO3(2.6mmol)，氩气置换后加入溴苯(1mmol)和1,4-二氧六环(2mL)。将反应混合物在80℃下加热12h，硅藻土过滤，乙酸乙酯冲洗。滤液用水洗涤，乙酸乙酯萃取水相(4mL)，萃取2次，有机层合并，无水Na2SO4干燥，过滤、浓缩后经硅胶柱层析纯化(PE:EA＝20:1)得到相应的产物。
催化活性评价结果如表2，以Organ等发展的Pd-PEPPSI-IPr作为参照催化剂。
表2.N-(4-吲哚基)NHC-Pd络合物催化2-溴苯甲酸甲酯与苯硼酸偶联反应
实施例13：2-氯甲苯与1-萘硼酸Suzuki-Miyaura偶联反应的测试
在装有磁力搅拌子的反应管中依次加入叔丁醇钾(1.30mmol)和N-(4-吲哚基)氮杂环卡宾钯络合物(1mol％)，氩气置换后加入异丙醇(1.5mL)，室温搅拌，颜色从淡黄色到红色(棕色或灰绿色，约30min)后加入1-萘硼酸(1.20mmol)和2-氯甲苯(1.00mmol)，反应在室温下搅拌约2h。反应液用乙醚(2mL)稀释，硅藻土过滤，乙醚冲洗。滤液用水洗涤，乙醚萃取水相(4mL)，萃取2次，有机层合并，无水Na2SO4干燥，过滤、浓缩后经硅胶柱层析纯化(PE:EA＝10:1)得到相应的产物。
催化活性评价结果如表3，以Organ等发展的Pd-PEPPSI-IPr作为参照催化剂。
表3.N-(4-吲哚基)NHC-Pd络合物催化2-氯甲苯与1-萘硼酸偶联反应
上述实施例制得的N-(4-吲哚基)氮杂环卡宾钯络合物的Buchwald–Hartwig偶联反应催化活性测试
实施例14：4-硝基氯苯与4-氨基苯甲醚Buchwald–Hartwig偶联反应测试
在装有磁力搅拌子的反应管中依次加入N-(4-吲哚基)氮杂环卡宾钯络合物(4mol％)、4-硝基氯苯(1mmol)、Cs2CO3(3mmol)、4-氨基苯甲醚(1.5mmol)和DME(1mL)，氩气置换后在80℃下加热24h。反应液用乙酸乙酯(2mL)稀释，硅藻土过滤，乙酸乙酯冲洗。滤液用水洗涤，乙酸乙酯萃取水相(4mL)，萃取2次，有机层合并，Na2SO4干燥，过滤、浓缩后经硅胶柱层析纯化(PE:EA＝5:1)，得到相应的产物。
催化活性评价结果如表4，以Organ等发展的Pd-PEPPSI-IPr作为参照催化剂。
表4.N-(4-吲哚基)NHC-Pd络合物催化4-硝基氯苯与4-氨基苯甲醚偶联反应
实施例15：4-硝基氯苯与苯胺Buchwald–Hartwig偶联反应测试
在装有磁力搅拌子的反应管中依次加入N-(4-吲哚基)氮杂环卡宾钯络合物(4mol％)、4-硝基氯苯(1mmol)、Cs2CO3(3mmol)、苯胺(1.5mmol)和DME(1mL)，氩气置换后将反应混合物在80℃下加热24h。反应液用乙酸乙酯(2mL)稀释，硅藻土过滤，乙酸乙酯冲洗。滤液用水洗涤，乙酸乙酯萃取水相(4mL)，萃取2次，有机层合并，Na2SO4干燥，过滤、浓缩后经硅胶柱层析纯化(PE:EA＝5:1)，得到相应的产物。
催化活性评价结果如表5，以Organ等发展的Pd-PEPPSI-IPr作为参照催化剂。
表5.N-(4-吲哚基)NHC-Pd络合物催化4-硝基氯苯与苯胺偶联反应
实施例16：4-硝基氯苯与邻甲苯胺Buchwald–Hartwig偶联反应测试
在装有磁力搅拌子的反应管中依次加入N-(4-吲哚基)氮杂环卡宾钯络合物(4mol％)、4-硝基氯苯(1mmol)、Cs2CO3(3mmol)、邻甲苯胺(1.5mmol)和DME(1mL)，氩气置换后将反应混合物在80℃下加热24h。反应液用乙酸乙酯(2mL)稀释，硅藻土过滤，乙酸乙酯冲洗。有机层用水洗涤，乙酸乙酯萃取水相(4mL)，萃取2次，有机层合并，Na2SO4干燥，过滤、浓缩后经硅胶柱层析纯化(PE:EA＝5:1)，得到相应的产物；
催化活性评价结果如表6，以Organ等发展的Pd-PEPPSI-IPr作为参照催化剂；
表6.N-(4-吲哚基)NHC-Pd络合物催化4-硝基氯苯与邻甲苯胺偶联反应
以上所述仅是本发明的优选实施方式。应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还可进行若干改进和补充，这些可能的改进和补充也应视为本发明的保护范围。
Claims (3)
1.化学结构通式如下式所示的N-(4-吲哚基)氮杂环卡宾钯络合物：
式中：R选自
；
Y选自H、Cl；
R1、R2、R3、R4、R5、R6、R7、R8、R9选自氢、C1-C15的饱和或芳香的取代基，其中C1-C15的饱和或芳香的取代基选自甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、戊基、3-戊基、环戊基、己基、环己基、庚基、环己基甲基、辛基、壬基、癸基、苄基、苯基。
2.根据权利要求1所述的N-(4-吲哚基)氮杂环卡宾钯络合物，其特征在于：R5通过C3-C8的饱和碳链与R6相连。
3.权利要求1-2任一项所述的N-(4-吲哚基)氮杂环卡宾钯络合物在作为交叉偶联反应催化剂中的应用。
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