CN115197279B - 一类(sp3)C^C螯合环钯金属配合物及其合成方法和应用 - Google Patents
一类(sp3)C^C螯合环钯金属配合物及其合成方法和应用 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 43
- -1 palladium metal complex Chemical class 0.000 title claims abstract description 33
- 239000013522 chelant Substances 0.000 title claims description 15
- 238000010189 synthetic method Methods 0.000 title description 2
- 238000005859 coupling reaction Methods 0.000 claims abstract description 8
- 238000001308 synthesis method Methods 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 13
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 11
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- KKKDZZRICRFGSD-UHFFFAOYSA-N 1-benzylimidazole Chemical compound C1=CN=CN1CC1=CC=CC=C1 KKKDZZRICRFGSD-UHFFFAOYSA-N 0.000 claims description 3
- PAPPEKHULAQSEJ-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)propanenitrile Chemical compound N#CC(C)C1=NC=CN1 PAPPEKHULAQSEJ-UHFFFAOYSA-N 0.000 claims description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 230000005595 deprotonation Effects 0.000 claims description 2
- 238000010537 deprotonation reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- FGOJCPKOOGIRPA-UHFFFAOYSA-N 1-o-tert-butyl 4-o-ethyl 5-oxoazepane-1,4-dicarboxylate Chemical compound CCOC(=O)C1CCN(C(=O)OC(C)(C)C)CCC1=O FGOJCPKOOGIRPA-UHFFFAOYSA-N 0.000 claims 1
- 235000010357 aspartame Nutrition 0.000 claims 1
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- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
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- 125000004122 cyclic group Chemical group 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- 150000000177 1,2,3-triazoles Chemical class 0.000 description 1
- VQDKUWYOXTUWGQ-UHFFFAOYSA-N 1-benzyl-2-propan-2-ylimidazole Chemical class CC(C)C1=NC=CN1CC1=CC=CC=C1 VQDKUWYOXTUWGQ-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- CQPGDDAKTTWVDD-UHFFFAOYSA-N 4-bromobutanenitrile Chemical compound BrCCCC#N CQPGDDAKTTWVDD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000010651 palladium-catalyzed cross coupling reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004445 quantitative analysis 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
- 239000000741 silica gel Substances 0.000 description 1
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- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
- B01J31/22—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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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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
- B01J2231/4261—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
- 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
- B01J2531/824—Palladium
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Abstract
本发明属于金属有机配合物的合成与性能技术领域,具体涉及一种(sp3)C^C螯合的环钯金属配合物及其合成方法和应用。13C核磁共振波谱法证明本发明的C^C二齿配体具有极强供电子能力。在Mizoroki‑Heck偶联反应中,这类环钯配合物较未成环的配合物和已有的环钯配合物均表现出更为优异的催化活性。
Description
技术领域
本发明属于金属有机配合物的合成与性能技术领域,具体涉及一类(sp3)C^C螯合环钯金属配合物及其合成方法和应用。
背景技术
钯金属配合物在金属有机领域,特别是金属催化方向占据重要作用,在工业上被广泛应用于C-C,C-X成键反应以高效构建结构复杂的功能分子(“钯催化交叉偶联反应”,2010年诺贝尔化学奖)。
1995年,Hermann最早报道了一种环钯配合物前驱体,并将其用于C-C偶联反应。环钯配合物因其结构所特有的富电子性而表现出了很高的催化活性[Angew.Chem.Int.Ed.1995,34,1844;Angew.Chem.Int.Ed.1995,34,1848]。随后,一系列由P,N,O,S^C螯合的环钯配合物被陆续合成,也在多类偶联反应中表现出了优异的催化活性[Angew.Chem.Int.Ed.2002,41,3668;J.Catal.2022,405,84;Coord.Chem.Rev.2021,427,213546]。
上述环钯配合物的配位C原子大多为芳基碳原子,或者特殊的苄基碳原子,而由更常见烷基(有βC-H的)参与配位的环钯配合物却较少报道。究其原因,可能一方面源于普通烷基更低的酸性,使C-H活化更为困难;另一方面,所得C-Pd配合物更易发生βC-H消除导致分解。
发明内容
为了发展C(sp3)参与螯合的环钯金属配合物及其应用,本发明提供了一类C(sp3)C^C螯合的稳定环钯金属配合物(本发明中也可简称为C^C二齿配体),结构式如下:
式中,R为吸电子基团,X为Cl、Br、I中的任意一种,n为1或2。
进一步的,R为取代基-CN、-COOCH3或-COPh中的任意一种。
本发明还提供了上述(sp3)C^C螯合环钯金属配合物的制备方法,反应路线如下:
当n=1时,包括如下步骤:
以含有吸电子基团取代烷基的氮杂环卡宾配合物为原料,在碱性条件下,取代基的α-CH2发生去质子化并与钯配位,生成n=1时的C^C螯合钯金属配合物C(carbene)^C(sp3)。
进一步的,在溶剂中,将含有吸电子基团取代烷基的氮杂环卡宾配合物与碱性物质NaOH室温搅拌反应(反应时间优选12小时),反应结束后,分离得到C^C螯合钯金属配合物,其中碱性物质选自NaOH、KOH、LiOH、NaH、叔丁醇钾中的任意一种。
更进一步的,溶剂为乙腈、四氢呋喃、丙酮、乙腈与四氢呋喃混合液、二氯甲烷与甲醇混合液中的任意一种。
当n=2时,包括如下步骤:以含有吸电子基团取代烷基的氮杂环卡宾配合物为原料,在惰性气体(优选氮气)保护下,以乙腈、四氢呋喃、二甲基甲酰胺、二甲基亚砜中的任意一种或多种的混合物做溶剂,加入碱性物质(用量优选1.5当量),在反应温度下制得n=2时的C^C螯合钯金属配合物,其中碱性物质为叔丁醇钾、氢化钠、双(三甲基硅烷基)氨基钾中的任意一种。
上述含有吸电子基团取代烷基的氮杂环卡宾配合物的结构式如下:
本发明还提供了上述含有吸电子基团取代烷基的氮杂环卡宾配合物的合成方法,包括以下步骤:含吸电子基团取代烷基咪唑前体盐与0.5当量的[PdX2(iPr2-bimy)]2溶解在二氯甲烷中,加入0.6当量的氧化银避光反应(反应时间优选4小时)得到。
含吸电子基团取代烷基咪唑前体盐的结构通式为:
本发明还提供了上述含吸电子基团取代烷基咪唑前体盐的合成方法,包括以下步骤:在溶剂中,以苄基咪唑和4-卤丁腈为原料(n=2),或以1-氰乙基咪唑、1-甲酯乙基咪唑、1-苯甲酮乙基咪唑和苄卤为原料(n=1),在反应温度下得到(反应条件优选90℃反应12小时)。
进一步的,溶剂为甲苯、四氢呋喃、乙腈、二甲基甲酰胺、二甲基亚砜中的任意一种或多种。
在成功获得并对上述配合物进行完全表征后,这些配合物中的探针iPr2-bimy卡宾碳的13C位移被用于分析右侧C^C二齿配体的供电子能力(HEP法),结果表明这类C(carbene)^C(sp3)二齿配体的推电子能力优于常见的N^N、C^N、C(carbene)^C(carbene)配体,但弱于一类1,2,3-三氮唑衍生的异常卡宾C^C二齿配体。
本发明还提供了上述(sp3)C^C环钯金属配合物在催化Heck偶联反应中的应用。
对比大多(sp2)C环钯配合物[J.Org.Chem.2012,77,2729;Dalton Trans.2015,44,5805],本发明中的(sp3)C^C环钯配合物具有对不同底物均具有明显更好的催化活性,周转数(TON)可高达105。相比已报道的(sp3)C环钯配合物,也体现出较强的竞争力[Angew.Chem.Int.Ed.1995,34,1844;J.Chem.Sci.2015,127,1919]。
相较未成环的配合物前体,环钯金属配合物普遍具有更高的催化活性。申请者推测,环钯配合物在催化条件下,能够经历如下步骤缓慢生成有效的Pd(0)活性物种(以4d为例),以催化溴代芳烃和丙烯酸叔丁酯的偶联反应。
本发明的优点和技术效果:
本发明基于设计合成的一系列含有吸电子基团取代烷基的氮杂环卡宾配合物首次成功制备了C(carbene)^C(sp3)螯合配位的环钯金属配合物。13C核磁共振波谱法证明这类新型的(sp3)C^C二齿配体具有极强的供电子能力,因而能够很好地稳定钯金属中心。在Heck偶联催化条件下,环钯配合物能够与底物作用,缓慢释放[Pd(0)]活性物种,因而表现出优异的催化活性。
附图说明:
图1为化合物3c单晶结构图。
图2为化合物4b单晶结构图(异丙基省略)。
图3为本发明C(carbene)^C(sp3)二齿配体及其他代表性二齿配体的推电子能力示意图(基于iPr2-bimy探针配体的13C NMR位移)。
具体实施方式
下面结合实施例对本发明作进一步详述说明,X为Br为例,但这并不表示对本发明的限制,当X为Cl、I两种卤素时亦可获得相应的C(carbene)^C(sp3)二齿配体,实施例中将不再一一给出。
以下实施例中配合物3与4的合成路线如下:
实施例1
(1)1-氰乙基-3-苄基咪唑盐1a的合成
将1-氰乙基咪唑(888mg,7.33mmol)和溴化苄(1.3mL,10.99mmol)溶于甲苯(5mL),置于密封管中90℃下搅拌3小时,减压蒸馏除去甲苯后,用二氯甲烷(2×5mL)洗涤残渣,得到产物。
1a:白色粘性固体,产率85%。1H NMR(300MHz,CDCl3+CD3OD):δ9.83(s,1H,NCHN),7.83(d,1H,3J=2Hz,Imi-H),7.34-7.30(m,6H,Ar-H&Imi-H),5.40(s,2H,NCH2),4.72-4.66(m,2H,NCH2),3.22-3.17(m,2H,NCCH2);13C{1H}NMR(75MHz,CDCl3+CD3OD):δ137.3(NCHN),133.0,130.2,130.0,129.3,123.8,122.8(Ar-C),117.3(CN),54.1,45.9,20.4(CH2).Anal.Calcd.for C13H14BrN3:C 53.44,H 4.83,N 14.38;found:C 53.67,H 4.82,N14.02.MS(ESI):m/z 212[M-Br]+.
(2)卡宾配合物3a的合成
50mL的圆底烧瓶中加入1a(188mg,0.64mmol)、化合物2(294mg,0.31mmol)、氧化银(89mg,0.38mmol)和二氯甲烷(20mL),避光反应4小时后,硅藻土过滤并真空脱除溶剂得产物。
3a:淡黄色固体,产率93%。1H NMR(500MHz,CDCl3):δ7.59-7.52(m,4H,Ar-H),7.45-7.33(m,3H,Ar-H),7.22-7.19(m,2H,Ar-H),7.02(d,3J=2Hz,1H,Imi-H),6.77(d,3J=2Hz,1H,Imi-H),6.13(m,3J=7Hz,1H,NCH),5.99(m,3J=7Hz,1H,NCH),5.76(s,2H,NCH2),4.88(t,3J=7Hz,2H,NCH2),3.40(t,3J=7Hz,2H,NCCH2),1.84(d,3J=7Hz,6H,CH3),1.68(d,3J=7Hz,6H,CH3);13C{1H}NMR(75MHz,CDCl3):δ178.1(Ccarbene-benz),172.9(Ccarbene-imi),136.2,134.21,134.17,129.6,129.3,129.1,122.8,122.2,121.1(Ar-C,两组峰重合),117.9(CN),113.32,113.27(Ar-C),55.4,54.8,54.5,47.4,21.7,21.6,20.4(CH,CH2 andCH3).Anal.Calcd.for C26H31Br2N5Pd:C 45.94,H 4.60,N 10.30;found:C 45.78,H 4.83,N10.06.MS(ESI):m/z 598[M-Br]+.
(3)C^C螯合环钯配合物4a的合成
将3a(85mg,0.12mmol)溶于乙腈(5mL)和四氢呋喃(5mL)混合溶液,加入氢氧化钠(8mg,0.20mmol)后的悬浮液室温搅拌12小时,真空脱除溶剂加入二氯甲烷(10mL)经硅藻土过滤后用乙醚(2×5mL)洗涤得产物。
4a:灰白色固体,产率98%。1H NMR(300MHz,CDCl3):δ7.64-7.61(m,1H,Ar-H),7.58-7.56(m,1H,Ar-H),7.47-7.45(m,2H,Ar-H),7.40-7.30(m,3H,Ar-H),7.23-7.20(m,2H,Ar-H),6.99(d,3J=2Hz,1H,Imi-H),6.72(d,3J=2Hz,1H,Imi-H),6.08-5.85(m,4H,NCH&NCH2),4.20-4.08(m,2H,NCH2),2.99-2.95(m,1H,CH),1.87(d,3J=7Hz,3H,CH3),1.79-1.74(m,9H,CH3);13C{1H}NMR(75MHz,CDCl3):δ185.8(Ccarbene-benz),175.9(Ccarbene-imi),137.6,134.7,134.1,129.4,129.3,128.6,127.2,122.7,122.6,121.9(Ar-C),118.4(CN),113.7,113.2(Ar-C),54.9,54.8,54.6,54.5,22.4,22.1,21.8,21.6,8.0(CH,CH2 and CH3).Anal.Calcd.for C26H30BrN5Pd:C 52.14,H 5.05,N 11.69;found:C 52.46,H 4.97,N11.58.MS(ESI):m/z 518[M-Br]+.
实施例2
(1)1-甲酯乙基-3-苄基咪唑盐1b的合成
将(719mg,4.66mmol)和溴化苄(665μL,5.59mmol)溶于甲苯(10mL)后,置于密封管中90℃下搅拌12小时,减压蒸馏除去甲苯后,用乙醚(2×5mL)洗涤残渣,得到产物。
1b:白色粘性固体,产率98%。1H NMR(300MHz,CDCl3):δ10.14(s,1H,NCHN),7.63(t,3J=2Hz,1H,Imi-H),7.45-7.42(m,2H,Ar-H)7.33-7.30(m,4H,Ar-H&Imi-H),5.52(s,2H,NCH2),4.61(t,3J=6Hz,2H,NCH2),3.58((s,3H,CH3),3.03(t,3J=6Hz,2H,CH2CO);13C{1H}NMR(75MHz,CDCl3):δ171.4(CO),137.4(NCHN),133.6,129.9 129.8,129.5(Ar-C),123.8,122.4(Ar-C),53.7,52.8,45.9,35.0(CH2,CH3).Anal.Calcd.for C14H17BrN2O2:C51.71,H 5.27,N 8.61;found:C 51.88,H 5.87,N 8.98(多次测试后的最佳结果).MS(ESI):m/z 245[M-Br]+.
(2)卡宾配合物3b的合成
50mL的圆底烧瓶中加入1b(104mg,0.32mmol)、化合物2(150mg,0.16mmol)、氧化银(46mg,0.20mmol)和二氯甲烷(20mL),避光反应4小时后,硅藻土过滤并浓缩,进行硅胶柱层析(洗脱剂:石油醚/乙酸乙酯/二氯甲烷=2/1/1,V/V/V),得到产物。
3b:淡黄色固体,产率73%。1H NMR(300MHz,CDCl3):δ7.57-7.51(m,4H,Ar-H),7.42-7.33(m,3H,Ar-H),7.21-7.16(m,2H,Ar-H),7.00(d,3J=2Hz,1H,Imi-H),6.70(d,3J=2Hz,1H,Imi-H),6.22(m,3J=7Hz,1H,NCH),5.99(m,3J=7Hz,1H,NCH),5.75(s,2H,NCH2),4.86(t,3J=7Hz,1H,NCH2),3.75(s,3H,OCH3),3.31(t,3J=7Hz,1H,NCH2),1.81(d,3J=7Hz,6H,CH3),1.68(d,3J=7Hz,6H,CH3);13C{1H}NMR(75MHz,CDCl3):δ179.2(Ccarbene-benz),172.4(CO),171.6(Ccarbene-imi),136.7,134.3,134.2,129.5,129.3,128.9,122.9,122.6,121.3,(Ar-C,两组峰重合),113.2(Ar-C,两组峰重合),55.3,54.6,54.4,52.7,47.1,36.2,21.7,21.6(CH,CH2 and CH3).Anal.Calcd.for C27H34Br2N4O2Pd:C 45.49,H 4.81,N 7.86;found:C 45.78,H 4.83,N 7.75.MS(ESI):m/z 631[M-Br]+.
(3)C^C螯合环钯配合物4b的合成
25mL的圆底烧瓶中加入3b(218mg,0.30mmol)、氢氧化钠(8mg,0.20mmol)、乙腈(5mL),室温搅拌12小时,真空脱除溶剂后加入二氯甲烷(10mL),硅藻土过滤浓缩进行硅胶柱层析(洗脱剂:石油醚/乙酸乙酯/二氯甲烷-甲醇/二氯甲烷=8/1/1-1/30,V/V/V),得到产物。
4b:黄色固体,产率34%。1H NMR(300MHz,CDCl3):δ7.60-7.57(m,2H,Ar-H),7.46-7.43(m,2H,Ar-H),7.37-7.29(m,3H,Ar-H),7.21-7.16(m,2H,Ar-H),6.99(d,3J=2Hz,1H,Imi-H),6.69(d,3J=2Hz,1H,Imi-H),6.12(m,3J=7Hz,1H,NCH),5.93(s,2H,NCH2),5.80(m,3J=7Hz,1H,NCH),4.41(dd,3J=7Hz,2J=12Hz,1H,NCHH),4.00(dd,3J=7Hz,2J=12Hz,1H,NCHH),3.53(t,3J=7Hz,1H,COCH),2.96(s,3H,OCH3),1.78(dd,3J=7Hz,2J=12Hz,9H,CH3),1.71(d,3J=7Hz,3H,CH3);13C{1H}NMR(75MHz,CDCl3):δ189.4(Ccarbene-benz),180.3(CO),175.7(Ccarbene-imi),138.2,134.3,134.0,129.2,128.4,122.4,122.3,121.4,118.3(Ar-C,),113.4,113.1,(Ar-C),54.8,54.6,54.3,54.2,54.1,50.7,21.7,21.1(CH,CH2 and CH3).Anal.Calcd.for C27H33BrN4O2Pd:C 51.32;H 5.26;N 8.87;found:C 51.48,H 5.62,N8.53.MS(ESI):m/z 551[M-Br]+.
实施例3
(1)1-苯甲酮乙基-3-苄基咪唑盐1c的合成
将3-咪唑基-1-苯乙酮(200mg,1.00mmol)、溴化苄(147μL,1.20mmol)溶于甲苯(10mL)置于密封管中50℃下搅拌12小时,减压蒸馏除去甲苯后,用甲苯(3×10mL)洗涤残渣,得到产物。
1c:白色固体,产率77%。1H NMR(300MHz,CDCl3):δ 10.44(s,1H,NCHN),7.94(d,3J=3Hz,2H,Ar-H),7.68(s,1H,Imi-H),7.55-7.51(m,1H,Ar-H),7.49-7.33(m,7H,Ar-H),7.19(s,1H,Imi-H),5.46(s,2H,NCH2),4.76(d,3J=6Hz,2H,NCH2),3.84(d,3J=6Hz,2H,CH2);13C{1H}NMR(75MHz,CDCl3):δ197.6(CO),137.9(NCHN),136.1,134.6,133.4,130.1,130.1,129.4,129.4,128.9(Ar-C),124.5,121.8(Ar-C),54.1,45.4,39.9(CH2).Anal.Calcd.for C19H19BrN2O:C 61.47,H 5.16,N 7.55;found:C 61.58,H 5.43,N7.76.MS(ESI):m/z 291[M-Br]+.
(2)卡宾配合物3c的合成
50mL的圆底烧瓶中加入1c(74mg,0.20mmol)、2(94mg,0.10mmol)、氧化银(25mg,0.11mmol)和二氯甲烷(20mL),避光反应4小时后,硅藻土过滤并浓缩,进行硅胶柱层析(洗脱剂:石油醚/乙酸乙酯/二氯甲烷=8/1/1-2/1/1,V/V/V),得到产物。
3c:黄色固体,产率69%。1H NMR(300MHz,CDCl3):δ8.06(d,3J=7Hz 2H,Ar-H),7.53-7.35(m,12H,Ar-H),7.19-7.16(m,2H,Ar-H),7.04(br s,1H,Imi-H),6.68(br-s,1H,Imi-H),6.17(m,3J=7Hz,1H,NCH),6.01(m,3J=7Hz,1H,NCH),5.75(s,2H,NCH2),5.01(t,3J=7Hz,2H,NCH2C),4.10(t,3J=7Hz,1H,CH2CO),1.70(d,3J=7Hz,12H,CH3);13C{1H}NMR(75MHz,CDCl3):δ 198.6(CO),179.2(Ccarbene-benz),171.2(Ccarbene-imi),137.1,136.6,134.2,134.1,129.5,129.4,129.3,128.9,128.8,123.3,122.6(Ar-C,两组峰重合),121.0,113.2(Ar-C),55.2,54.5,54.4,46.5,40.6,21.6,21.5(CH,CH2 and CH3).Anal.Calcd.forC32H36Br2N4OPd:C 50.65,H 4.78,N 7.38;found:C 50.78,H 4.99,N 7.36.MS(ESI):m/z677[M-Br]+.
(3)C^C螯合环钯配合物4c的合成
25mL的圆底烧瓶中加入3c(60mg,0.08mmol)、氢氧化钠(5.5mg,0.14mmol)、乙腈(5mL),室温搅拌12小时,真空脱除溶剂加入二氯甲烷(10mL)经硅藻土过滤后用乙醚(2×5mL)洗涤得产物。
4c:淡黄色固体,产率98%。1H NMR(300MHz,CDCl3):δ7.59-7.56(m,2H,Ar-H),7.45-7.28(m,10H,Ar-H),7.19-7.15(m,2H,Ar-H),7.06(d,3J=2Hz,1H,Imi-H),6.70-6.85(m,2H,Ar-H),6.71(d,3J=2Hz,1H,Imi-H),6.24-6.11(m,3J=7Hz,1H,NCH),5.89(d,3J=7Hz,2H,NCH2),5.40-5.30(m,3J=7Hz,1H,NCH),4.73-4.70(m,1H,CHC0),4,35-4.30(m,1H,NCH2CH),1.84-1.74(m,9H,CH3),1.53(d,3J=7Hz,3H,CH3);13C{1H}NMR(75MHz,CDCl3):δ201.9(CO)187.8(Ccarbene-benz),175.2(Ccarbene-imi),138.8,138.1,134.8,134.0,131.7,129.2,129.1,128.5,128.2,128.0,122.4,122.3,121.3,118.3(Ar-C),113.3,113.0(Ar-C),54.5,54.4,54.3,54.2,41.3,22.1,21.9,21.7,20.4(CH,CH2 and CH3).Anal.Calcd.forC32H35BrN4OPd:C 56.69,H 5.20,N 8.26;found:C 56.89,H 5.48,N 8.46.MS(ESI):m/z 597[M-Br]+.
实施例4
(1)1-氰丙基-3-苄基咪唑盐1d的合成
将苄基咪唑(475mg,3mmol)和4-溴丁腈(327μL,3.3mmol)溶于甲苯(10mL)后,置于密封管中90℃下搅拌3小时,减压蒸馏除去甲苯后,用乙醚(3×10mL)洗涤残渣,得到产物。
1d:白色固体,产率83%。1H NMR(300MHz,CDCl3):δ10.42(s,1H,NCHN),7.65(d,3J=3Hz,1H,Imi-H),7.45-7.37(m,5H,Ar-H)7.23(d,3J=3Hz,1H,Imi-H),5.50(s,2H,NCH2),4.62(t,3J=6Hz,2H,NCH2),2.69(t,3J=6Hz,2H,CH2),2.42-2.33(m,2H,NCCH2);13C{1H}NMR(75MHz,CDCl3):δ137.4(NCHN),132.5,129.8,129.7,129.1(Ar-C),122.8,121.9(Ar-C),118.7(CN),53.8,48.6,26.2,14.7(CH2).Anal.Calcd.for C14H16BrN3:C 54.92,H5.27,N13.72;found:C 55.02,H 5.39,N 13.48.MS(ESI):m/z 226[M-Br]+.
(2)卡宾配合物3d的合成
50mL的圆底烧瓶中加入1a(15mg,0.05mmol)、2(24mg,0.025mmol)氧化银(6mg,0.0275mmol)和二氯甲烷(5mL),避光反应4小时后,硅藻土过滤并真空脱除溶剂得产物。
3d:淡黄色固体,产率94%。1H NMR(300MHz,CDCl3):δ7.58-7.50(m,4H,Ar-H),7.43-7.35(m,3H,Ar-H),7.20-7.17(m,2H,Ar-H),6.94(d,3J=2Hz,1H,Imi-H),6.78(d,3J=2Hz,1H,Imi-H),6.11(m,3J=7Hz,1H,NCH),6.03(m,3J=7Hz,1H,NCH),5.81(s,2H,NCH2),4.67(t,3J=7Hz,1H,NCH2),2.63(t,3J=7Hz,1H,CCH2C),2.54(t,3J=7Hz,1H,NCCH2),1.81(d,3J=7Hz,6H,CH3),1.63(d,3J=7Hz,6H,CH3);13C{1H}NMR(75MHz,CDCl3):δ178.5(Ccarbene-benz),171.8(Ccarbene-imi),136.5,134.1,134.2,129.6,129.0,128.9,122.7,122.5,122.0(Ar-C),119.5(CN),113.3,113.3(Ar-C),55.3,54.6,54.4,49.8,27.09,21.66,21.45(CH2,CH3),15.32(CCN).Anal.Calcd.for C27H33Br2N5Pd:C 46.74,H4.79,N 10.09;found:C46.87,H 4.98,N 10.45.MS(ESI):m/z 612[M-Br]+.
(3)C^C螯合环钯配合物4d的合成
在氮气保护下,50mL Schlenk反应管中加入4d(310mg,0.45mmol)(15mL)和叔丁醇钾(76mg,0.67mmol)。加热60°反应12小时,真空干燥除去溶剂,加入10mL二氯甲烷悬浮液经硅藻土过滤后浓缩进行硅胶柱层析(洗脱剂:石油醚/乙酸乙酯/二氯甲烷=2/1/1,V/V/V),得到产物。
4d:淡黄色固体,产率96%。1H NMR(300MHz,CDCl3):δ7.60-7.54(m,2H,Ar-H),7.49-7.47(m,2H,Ar-H),7.42-7.32(m,3H,Ar-H),7.22-7.18(m,2H,Ar-H),6.88(d,3J=2Hz,1H,Imi-H),6.74(d,3J=2Hz,1H,Imi-H),6.17(d,3J=15Hz,1H,CH2),5.89(m,3J=7Hz,2H,NCH),5.59(d,3J=15Hz,1H,CH2),4.15-4.08(m,2H,CH2),2.66(t,3J=7Hz 1H,NCH),2.20-2.09(m,1H,CH2),1.77(d,3J=7Hz,3H,CH3),1.74-1.71(m,7H,CH2&CH3),1.67(d,3J=7Hz,3H,CH3).13C{1H}NMR(75MHz,CDCl3):δ188.4(Ccarbene-benz),175.9(Ccarbene-imi),137.8,134.4,134.0,129.4,129.1,128.8,128.4,122.7,122.6,121.5(Ar-C),120.9(CN),113.5,113.2(Ar-C),55.2,54.6,54.5,52.5,22.3,22.0,21.7,21.5(CH,CH2 and CH3).Anal.Calcd.for C27H32BrN5Pd:C52.91,H 5.26,N 11.43;found:C 52.79,H 5.60,N11.67.MS(ESI):m/z 532[M-Br]+.
实施例5本发明C^C二齿配体推电子能力
配合物4a-d均含有一个苯并咪唑衍生的iPr2-bimy探针配体,其13Ccarbene核磁共振位移可用于确定这类C^C二齿配体的推电子能力(HEP法)。对比有相同吸电子基团的配合物4a和4d,配合物4d的13Ccarbene-benz在更低场位置(表1),表明氰丙基取代卡宾具有更强的推电子能力,这是由于丙基中额外的CH2的+I效应所致。相同碳数、不同吸电子基团的配合物4a、4b和4c的13Ccarbene-benz位移比较则表明,甲酯取代的卡宾配体的推电子能力最强,其次为苯甲酮乙基和氰乙基取代的卡宾配体。与已报道的其它二齿配体相比,这类C(carbene)^C(sp3)二齿配体的推电子能力优于常见的N^N、C^N、C(carbene)^C(carbene)配体,但弱于一类1,2,3-三氮唑衍生的异常卡宾C^C二齿配体[Inorg.Chem.2014,53,10964;Dalton.Trans.2018,47,7830;Dalton Trans.,2019,48,7546]。
表1
实施例6本发明配合物的催化应用
空气氛围下,将芳基卤化物(0.20mmol)、丙烯酸叔丁酯(0.30mmol)、钯催化剂(3d/4d)、醋酸钠(0.30mmol)和DMF(200μL)溶剂和内标十二烷(0.20mmol)加入到反应瓶中,120℃下反应14h后,吸取一滴反应液加二氯甲烷稀释至2mL,气相色谱法进行定量分析。
结果表明对三种不同取代的溴代芳烃底物参与的Heck偶联反应,环钯配合物4d较未成环的配合物3d均表现出更高的催化活性(表2)。特别是在低催化剂计量下(0.001mol%),4d仍能表现出较好的催化活性,最高周转数可达到105。这比绝大多数(sp2)C环钯配合物的催化活性高,即使相比已报道的(sp3)C环钯配合物,也体现出较强的竞争力。
表2
。
Claims (8)
1.一类(sp3)C^C螯合的环钯金属配合物,其特征在于:结构式如下:
,
式中,X为Cl、Br、I中的任意一种,n为1或2;
R为取代基-CN、-COOCH3或-COPh中的任意一种。
2.如权利要求1所述的(sp3)C^C螯合环钯金属配合物的制备方法,其特征在于:当n=1时,包括如下步骤:以含有吸电子基团取代烷基的氮杂环卡宾配合物为原料,在碱性条件下,取代基的a-CH2发生去质子化并与钯配位,生成n=1时的C^C螯合钯金属配合物;
或者,当n=2时,包括如下步骤:以含有吸电子基团取代烷基的氮杂环卡宾配合物为原料,在惰性气体保护下,以乙腈、四氢呋喃、二甲基甲酰胺、二甲基亚砜中的任意一种或多种的混合物做溶剂,加入碱性物质,在反应温度下制得n=2时的C^C螯合钯金属配合物,其中碱性物质为叔丁醇钾、氢化钠、双(三甲基硅烷基)氨基钾中的任意一种;
上述含有吸电子基团取代烷基的氮杂环卡宾配合物的结构式如下:
。
3.如权利要求2所述的(sp3)C^C螯合环钯金属配合物的制备方法,其特征在于:当n=1时,步骤还包括在溶剂中,将含有吸电子基团取代烷基的氮杂环卡宾配合物与碱性物质在反应温度下搅拌反应,反应结束后,分离得到C^C螯合环钯金属配合物,其中碱性物质选自NaOH、KOH、LiOH、NaH、叔丁醇钾中的任意一种。
4.如权利要求3所述的(sp3)C^C螯合环钯金属配合物的制备方法,其特征在于:当n=1时,步骤中溶剂为乙腈、四氢呋喃、丙酮、乙腈与四氢呋喃混合液、二氯甲烷与甲醇混合液中的任意一种。
5. 如权利要求2所述的(sp3)C^C螯合环钯金属配合物的制备方法,其特征在于:含有吸电子基团取代烷基的氮杂环卡宾配合物的合成方法,包括以下步骤:含吸电子基团取代烷基咪唑前体盐与0.5当量的 [PdX2( i Pr2-bimy)]2溶解在二氯甲烷中,加入0.6当量的氧化银避光反应得到;
含吸电子基团取代烷基咪唑前体盐的结构通式为:
;
[PdX2( i Pr2-bimy)]2结构式为:
。
6.如权利要求5所述的(sp3)C^C螯合环钯金属配合物的制备方法,其特征在于:所述含吸电子基团取代烷基咪唑前体盐的合成方法,包括以下步骤:n=2,在溶剂中,以苄基咪唑和4-卤丁腈为原料,在反应温度下得到;
或者,n=1,在溶剂中,以1-氰乙基咪唑、1-甲酯乙基咪唑、1-苯甲酮乙基咪唑和苄卤为原料,在反应温度下得到。
7.如权利要求5所述的(sp3)C^C螯合环钯金属配合物的制备方法,其特征在于:含吸电子基团取代烷基咪唑前体盐的合成方法中所用溶剂为甲苯、四氢呋喃、乙腈、二甲基甲酰胺、二甲基亚砜中的任意一种或多种。
8.根据权利要求1所述的(sp3)C^C螯合的环钯金属配合物的应用,其特征在于:用作Heck偶联反应的催化剂。
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