CN107262151B - 芳杂环醇环钯金属催化剂及其应用 - Google Patents
芳杂环醇环钯金属催化剂及其应用 Download PDFInfo
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- CN107262151B CN107262151B CN201710516767.3A CN201710516767A CN107262151B CN 107262151 B CN107262151 B CN 107262151B CN 201710516767 A CN201710516767 A CN 201710516767A CN 107262151 B CN107262151 B CN 107262151B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 125000006615 aromatic heterocyclic group Chemical group 0.000 title claims abstract description 17
- 125000003158 alcohol group Chemical group 0.000 title claims abstract description 14
- -1 camphoryl Chemical group 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 238000007341 Heck reaction Methods 0.000 claims abstract description 6
- 238000006254 arylation reaction Methods 0.000 claims abstract description 6
- 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 abstract description 6
- 238000007333 cyanation reaction Methods 0.000 claims abstract description 5
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims abstract description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 3
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003446 ligand Substances 0.000 description 9
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010499 C–H functionalization reaction Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 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
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910004373 HOAc Inorganic materials 0.000 description 1
- QPIBFUDWZPSXSZ-UHFFFAOYSA-N [CH-]1C=CC=C1.[CH-]1C=CC=C1.[Fe+2].C1(=CC=CC=C1)PC1=CC=CC=C1.C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical compound [CH-]1C=CC=C1.[CH-]1C=CC=C1.[Fe+2].C1(=CC=CC=C1)PC1=CC=CC=C1.C1(=CC=CC=C1)PC1=CC=CC=C1 QPIBFUDWZPSXSZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical group 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
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- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D215/14—Radicals substituted by oxygen atoms
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- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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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
本发明提供了一种芳杂环醇环钯金属催化剂，其为具有式(1)或式(2)所示的结构的化合物或相应化合物的盐；式中，n为1或2；R1、R2和R3独立的为氢(H)、甲基(CH3)、丙基(C3H7)、正丁基(n‑C4H9)、正己基(n‑C6H13)、环己基、金刚烷基、樟脑基、Ph、p‑OCH3‑Ph、p‑F‑Ph或芴基。本发明还提供了所述的芳杂环醇环钯金属催化剂在芳杂环醇环钯金属催化剂在芳环氰基化反应、芳杂环C‑H活化芳基化反应、芳杂环氧化脱氢Heck反应和Suzuki偶联反应中的应用。
Description
技术领域
本发明属于有机金属化学领域，具体涉及一种芳杂环醇环钯金属催化剂及其应用，更具体涉及吡啶或喹啉杂环醇为配体的环钯金属催化剂的合成及应用。
背景技术
众所周知，普通的金属钯盐催化剂因为廉价、效能高不仅在有机合成而且在工业上都有着广泛地应用。但该类催化剂通常存在投用量大、反应条件苛刻、副反应多等问题，且大都需要引入价格昂贵的配体，既提高了转化成本也造成了环境污染。相较之下，有机环钯类催化剂具有反应条件温和、催化活性和选择性高、大多无需外加配体等优势，更经济环保和符合绿色化学的理念。
但是目前的有机环钯类催化剂种类仍十分单一，且存在部分缺陷亟待解决的问题。
此处列举出若干环钯催化剂及其存在的缺陷，具体如下：
中国专利文献CN1741797A公开了一类含有双二苯基膦-二茂铁配位配体的环钯催化剂，其具有如下的结构，其可以作为肽和酶的抑制剂，通过作用于酶并参与DNA分子的插入，这些化合物调控免疫系统，但该专列并未对其催化性能进行研究，更未将其应用于有机催化领域。
中国专利文献CN101007825A公开了一种二茂铁基咪唑啉环钯化合物，其具有如下的结构，其作为催化剂可催化Suzuki偶联反应，但反应温度相对较高(70-150℃)，且未将其应用于其他有机催化领域。
CN101903865A公开了一种环钯化二茂铁亚胺-氨基膦配合物催化剂，其具有如下的结构，对其反应活性的研究仅局限于催化氯代芳烃制备芳香胺衍生物的反应，未涉及其他类型有机反应。
CN101113138A公开了一种环钯化二茂铁亚胺-氨基膦配合物催化剂，其具有如下的结构，其可以用于催化芳基腈类衍生物的合成，但存在着反应温度较高(100-150℃)等问题，且未涉及其他有机反应。
CN101274288A公开了一种可循环叔胺环钯化合物催化剂，其具有如下的结构，其可以用于Suzuki偶联反应中，其反应温度也较高(105℃)，而且需要联吡啶作为配体。
CN101306388A公开了一种具有轴手性联萘骨架含膦配体的环钯催化剂，其具有如下的结构，其可以用于S在不对称催化有机硼试剂对杂原子降冰片二烯开环，该类环钯配合物含有芳基膦配体。
CN102500417A公开了一种磁性肟环钯催化剂，其具有如下的结构，可循环用于Suzuki偶联反应中，但是该类催化剂制备步骤较为复杂。
CN1188481A公开了一种基于含吡啶或喹啉部分的二齿配位体的钯催化剂，其具有如下的结构，其可以用于催化乙烯聚合，但未涉及有机小分子的官能化或偶联。
目前罕有环钯催化剂能同时在多种不同类型的有机催化反应中均取得较好技术效果的报道，且大多数环钯催化剂在有机催化领域的应用仍然存在各种技术效果较差的缺陷。
发明内容
本发明的一个目的在于克服现有技术合成部分化合物存在的合成路线复杂、普适性差等缺陷，同时进一步拓展丰富环钯催化剂的种类，提供一种新的芳杂环醇环钯金属催化剂，该芳杂环醇环钯金属催化剂可以用于Suzuki偶联反应、芳杂环的氧化脱氢Heck反应、卤代(杂)芳烃的氰化反应和多种芳杂环的C-H活化芳基化反应的催化。
本发明提供的芳杂环醇环钯金属催化剂为为具有式(1)或式(2)所示的结构的化合物或相应化合物的盐：
上式中，n为1或2。
作为上述技术方案一种更好的选择，所述n为1。
作为上述技术方案一种更好的选择，所述n为2。
上式中，R1、R2和R3独立的为氢(H)、甲基(CH3)、丙基(C3H7)、正丁基(n-C4H9)、正己基(n-C6H13)、环己基、金刚烷基、樟脑基、Ph、p-OCH3-Ph、p-F-Ph或芴基。
作为上述技术方案一种较好的选择，所述R1和R2独立的为Ph、CH3、C3H7，且环合为环己基。
作为上述技术方案一种较好的选择，所述n为1，所述R1为Ph，所述R2为Ph。
作为上述技术方案一种较好的选择，所述n为1，所述R1为Ph，所述R2为CH3。
作为上述技术方案一种较好的选择，所述n为1，所述R1为C3H7，所述R2为CH3。
作为上述技术方案一种较好的选择，所述n为1，所述R1和R2环合为环己基。
作为上述技术方案一种较好的选择，所述n为2，所述R1为H，所述R2为Ph，所述R3为H。
作为上述技术方案一种较好的选择，所述n为2，所述R1为H，所述R2为CH3，所述R3为CH3。
作为上述技术方案一种较好的选择，所述n为2，所述R1为H，所述R2为Ph，所述R3为Ph。
作为上述技术方案一种较好的选择，所述盐为催化剂的硝酸盐、碳酸盐、草酸盐、铵盐和醋酸盐。
本发明还提供了一种上述芳杂环醇环钯金属催化剂的制备方法，其典型的包括如下的步骤：
上述步骤中，2,6-二甲基吡啶和二取代基酮或者环醚反应后酸化得到吡啶取代的醇，其再和醋酸钯反应得到相应芳杂环醇环钯金属催化剂；2-甲基喹啉和二取代基酮或者环醚反应后酸化得到喹啉取代的醇，其再和醋酸钯反应得到相应芳杂环醇环钯金属催化剂。
本发明还提供了芳杂环醇环钯金属催化剂在Suzuki反应中的应用,卤代芳烃(1mmol)，苯硼酸(1.5mmol)，催化剂(0.1-0.5mol％)，K2CO3(2mmol)，乙醇(1.5mL)为溶剂，大气环境下25-50℃反应1小时即可使底物基本完全反应，可以优秀产率(>90％)分离得到目标物。
本发明还提供了芳杂环醇环钯金属催化剂在芳环氰基化反应中的应用，卤代芳烃(1mmol)，K4[Fe(CN)6]·3H2O(0.3mmol)，催化剂(0.5-1.0mol％)，Na2CO3(1.5mmol)，DMAc/H2O(1mL,v/v＝19/1)中氩气保护下90-110℃反应8小时，目标物的分离收率大致分布于65％-90％之间。而对于氰基化反应，本发明的方法更绿色环保，产率显著的高于绝大多数现有的催化剂。
本发明还提供了芳杂环醇环钯金属催化剂在芳杂环C-H活化芳基化反应中的应用，卤代芳烃(0.5mmol)，芳杂环(0.75mmol)，催化剂(0.5-1.0mol％)，K2CO3(0.75mmol)，PivOH(30mol％)，DMAc(1.0mL)为溶剂，氩气环境下100℃反应24小时，目标物的分离收率大致分布于60％-95％之间。而对于芳杂环C-H活化芳基化反应，本发明的方法催化剂用量较低，条件也相对温和，产率显著的高于绝大多数现有的催化剂。
本发明还提供了芳杂环醇环钯金属催化剂在芳杂环氧化脱氢Heck反应中的应用，苯乙烯(0.5mmol)，芳杂环(1.0mmol)，催化剂(1.0-2.0mol％)，BQ(1mmol)，HOAc/DMSO(1.2mL,v/v＝1/1)为溶剂，大气环境下25-50℃反应24小时，目标物的收率大致分布于75％-95％之间。而对于芳杂环氧化脱氢Heck反应，本发明的方法条件更相对更温和，产率显著的高于绝大多数现有的催化剂。
本发明提供的环钯配合物是一类简单实用、用量较低、环境友好且具有普适性的新型催化剂，具有较好的应用前景。
具体实施方式
如下为本发明的具体实施例，其仅用作对本发明的解释而并非限制。
如下为本发明的芳杂环醇环钯金属催化剂的合成方法：
具体的，吡啶或喹啉杂环醇类化合物的合成方法典型包括：
以2,6-二甲基吡啶或2-甲基喹啉为原料，无水四氢呋喃(加钠重蒸)为溶剂，在无氧无水的超低温环境(-78℃)下，通过控制正丁基锂的用量，夺取一个甲基上的一个质子，然后通过对所选酮类或醛类或者环醚类化合物的亲核加成，即可高产率得到相应的杂环醇类化合物。
吡啶或喹啉杂环醇类环钯配合物的合成典型方法如下：
选用无水甲苯(加钠重蒸)为反应溶剂，Pd(OAc)2为环钯化试剂，将Pd(OAc)2与配体(当量比为1:2)溶于无水甲苯中，室温避光搅拌3天，至有大量白色或者浅黄色不溶物生成，反应即可终止。反应液经抽滤所得固体不溶物，经无水甲苯洗涤、烘干即可得到相应的目标产物。所得目标产物为白色或浅黄色固体。该类环钯配合物对水、空气和光照都有较好的稳定性，便于使用和长期保存。
按照上述制备方式制备获得了如下几类催化剂：
如下列出了本发明提供的吡啶或喹啉杂环醇类环钯配合物在催化反应中的应用。
从上述实施例可以看出，本发明的催化剂可以高效地应用于多种不同类型(芳环氰基化反应、芳杂环C-H活化芳基化反应、芳杂环氧化脱氢Heck反应和Suzuki偶联反应)的反应，且均获得了较高的产率，这证实该类配合物是一种简单实用、用量较低、环境友好且具有普适性的新型催化剂。
以上实施例用于理解本发明的方法和核心思想,对于本领域的技术人员来说,在不脱离本发明构思的前提下,进行任何可能的变化或替换,其均属于本发明的保护范围。
Claims (7)
1.一种芳杂环醇环钯金属催化剂，其特征在于：所述芳杂环醇环钯金属催化剂为具有式(1)或式(2)所示的结构的化合物或相应化合物的盐：
上式中，所述n为2；
R1、R2和R3独立的为-H、-CH3、-C3H7、正丁基、正己基、环己基、金刚烷基、樟脑基、Ph、p-OCH3-Ph、p-F-Ph或芴基。
2.根据权利要求1所述的芳杂环醇环钯金属催化剂，其特征在于：所述R1和R2独立的为Ph、CH3、C3H7，且环合为环己基。
3.根据权利要求1所述的芳杂环醇环钯金属催化剂，其特征在于：所述R1为H，所述R2为Ph，所述R3为H。
4.根据权利要求1所述的芳杂环醇环钯金属催化剂，其特征在于：所述R1为H，所述R2为CH3，所述R3为CH3。
5.根据权利要求1所述的芳杂环醇环钯金属催化剂，其特征在于：所述R1为H，所述R2为Ph，所述R3为Ph。
6.根据权利要求1所述的芳杂环醇环钯金属催化剂，其特征在于：所述盐为硝酸盐、碳酸盐、草酸盐、铵盐或醋酸盐。
7.权利要求1-6任一所述的芳杂环醇环钯金属催化剂在芳环氰基化反应、芳杂环C-H活化芳基化反应、芳杂环氧化脱氢Heck反应和Suzuki偶联反应中的应用。
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| CN106000469A (zh) * | 2016-05-25 | 2016-10-12 | 天津师范大学 | 含有钯配合物的催化剂及其制备方法与应用 |
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| CN106000469A (zh) * | 2016-05-25 | 2016-10-12 | 天津师范大学 | 含有钯配合物的催化剂及其制备方法与应用 |
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| Direct CeH arylation of heterocycles with heteroaryl chlorides using a bis(alkoxo)palladium complex;Yabo Li 等;《Tetrahedron》;20150328;第71卷;2729-2735 * |
| 吡啶乙醇类双[N,O]环钯配合物的设计合成及其催化性能研究;李亚波;《中国博士学位论文全文数据库工程科学I辑》;20151015(第10期);20-21，40 * |
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