CN110483502A - A kind of pyrido [1,2-a] [1,2,4] triazole carbenes and its synthetic method and application - Google Patents
A kind of pyrido [1,2-a] [1,2,4] triazole carbenes and its synthetic method and application Download PDFInfo
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- CN110483502A CN110483502A CN201910706849.3A CN201910706849A CN110483502A CN 110483502 A CN110483502 A CN 110483502A CN 201910706849 A CN201910706849 A CN 201910706849A CN 110483502 A CN110483502 A CN 110483502A
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- triazole
- pyrido
- carbenes
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- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000010189 synthetic method Methods 0.000 title claims abstract description 6
- 239000010931 gold Substances 0.000 claims abstract description 30
- 229910052737 gold Inorganic materials 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- 238000007259 addition reaction Methods 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 239000003480 eluent Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011541 reaction mixture Substances 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000013459 approach Methods 0.000 claims description 6
- 238000012805 post-processing Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 5
- HHIZISRHAQPAMY-UHFFFAOYSA-N 5-bromo-1h-1,2,4-triazole Chemical compound BrC1=NC=NN1 HHIZISRHAQPAMY-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- -1 phenyl-iodide tetrafluoroborates Chemical class 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 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 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 8
- 239000002841 Lewis acid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 3
- 150000007517 lewis acids Chemical class 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GUJAGMICFDYKNR-UHFFFAOYSA-N 1,4-benzodiazepine Chemical compound N1C=CN=CC2=CC=CC=C12 GUJAGMICFDYKNR-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- KVBWBCRPWVKFQT-UHFFFAOYSA-N 3-iodobenzoic acid Chemical compound OC(=O)C1=CC=CC(I)=C1 KVBWBCRPWVKFQT-UHFFFAOYSA-N 0.000 description 2
- DTELTOREECFDBC-UHFFFAOYSA-N 3-iodobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC(I)=C1 DTELTOREECFDBC-UHFFFAOYSA-N 0.000 description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- JEYWNNAZDLFBFF-UHFFFAOYSA-N Nafoxidine Chemical compound C1CC2=CC(OC)=CC=C2C(C=2C=CC(OCCN3CCCC3)=CC=2)=C1C1=CC=CC=C1 JEYWNNAZDLFBFF-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229950002366 nafoxidine Drugs 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- 150000003851 azoles Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940049706 benzodiazepine Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- HSYLTRBDKXZSGS-UHFFFAOYSA-N silver;bis(trifluoromethylsulfonyl)azanide Chemical compound [Ag+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HSYLTRBDKXZSGS-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
- C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
- C07D243/10—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems
- C07D243/12—1,5-Benzodiazepines; Hydrogenated 1,5-benzodiazepines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/12—Gold 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
-
- 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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/18—Gold
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a kind of pyridos [1,2-a] [1,2,4] triazole carbenes and its synthetic method and application, it is described such as V pyrido [1 of formula, 2-a] [1,2,4] triazole carbenes and gold formed pyrido [1,2-a] [1,2,4] triazole Cabbeen-gold complex can be applied to alkynes catalytic addition reaction, with Lewis acid/The dual active centre of alkali, can rely on " synergistic activation effect " at its bis-activated center, to realize the catalytic effect that conventional ligands cannot or be unable to reach, can significantly speed up addition reaction of the nucleopilic reagent to Multiple Bonds.
Description
Technical field
The present invention relates to catalyst technical field more particularly to pyrido [1,2-a] [1,2,4] triazole carbenes, its
Synthetic method and its gold complex and application.
Background technique
Past, gold was in one of the important milestone that the successful application of catalytic field is chemical research development for over ten years.In
In homogeneous gold research, how to effectively improve the stability, catalytic activity and selectivity of Au catalyst is Au catalyst design always
Core content.Wherein in the ligand design of Au catalyst using it is very extensive be the nitrogen with the big steric hindrance characteristic of electron rich
Heterocyclic carbene ligand, because the big steric hindrance of this kind of electron rich is with cognition with their unique electronic effects and space multistory effects
The electronic state and space multistory environment of central metal gold, and then have a deep effect on Au catalyst stability, catalysis live
Property and reaction selectivity.
However, being that some classical Cabbeens either modify card with some groups mostly in the design of ligand so far
Guest is to improve its electron rich and sterically hindered property, but the electron rich of ligand and sterically hindered property are can not to accomplish unlimitedly
It improves, so the stability of Au catalyst, catalytic activity and selectivity can not just be further continued for improving.This is just badly in need of from new concept
Design and develop the homogeneous Au catalyst with more high stability or catalytic activity and reaction selectivity.
Summary of the invention
The technical problems to be solved by the present invention are: in order to effectively improve the stability of Au catalyst, catalytic activity and choosing
Selecting property, present invention design and synthesis have the nitrogen heterocycle carbine ligand of nitrogen-containing basic group, i.e. pyrido [1,2-a] [1,2,4]
Triazole carbenes, using this bi-functional ligands and gold preparation have Lewis acid/The dual active centre of alkali
The Au catalyst of characteristic probes into its application in Multiple Bonds nucleophilic addition.
The technical scheme is that
In a first aspect, the present invention provides one kind pyrido as shown in formula V [1,2-a] [1,2,4] triazole Cabbeens to match
Body,
Second aspect, the present invention provides the synthetic method of the pyrido [1,2-a] [1,2,4] triazole carbenes,
Specifically comprise the following steps:
(1) under inert atmosphere, by Formula II compound represented and connection pinacol borate in palladium catalyst A and alkaline matter
Under the action of A, in Isosorbide-5-Nitrae-dioxane after 80~120 DEG C of 10~18h of reaction, reaction mixture A is obtained, it is post-treated to obtain
To borate shown in formula III；II compound represented, connection pinacol borate, palladium catalyst A and the alkaline matter A
The ratio between the amount of substance are as follows: 1:1.1~1.5:0.02~0.05:2~5；
(2) under inert atmosphere, by bromo- [1,2,4] triazol [4, the 3-a] pyridine of borate shown in formula III and 5- in palladium
Under the action of catalyst B and alkaline matter B, in the in the mixed solvent of n,N-Dimethylformamide and water, reacted in 80~120 DEG C
12~for 24 hours after, obtain reaction mixture B, it is post-treated to obtain intermediate shown in formula IV；Boric acid shown in the formula III
The ratio between bromo- [1,2,4] triazol [4,3-a] pyridine of ester, 5-, amount of substance of palladium catalyst B and alkaline matter B are as follows: 1:0.7~
0.9:0.02~0.05:2~5；
(3) by intermediate shown in formula IV and double phenyl-iodide tetrafluoroborates under the action of copper catalyst C, in N, N- bis-
In methylformamide, in 80~120 DEG C react 12~for 24 hours after, obtain reaction mixture C, it is post-treated to obtain pyrrole shown in Formula V
Pyridine simultaneously [1,2-a] [1,2,4] triazole carbenes；The object of intermediate shown in the formula IV, high iodine reagent and copper catalyst C
The ratio between amount of matter is 1:1~3:0.1~0.5.
Its synthetic route is as follows:
Further, in step (1), the palladium catalyst A is [1,1'- bis- (diphenylphosphino) ferrocene] dichloride
Palladium, bis-triphenylphosphipalladium palladium dichloride or palladium acetate.
Further, in step (1), the alkaline matter A is potassium acetate, potassium carbonate or sodium carbonate.
Further, in step (1), Isosorbide-5-Nitrae-dioxane additional amount is with intermediate shown in the Formula II
The amount of substance is calculated as 1~3mL/mol.
Further, in step (1), the post-processing approach of the reaction mixture A are as follows: by the reaction mixture A
It is filtered to remove insoluble matter, solution is diluted with ethyl acetate, water and salt water washing is successively used, is dried and evaporated with anhydrous sodium sulfate
Solvent, then by column chromatography for separation, using volume ratio for the petrol ether/ethyl acetate of 1:1 mixed solvent as eluant, eluent, collect
Eluent containing target product is spin-dried for obtaining borate shown in formula III.
Further, in step (2), the palladium catalyst B is [1,1'- bis- (diphenylphosphino) ferrocene] dichloride
Palladium, bis-triphenylphosphipalladium palladium dichloride or palladium acetate.
Further, in step (2), the alkaline matter B is potassium acetate, potassium carbonate or sodium carbonate.
Further, in step (2), the volume ratio of the n,N-Dimethylformamide and water is 5:1~3.
Further, in step (2), the addition total amount of n,N-Dimethylformamide and water is with bromo- [1,2,4] three 5-
The amount of the azoles simultaneously substance of [4,3-a] pyridine is calculated as 1~1.5mL/mol.
Further, in step (2), the post-processing approach of the reaction mixture B are as follows: by the reaction mixture B
It is filtered to remove insoluble matter, obtained solution is diluted with ethyl acetate, successively uses water and salt water washing, and it is dry with anhydrous sodium sulfate,
Evaporate solvent, then by column chromatography for separation, using volume ratio for the ethanol/methylene of 1:30 mixed solvent as eluant, eluent,
The eluent containing target product is collected, is spin-dried for obtaining intermediate shown in formula IV.
Further, in step (3), the copper catalyst C is copper acetate, copper chloride or cupric iodide.
Further, in step (3), the additional amount of the n,N-Dimethylformamide is with intermediate shown in the formula IV
The amount of the substance of body is calculated as 1~3mL/mol.
Further, in step (3), the post-processing approach of the reaction mixture C are as follows: by the reaction mixture C
It is filtered to remove insoluble matter, is precipitated crystal after methylene chloride is added into obtained solution, as pyrido [1,2- shown in Formula V
A] [1,2,4] triazole carbenes.
Further, the Formula II compound represented body the preparation method comprises the following steps: by 3- iodo-benzoic acid and oxalyl chloride in N,
Under dinethylformamide effect, room temperature reaction completely, obtains reaction mixture evaporating solvent under reduced pressure and obtains in methylene chloride
3- iodobenzoyl chloride, then under an inert atmosphere, by the 3- iodobenzoyl chloride and nafoxidine room temperature in methylene chloride
After reacting 1h, obtain that reaction mixture D is post-treated to obtain Formula II compound represented.
Further, the post-processing approach of the reaction mixture D are as follows: water is added in the reaction mixture D of Xiang Suoshu
With methylene chloride processing, merge organic phase, be dried and evaporated solvent, is the stone of 1:3 with volume ratio then by column chromatography for separation
The mixed solvent of oily ether/ethyl acetate is eluant, eluent, collects the eluent containing target product, is spin-dried for obtaining chemical combination shown in Formula II
Object.
The third aspect, the present invention provides pyrido [1,2-a] [1,2,4] triazole Cabbeen-gold complex, which is
It is formed by compound V and gold, and there is the general formula as described in formula VI:
Fourth aspect, the preparation method of pyrido [1,2-a] [1,2,4] triazole Cabbeen-gold complex of the present invention
Are as follows:
It is protected from light, under inert atmosphere, pyrido shown in Formula V [1,2-a] [1,2,4] triazole carbenes is dissolved in tetrahydro furan
In muttering, lithium hexamethyldisilazide is added at -78 DEG C, after mixing evenly, dimethyl sulphide chlorauride is added, is stirred to react 9
After~13 hours, solvent is evaporated, is the ethanol/methylene of 1:100~1:200 with volume ratio then by column chromatography for separation
Mixed solvent be eluant, eluent, collect the eluent containing target product, be spin-dried for obtaining pyrido shown in Formula IV [1,2-a] [1,
2,4] triazole Cabbeen-gold complex.
5th aspect, pyrido [1,2-a] [1,2,4] triazole Cabbeen-gold complex provided by the invention is as catalyst
Application in efficient catalytic alkynes addition reaction.
Further, the pyrido [1,2-a] [1,2,4] triazole Cabbeen-gold complex is preferably catalyzed phenylacetylene and closes
It is reacted at 1,4- Benzodiazepine.
Compared with prior art, the beneficial effects of the present invention are:
The present invention provides a kind of new pyridine, simultaneously [1,2-a] [1,2,4] triazole carbenes can form stabilization with gold
Metal complex, the Au catalyst have Lewis acid/The dual active centre of alkali, can rely on its it is bis-activated in
" synergistic activation effect " of the heart can be significantly speeded up to realize the catalytic effect that conventional ligands cannot or be unable to reach
Addition reaction of the nucleopilic reagent to Multiple Bonds.
Specific embodiment
Below with reference to specific embodiment, the present invention is further described.But the purposes and mesh of these exemplary embodiments
Be only used to enumerate the present invention, any type of any restriction not is constituted to real protection scope of the invention, it is more non-to incite somebody to action this
The protection scope of invention is confined to this.
Embodiment 1
Pyrido [1,2-a] [1,2,4] triazole carbenes are compound described in formula (1):
The compound is prepared with the following method:
Step 1: oxalyl chloride is added into the anhydrous methylene chloride solution (50mL) of 3- iodo-benzoic acid (10mmol)
(25mmol) and three drop n,N-Dimethylformamide, and mixture is stirred at room temperature 2-4 hours.Reaction mixing is evaporated under reduced pressure
Object is simultaneously dried under vacuum, and obtains 3- iodobenzoyl chloride, is again dissolved in 50mL anhydrous methylene chloride and cold in ice bath
But, the dichloromethane solution (10mL) of nafoxidine (15mmol) and triethylamine (20mmol) is then added, under an inert atmosphere
Then room temperature reaction 1 hour is handled solution 50mL water and 100mL methylene chloride, separate organic phase, be dried and evaporated solvent,
Then by column chromatography for separation, using volume ratio for the petrol ether/ethyl acetate of 1:3 mixed solvent as eluant, eluent, collect and contain mesh
The eluent for marking product, is spin-dried for obtaining intermediate II.
White solid, yield 90%, testing result is as follows:
1H NMR (500MHz, CDCl3) δ 7.83 (t, J=1.6Hz, 1H), 7.73-7.69 (m, 1H), 7.45-7.42 (m,
1H), 7.11 (t, J=7.8Hz, 1H), 3.59 (t, J=7.0Hz, 2H), 3.37 (t, J=6.6Hz, 2H), 1.96-1.90 (m,
2H),1.88–1.82(m,2H).
Step 2: intermediate II (10mmol) is added in reaction flask under inert atmosphere, join pinacol borate
(11mmol), potassium acetate (30mmol) and [1,1'- bis- (diphenylphosphino) ferrocene] palladium chloride (0.3mmol), then plus
Enter Isosorbide-5-Nitrae-dioxane (20mL), stirs 12 hours, then cool to room temperature at 80 DEG C.After being filtered to remove insoluble matter, by solution
It is diluted with ethyl acetate, successively uses water and salt water washing, be dried and evaporated solvent with anhydrous sodium sulfate, then pass through column chromatography point
From, using volume ratio for the petrol ether/ethyl acetate of 1:1 mixed solvent as eluant, eluent, collect the eluent containing target product, rotation
It is dry to obtain intermediate III.
Rufous grease, yield 70%, testing result is as follows:
1H NMR (500MHz, CDCl3) δ 7.88 (s, 1H), 7.78 (d, J=7.3Hz, 1H), 7.53 (d, J=8.8Hz,
1H), 7.33 (t, J=7.5Hz, 1H), 3.57 (t, J=6.8Hz, 2H), 3.35 (t, J=6.5Hz, 2H), 1.88 (dd, J=
13.2,6.4Hz, 2H), 1.80 (dd, J=12.9,6.4Hz, 2H), 1.28 (s, 12H)
Step 3: intermediate III (11mmol) is added in reaction flask under inert atmosphere, bromo- [1,2, the 4] triazol of 5- [4,
3-a] pyridine (10mmol), potassium carbonate (30mmol) and bis-triphenylphosphipalladium palladium dichloride (0.3mmol), N, N- diformazan is then added
Base formamide (10mL) and water (4mL) are stirred 24 hours at 80 DEG C, are then cooled to room temperature.It, will be molten after being filtered to remove insoluble matter
Liquid is diluted with ethyl acetate, is successively used water and salt water washing, is dried and evaporated solvent with anhydrous sodium sulfate, is then chromatographed by column
Separation, using volume ratio for the ethanol/methylene of 1:30 mixed solvent as eluant, eluent, collect the eluent containing target product,
It is spin-dried for obtaining intermediate compound IV.
Yellow solid, yield 70%, testing result is as follows:
1H NMR (500MHz, DMSO) δ 10.50 (d, J=0.8Hz, 2H), 8.45-7.44 (m, 14H), 3.49 (t, J=
6.6Hz, 4H), 1.88 (dq, J=17.5,6.5Hz, 4H)
Step 4: intermediate compound IV (10mmol) is added in reaction flask, and double phenyl-iodide tetrafluoroborates (20mmol), copper acetate
(1mmol) and n,N-Dimethylformamide (10mL) stirs 24 hours at 100 DEG C, then cools to room temperature, be filtered to remove
After insoluble matter, is precipitated crystal after methylene chloride (60mL) is added, obtain pyrido [1,2-a] [1,2,4] triazole carbenes V.
Faint yellow solid, yield 65%, testing result is as follows:
1H NMR(500MHz,DMSO-d6)δ10.06(s,1H),8.42–8.31(m,2H),8.03–7.72(m,10H),
3.53 (t, J=6.6Hz, 4H), 1.90 (dq, J=17.5,6.5Hz, 4H)
13C NMR(126MHz,DMSO)δ167.00,142.66,139.58,139.05,138.39,136.50,134.83,
130.67,130.46,130.23,130.04,129.90,129.72,127.90,124.31,119.47,109.79,48.87,
46.09,25.99,23.95.
Embodiment 2
The synthesis of pyrido [1,2-a] [1,2,4] triazole Cabbeen-gold complex:
It is protected from light, under inert atmosphere, pyrido [1,2-a] [1,2,4] triazole carbenes V (1mmol) is added in reaction tube,
Lithium hexamethyldisilazide (1.1mmol) is added at -78 DEG C in dry tetrahydrofuran (2mL), after stirring 15min, is added two
Methyl sulfide chlorauride after being stirred to react 16 hours, evaporates solvent, is the first of 1:100 with volume ratio then by column chromatography for separation
Alcohol/methylene chloride mixed solvent is eluant, eluent, collects the eluent containing target product, be spin-dried for obtaining pyrido [1,2-a] [1,
2,4] triazole Cabbeen-gold complex VI, white solid, yield 85%.
Embodiment 3
Pyrido [1,2-a] [1,2,4] triazole Cabbeen-gold complex catalysis phenylacetylene synthesis 1,4- Benzodiazepine reaction
Pyrido [1,2-a] [1,2,4] triazole Cabbeen-gold complex (0.01mmol) is added in reaction tube for room temperature,
AgNTf2(0.02mmol) is stirred 15 minutes.Then it is added 1,2- phenylenediamine (0.2mmol), phenylacetylene (0.5mmol), then
Column chromatography for separation after being stirred at room temperature 6 hours, using volume ratio for the petrol ether/ethyl acetate of 1:20 mixed solvent as elution
Agent collects the eluent containing target product, is spin-dried for obtaining Isosorbide-5-Nitrae-Benzodiazepine product.
Yellow solid, yield 80%.1H NMR(500MHz,CDCl3)δ7.66–7.58(m,4H),7.38–7.23(m,
6H), 7.20 (t, J=7.3Hz, 1H), 7.09 (m, J=11.9,7.4,1.5Hz, 2H), 6.87 (dd, J=7.5,1.3Hz,
1H), 3.56 (s, 1H), 3.17 (d, J=13.2Hz, 1H), 3.00 (d, J=13.2Hz, 1H), 1.78 (s, 3H)
Embodiment 4
Chlorauride is catalyzed phenylacetylene synthesis 1,4- Benzodiazepine reaction
Chlorauride (0.01mmol) is added in reaction tube, AgNTf in room temperature2(0.02mmol) is stirred 15 minutes.Then plus
Enter 1,2- phenylenediamine (0.2mmol), phenylacetylene (0.5mmol) is then stirred at room temperature 6 hours, after reaction through liquid phase-
Mass spectrum monitors product less than 10%.
Claims (10)
1. a kind of pyrido as shown in formula V [1,2-a] [1,2,4] triazole carbenes,
2. a kind of synthetic method of pyrido as described in claim 1 [1,2-a] [1,2,4] triazole carbenes, feature
Be: the method carries out as follows:
(1) under inert atmosphere, by Formula II compound represented and connection pinacol borate palladium catalyst A's and alkaline matter A
Under effect, in Isosorbide-5-Nitrae-dioxane after 80~120 DEG C of 10~18h of reaction, reaction mixture A is obtained, it is post-treated to obtain
Borate shown in formula III；The II compound represented, connection pinacol borate, palladium catalyst A and alkaline matter A
The ratio between amount of substance are as follows: 1:1.1~1.5:0.02~0.05:2~5；
(2) under inert atmosphere, by bromo- [1,2,4] triazol [4, the 3-a] pyridine of borate shown in formula III and 5- in palladium chtalyst
Under the action of agent B and alkaline matter B, in the in the mixed solvent of n,N-Dimethylformamide and water, react 12 in 80~120 DEG C~
After for 24 hours, reaction mixture B is obtained, it is post-treated to obtain intermediate shown in formula IV；Borate shown in the formula III, 5-
The ratio between bromo- [1,2,4] triazol [4,3-a] pyridine, amount of substance of palladium catalyst B and alkaline matter B are as follows: 1:0.7~0.9:
0.02~0.05:2~5；
(3) by intermediate shown in formula IV and double phenyl-iodide tetrafluoroborates under the action of copper catalyst C, in N, N- dimethyl
In formamide, in 80~120 DEG C react 12~for 24 hours after, obtain reaction mixture C, it is post-treated to obtain pyrido shown in Formula V
[1,2-a] [1,2,4] triazole carbenes；The substance of intermediate shown in the formula IV, high iodine reagent and copper catalyst C
The ratio between amount is 1:1~3:0.1~0.5；
。
3. method according to claim 2, it is characterised in that: the palladium catalyst A or B respectively stands alone as that [1,1'- is bis-
(diphenylphosphino) ferrocene] palladium chloride, bis-triphenylphosphipalladium palladium dichloride or palladium acetate.
4. method according to claim 2, it is characterised in that: the alkaline matter A or B respectively stands alone as potassium acetate, carbon
Sour potassium or sodium carbonate.
5. method according to claim 2, it is characterised in that: in step (1), Isosorbide-5-Nitrae-dioxane additional amount with
The amount of the substance of intermediate shown in the Formula II is calculated as 1~3mL/mol；The post-processing approach of the reaction mixture A
Are as follows: the reaction mixture A is filtered to remove insoluble matter, solution is diluted with ethyl acetate, successively uses water and salt water washing,
It is dried and evaporated solvent with anhydrous sodium sulfate, is the petrol ether/ethyl acetate of 1:1 with volume ratio then by column chromatography for separation
Mixed solvent is eluant, eluent, collects the eluent containing target product, is spin-dried for obtaining borate shown in formula III.
6. method according to claim 2, it is characterised in that: in step (2), the n,N-Dimethylformamide and water
Volume ratio is 5:1~3；The addition total amount of N,N-dimethylformamide and water is with bromo- [1,2,4] triazol [4,3- of 5-
A] amount of substance of pyridine is calculated as 1~1.5mL/mol；The post-processing approach of the reaction mixture B are as follows: by the reaction
Mixed liquid B is filtered to remove insoluble matter, and obtained solution is diluted with ethyl acetate, successively uses water and salt water washing, uses anhydrous slufuric acid
Sodium is dried and evaporated solvent, and then by column chromatography for separation, the mixed solvent with volume ratio for the ethanol/methylene of 1:30 is
Eluant, eluent collects the eluent containing target product, is spin-dried for obtaining intermediate shown in formula IV.
7. method according to claim 2, it is characterised in that: in step (3), the copper catalyst C is copper acetate, chlorination
Copper or cupric iodide.
8. method according to claim 2, it is characterised in that: in step (3), the addition of the n,N-Dimethylformamide
Amount is calculated as 1~3mL/mol with the amount of the substance of intermediate shown in the formula IV；The reaction mixture C is crossed and is filtered out
Remove insoluble matter, into obtained solution be added methylene chloride after precipitate crystal, as pyrido shown in Formula V [1,2-a] [1,2,
4] triazole carbenes.
9. a kind of pyrido as described in claim 1 [1,2-a] [1,2,4] triazole carbenes and gold are formed as shown in formula VI
Pyrido [1,2-a] [1,2,4] triazole Cabbeen-gold complex:
10. a kind of pyrido as claimed in claim 9 [1,2-a] [1,2,4] triazole Cabbeen-gold complex exists as catalyst
Application in efficient catalytic alkynes addition reaction.
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| MANUEL ALCARAZO 等: "Steering the Surprisingly Modular p-Acceptor Properties of N-Heterocyclic Carbenes: Implications for Gold Catalysis", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| SANDRO CACCHI 等: "Construction of the 1,5-Benzodiazepine Skeleton from o‑ Phenylendiamine and Propargylic Alcohols via a Domino Gold-Catalyzed Hydroamination/Cyclization Process", 《ORGANIC LETTERS》 * |
| YANZHAO WANG 等: "A general ligand design for gold catalysis allowing", 《NATURE COMMUNICATIONS》 * |
| YOUNGSUK KIM 等: "Ef ficient synthesis of bulky N -Heterocyclic car bene ligands for coinage metal complexes", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
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