CN103833729A - Method using visible light catalyzed cross-coupling reaction to prepare coupling product and release hydrogen - Google Patents
Method using visible light catalyzed cross-coupling reaction to prepare coupling product and release hydrogen Download PDFInfo
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- CN103833729A CN103833729A CN201210477433.7A CN201210477433A CN103833729A CN 103833729 A CN103833729 A CN 103833729A CN 201210477433 A CN201210477433 A CN 201210477433A CN 103833729 A CN103833729 A CN 103833729A
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- visible light
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 131
- 239000001257 hydrogen Substances 0.000 title claims abstract description 126
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000006880 cross-coupling reaction Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000008878 coupling Effects 0.000 title abstract description 5
- 238000010168 coupling process Methods 0.000 title abstract description 5
- 238000005859 coupling reaction Methods 0.000 title abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 40
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 22
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 150000004700 cobalt complex Chemical class 0.000 claims description 28
- 230000003197 catalytic effect Effects 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 239000012434 nucleophilic reagent Substances 0.000 claims description 17
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 238000005286 illumination Methods 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 8
- 229940054051 antipsychotic indole derivative Drugs 0.000 claims description 8
- 150000002475 indoles Chemical class 0.000 claims description 8
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 5
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical group COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims description 4
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- RYFCSKVXWRJEOB-UHFFFAOYSA-N dibenzyl propanedioate Chemical compound C=1C=CC=CC=1COC(=O)CC(=O)OCC1=CC=CC=C1 RYFCSKVXWRJEOB-UHFFFAOYSA-N 0.000 claims description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 3
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical group COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- RQKYHDHLEMEVDR-UHFFFAOYSA-N oxo-bis(phenylmethoxy)phosphanium Chemical compound C=1C=CC=CC=1CO[P+](=O)OCC1=CC=CC=C1 RQKYHDHLEMEVDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 2
- 239000010941 cobalt Substances 0.000 abstract 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 239000012038 nucleophile Substances 0.000 abstract 2
- 239000000370 acceptor Substances 0.000 abstract 1
- 239000003504 photosensitizing agent Substances 0.000 description 73
- 239000002994 raw material Substances 0.000 description 52
- 230000009466 transformation Effects 0.000 description 51
- 239000000243 solution Substances 0.000 description 47
- ZFMATGCSINTILY-UHFFFAOYSA-N 1-(1h-indol-3-yl)-2-phenyl-3,4-dihydro-1h-isoquinoline Chemical compound C1CC2=CC=CC=C2C(C=2C3=CC=CC=C3NC=2)N1C1=CC=CC=C1 ZFMATGCSINTILY-UHFFFAOYSA-N 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 150000007960 acetonitrile Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003810 ethyl acetate extraction Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BGPSSHKYYOXNTD-UHFFFAOYSA-N 1-(1H-indol-3-yl)-2-(2-methoxyphenyl)-3,4-dihydro-1H-isoquinoline Chemical group N1C=C(C2=CC=CC=C12)C1N(CCC2=CC=CC=C12)C1=C(C=CC=C1)OC BGPSSHKYYOXNTD-UHFFFAOYSA-N 0.000 description 1
- DSZWQQZULPUDLE-UHFFFAOYSA-N 1-(1H-indol-3-yl)-2-(4-methoxyphenyl)-3,4-dihydro-1H-isoquinoline Chemical group C1=CC(OC)=CC=C1N1C(C=2C3=CC=CC=C3NC=2)C2=CC=CC=C2CC1 DSZWQQZULPUDLE-UHFFFAOYSA-N 0.000 description 1
- FOQKOFJAXJDQKL-UHFFFAOYSA-N 1-(1H-indol-3-yl)-2-(4-methylphenyl)-3,4-dihydro-1H-isoquinoline Chemical compound Cc1ccc(cc1)N1CCc2ccccc2C1c1c[nH]c2ccccc12 FOQKOFJAXJDQKL-UHFFFAOYSA-N 0.000 description 1
- VFMQVTVYJNVVEP-UHFFFAOYSA-N 1-(2-methyl-1h-indol-3-yl)-2-phenyl-3,4-dihydro-1h-isoquinoline Chemical group CC=1NC2=CC=CC=C2C=1C(C1=CC=CC=C1CC1)N1C1=CC=CC=C1 VFMQVTVYJNVVEP-UHFFFAOYSA-N 0.000 description 1
- AOUGWBRILZINCI-UHFFFAOYSA-N 1-(5-methoxy-1h-indol-3-yl)-2-phenyl-3,4-dihydro-1h-isoquinoline Chemical group C12=CC(OC)=CC=C2NC=C1C(C1=CC=CC=C1CC1)N1C1=CC=CC=C1 AOUGWBRILZINCI-UHFFFAOYSA-N 0.000 description 1
- RWYONRMHAGPBPN-UHFFFAOYSA-N 1-(6-chloro-1H-indol-3-yl)-2-phenyl-3,4-dihydro-1H-isoquinoline Chemical group C=1NC2=CC(Cl)=CC=C2C=1C(C1=CC=CC=C1CC1)N1C1=CC=CC=C1 RWYONRMHAGPBPN-UHFFFAOYSA-N 0.000 description 1
- YZVGLZYUXHDLSN-UHFFFAOYSA-N 1-(6-methoxy-1H-indol-3-yl)-2-phenyl-3,4-dihydro-1H-isoquinoline Chemical group COc1ccc2c(c[nH]c2c1)C1N(CCc2ccccc12)c1ccccc1 YZVGLZYUXHDLSN-UHFFFAOYSA-N 0.000 description 1
- UVRHQKMSCGRJCJ-UHFFFAOYSA-N 1-bromo-1-phenyl-3,4-dihydro-2H-isoquinoline Chemical compound BrC1(NCCC2=CC=CC=C12)C1=CC=CC=C1 UVRHQKMSCGRJCJ-UHFFFAOYSA-N 0.000 description 1
- OUCSOGNZRPDGMO-UHFFFAOYSA-N C1CN(C(C2=CC=CC=C21)C3CNC4=C3C=C(C=C4)[N+](=O)[O-])C5=CC=CC=C5 Chemical group C1CN(C(C2=CC=CC=C21)C3CNC4=C3C=C(C=C4)[N+](=O)[O-])C5=CC=CC=C5 OUCSOGNZRPDGMO-UHFFFAOYSA-N 0.000 description 1
- URNGTNUESCVEQS-UHFFFAOYSA-N C1CNC(C2=CC=CC=C21)(C#N)C3=CC=CC=C3 Chemical compound C1CNC(C2=CC=CC=C21)(C#N)C3=CC=CC=C3 URNGTNUESCVEQS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- -1 olefin hydrocarbon Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000006362 organocatalysis Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000006692 trifluoromethylation reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
- C07D217/14—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/62—Isoquinoline or hydrogenated isoquinoline ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Indole Compounds (AREA)
Abstract
The invention discloses a method using visible light catalyzed cross-coupling reaction to prepare a coupling product and release hydrogen. The method is as follows: a tertiary amine, a nucleophile, a cobalt complexe 1 or a cobalt complexe 2 and eosin Y are added into a solvent to obtain a mixed solution, and under the protection of an inert gas, visible light is used to irradiate the mixed solution to obtain the cross-coupling product of the tertiary amine and the nucleophile and release the hydrogen. The reaction can be achieved by visible light irradiation in the presence of the inert gas, and is mild in reaction conditions, the whole system is free of externally-applied electron donors or acceptors, and the method is energy-saving and environmentally-friendly.
Description
Technical field
The invention belongs to catalytic synthetic techniques field, a kind of method that relates to cross-coupling and put hydrogen, particularly the cross-coupling of a kind of visible light catalytic tertiary amine and nucleophilic reagent is put hydrogen methods.
Background technology
In chemical field, the reaction of high, the mild condition of development selectivity, environmental protection is the target that chemists pursue always.In traditional chemistry, often need comparison exacting terms, as high temperature, high pressure, strong acid, highly basic etc.Before a century, famous photochemical scholar Ciamician with regard to bewrite and looked forward to light as a kind of clean energy in advantage and the importance of ordering about in chemical reaction.Since two thousand eight, visible light catalytic organic reaction has obtained a series of achievements in research that attract people's attention.As, the Yoon group of Univ. of Wisconsin-Madison utilizes ruthenium complexe under visible ray condition, to realize in a series of electron deficiency or electron rich olefin hydrocarbon molecules as photosensitizers or intermolecular cycloaddition reaction; The title complex that Stephenson group of Boston University utilizes ruthenium or iridium has been realized the linked reaction of the dehalogenation reaction, radical cycloaddition reaction and tertiary amine and the nucleophilic reagent of organic halogen etc. as photocatalyst, and successfully visible light catalytic has been applied in the committed step of complete synthesis reaction; Macmillan group of Princeton University adopts the visible light catalytic of ruthenium complexe and the combination of organocatalysis to realize the asymmetric alkylation reaction of aldehyde α position, has also realized in addition the trifluoromethylation reaction of aromatic base by visible light catalytic; The organic dye of Metal free is also used for the cross-coupling reaction of visible light catalytic by groups such as Konig, Wu Lizhu.
At present, the system of visible light catalytic is to remove a part hydrogen by oxygenant, thereby realizes two intermolecular cross-couplings.Report respectively using dyestuff eosin eosinY(sodium salt or tetra-n-butyl amine salt as Konig group and Wu Lizhu organize) as photosensitizers, in oxygen atmosphere, under the irradiation of visible ray, that has realized N-phenyltetrahydroisoq,inolines derivative and the nucleophilic reagents such as Xiao base Wan Ting ﹑ dialkyl malonate compounds intersects dehydrogenation coupling (Org.Lett.2011,13,3852, Chem.Eur.J.2012,18,620); C.R.J.Stephenson etc. are using bromo chloroform as terminal oxygenant, the title complex of many pyridines ruthenium is as photosensitizers, that has realized N-phenyltetrahydroisoq,inolines derivative and Xiao base Wan Ting ﹑ Yin Duo ﹑ alkynes analog derivative intersects dehydrogenation coupling (Org.Lett.2012,14,94).The optimal mode of cross-coupling reaction that realizes " Atom economy (atom economy) " is in successfully building carbon-carbon bond, to emit a part hydrogen, but in most cases because the motivating force of reaction releasing hydrogen gas is inadequate, be conventionally difficult to realize.So the report of most is all the product of being taken off a part hydrogen and obtained coupling by oxygenant, also without any patent and bibliographical information in the atmosphere of rare gas element, utilize visible light catalytic to be attended by emitting of hydrogen in realizing tertiary amine and nucleophilic reagent cross-coupling reaction.
Summary of the invention
The object of the invention is to design a kind of method that visible light catalytic cross-coupling is prepared coupled product and put hydrogen, it can realize releasing hydrogen gas in the cross-coupling reaction of tertiary amine and nucleophilic reagent under visible ray condition, protection of inert gas.This reaction, using eosin W or W S as photosensitizers, using cobalt complex as catalyzer, can realize efficiently the cross-coupling of tertiary amine and nucleophilic reagent under protection of inert gas with radiation of visible light, and releasing hydrogen gas.
The invention provides a kind of method that visible light catalytic cross-coupling is prepared coupled product and put hydrogen, comprise the following steps: tertiary amine, nucleophilic reagent, cobalt complex 1 or cobalt complex 2, eosin W or W S are added in solvent, obtain mixing solutions, under protection of inert gas, use radiation of visible light mixing solutions, obtain cross-coupling product the releasing hydrogen gas of tertiary amine and nucleophilic reagent;
Wherein, described nucleophilic reagent is dialkyl malonate, dialkyl phosphite or indole derivatives;
Described solvent is the mixed solvent of water or water and acetonitrile;
The structural formula of described cobalt complex 1 and cobalt complex 2 is as follows respectively:
Further, the structural formula of described tertiary amine is as follows:
In formula, X is H, and Y is OCH
3; Y is H, and X is H, F, Cl, Br, CH
3, OCH
3or CN.
The structural formula of described indole derivatives is:
In formula, R
1﹑ R
2﹑ R
3﹑ R
4﹑ R
5complete is H; Or, R
1﹑ R
2﹑ R
3﹑ R
4﹑ R
5in one be CH
3, all the other are H; Or, R
3﹑ R
4in one be OCH
3, all the other are H; Or, R
3﹑ R
4in one be COOCH
3, all the other are H; Or, R
3for NO
2, all the other are H; Or, R
4for Cl, all the other are H.
Described dialkyl malonate is dimethyl malonate, diethyl malonate or propanedioic acid dibenzyl ester.Described dialkyl phosphite is dimethylphosphite, diethyl phosphite or dibenzyl phosphite.
In actually operating, can first tertiary amine, nucleophilic reagent, cobalt complex 1 or cobalt complex 2 or eosin W or W S be dissolved in respectively to solvent, obtain each solution, more each solution is mixed afterwards, obtain mixing solutions.Or, tertiary amine and nucleophilic reagent are dissolved in to same solvent, cobalt complex 1 or cobalt complex 2 and eosin W or W S are dissolved in respectively solvent separately, these three solution are mixed afterwards again, obtain mixing solutions.Each solvent can be identical or different, but at least contain water.For example, tertiary amine and nucleophilic reagent are dissolved in acetonitrile, cobalt complex 1 is dissolved in water and acetonitrile mixing solutions, and eosin W or W S is dissolved in water.In the time that solvent is the mixed solvent of water and acetonitrile, both blending ratios do not limit.The difference of ethane nitrile content can cause the difference of productive rate.
Preferably, in the time that solvent is the mixed solvent of water and acetonitrile, the volume ratio of water and acetonitrile is not less than 1:9.
Further, described cobalt complex 1 is not less than 0.072mg:1mL with the ratio of solvent; Described cobalt complex 2 is not less than 0.084mg:1mL with the ratio of solvent; The ratio of described eosin W or W S and solvent is not less than 0.136mg:1mL; The ratio of described tertiary amine and solvent is not less than 0.02mmol:1mL; The ratio of described indole derivatives and solvent is not less than 0.022mmol:1mL; The ratio of described dialkyl malonate and solvent is not less than 0.02mmol:1mL; The ratio of described dialkyl phosphite and solvent is not less than 0.02mmol:1mL.In the time of reaction, only need meet minimum scope, concentration is excessive does not have many contributions to productive rate again, also can cause the waste of raw material.
Preferably, described cobalt complex 1 is 0.072 ~ 1.44mg:1mL with the ratio of solvent; Described cobalt complex 2 is 0.084 ~ 1.68mg:1mL with the ratio of solvent; The ratio of described eosin W or W S and solvent is 0.136 ~ 0.72mg:1mL; The ratio of described tertiary amine and solvent is 0.02mmol:1mL; The ratio of described indole derivatives and solvent is 0.022 ~ 0.06mmol:1mL; The ratio of described dialkyl malonate and solvent is 0.02 ~ 0.06mmol:1mL; The ratio of described dialkyl phosphite and solvent is 0.02mmol:1mL.
Eosin W or W S is photosensitizers, and its structural formula is as follows:
Further, described radiation of visible light is to adopt the Green LEDs of 525nm ± 10nm to irradiate, and illumination temperature is room temperature～40 DEG C, and light application time is 12～16h.
The present invention has following beneficial effect:
1. this reaction just can realize with radiation of visible light under inert gas conditions, reaction conditions gentleness.
2. what the catalyst system of reaction was used is all molecular catalyst, is conducive to further carry out the mechanism research of such reaction.
3. what this catalyst system was used is relatively inexpensive photosensitizers and catalyzer, whole system economical environment-protective.
4. this catalyst system can be realized efficiently the cross-coupling of tertiary amine and nucleophilic reagent under radiation of visible light, and while releasing hydrogen gas, tertiary amine and nucleophilic reagent applied widely, whole system does not have additional electron donor or electron acceptor(EA), embody Atom economy, whole system environmental protection.
Embodiment
With specific embodiment, the present invention is described in detail below, but be not to concrete restriction of the present invention.
In the present invention, the preparation of cobalt complex 1 and cobalt complex 2 can be with reference to the method (Inorg.Chem.1992,31,1152) of L.G.Marzilli group report.
Embodiment 1
Taking cobalt complex 1 as catalyzer, in 2mL water, add this catalyzer of 0.36mg; Taking eosin eosinY as photosensitizers, in 2mL water, add this photosensitizers of 0.7mg; Catalyst solution and photosensitizers solution are mixed, obtain 4mL mixed aqueous solution.Getting 0.1mmol tertiary amine-1(X, Y is H) ﹑ and 0.2mmol indoles-1(R
1﹑ R
2﹑ R
3﹑ R
4﹑ R
5for H) be dissolved in 1mL acetonitrile, obtain acetonitrile solution.Again 4mL mixed aqueous solution is joined to this acetonitrile solution, obtain 5mL mixing solutions.Wherein the concentration of photosensitizers is 2.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-4m.Logical nitrogen deoxygenation 30min, with the mouth of sealing with wax, squeeze into interior mark methane 600 μ L, then use Green LEDs illumination 12h at 40 DEG C of 525nm ± 10nm, by gas-chromatography, (TCD is detector, Shanghai Techcomp Instrument Ltd., day beautiful 7890II type) detect the growing amount of hydrogen, probably there is the hydrogen of 227 μ L to produce.After reaction finishes, add ethyl acetate extraction, use saturated common salt water washing, anhydrous sodium sulfate drying, finally separates after post.Nuclear-magnetism Qing Pu ﹑ Tan Pu ﹑ and Mass Spectrometric Identification product are 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 15%, and the productive rate of coupled product is 6%, and the amounts of hydrogen of emitting is 10% with respect to theoretical value.
Embodiment 2
With embodiment 1, difference is: add 1.44mg photosensitizers, the concentration of photosensitizers is 4.0 × 10
-4m.Probably there is the hydrogen of 315 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 15%, and the productive rate of coupled product is 11%, and the amounts of hydrogen of emitting is 14% with respect to theoretical value.
Embodiment 3
With embodiment 1, difference is: add 2.04mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m.Probably there is the hydrogen of 427 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 21%, and the productive rate of coupled product is 13%, and the amounts of hydrogen of emitting is 19% with respect to theoretical value.
Embodiment 4
With embodiment 1, difference is: add 3.44mg photosensitizers, the concentration of photosensitizers is 1.0 × 10
-3m.Probably there is the hydrogen of 435 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 22%, and the productive rate of coupled product is 13%, and the amounts of hydrogen of emitting is 19% with respect to theoretical value.
Embodiment 5
With embodiment 1, difference is: add 1.08mg catalyzer, and 2.04mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 6.0 × 10
-4m.Probably there is the hydrogen of 458 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 25%, and the productive rate of coupled product is 18%, and the amounts of hydrogen of emitting is 20% with respect to theoretical value.
Embodiment 6
With embodiment 1, difference is: add 1.8mg catalyzer, and 2.04mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 1.0 × 10
-3m.Probably there is the hydrogen of 824 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 41%, and the productive rate of coupled product is 35%, and the amounts of hydrogen of emitting is 37% with respect to theoretical value.
Embodiment 7
With embodiment 1, difference is: add 2.9mg catalyzer, and 2.04mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 1.6 × 10
-3m.Probably there is the hydrogen of 1.14mL to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 55%, and the productive rate of coupled product is 48%, and the amounts of hydrogen of emitting is 51% with respect to theoretical value.
Embodiment 8
With embodiment 1, difference is: add 3.6mg catalyzer, and 2.04mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-3m.Probably there is the hydrogen of 1.54mL to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 70%, and the productive rate of coupled product is 68%, and the amounts of hydrogen of emitting is 69% with respect to theoretical value.
Embodiment 9
With embodiment 1, difference is: add 7.2mg catalyzer, and 2.04mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 4.0 × 10
-3m.Probably there is the hydrogen of 1.60mL to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 75%, and the productive rate of coupled product is 68%, and the amounts of hydrogen of emitting is 71% with respect to theoretical value.
Embodiment 10
With embodiment 1, difference is: add 3.6mg catalyzer, and 2.04mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-3m, illumination 16h at 40 DEG C.Probably there is the hydrogen of 1.99mL to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 81%, and the amounts of hydrogen of emitting is 89% with respect to theoretical value.
Embodiment 11
With embodiment 1, difference is: in 2.5mL water, add 3.6mg catalyzer; In 2.5mL water, add 2.04mg photosensitizers; Catalyst solution and photosensitizers solution mix, and obtain 5mL mixed aqueous solution.Tertiary amine-1 and indoles-1 are added, obtain 5mL mixing solutions.Wherein the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-3m.Illumination 16h at 40 DEG C.Probably there is the hydrogen of 358.4 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 20%, and the productive rate of coupled product is 13%, and the amounts of hydrogen of emitting is 16% with respect to theoretical value.
Embodiment 12
With embodiment 1, difference is: in 2.5mL water, add 3.6mg catalyzer; In 2.0mL water, add 2.04mg photosensitizers; Catalyst solution and photosensitizers solution mix, and obtain 4.5mL mixed aqueous solution.Get tertiary amine-1 and indoles-1 and be dissolved in 0.5mL acetonitrile, then 4.5mL mixed aqueous solution is joined to this acetonitrile solution, obtain 5mL mixing solutions.Wherein the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-3m.Illumination 16h at 40 DEG C.Probably there is the hydrogen of 1.79mL to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 91%, and the productive rate of coupled product is 75%, and the amounts of hydrogen of emitting is 80% with respect to theoretical value.
Embodiment 13
With embodiment 1, difference is: in 1.5mL water, add 3.6mg catalyzer; In 1.5mL water, add 2.04mg photosensitizers; Catalyst solution and photosensitizers solution mix, and obtain 3.0mL mixed aqueous solution.Get tertiary amine-1 and indoles-1 and be dissolved in 2.0mL acetonitrile, then 3.0mL mixed aqueous solution is joined to this acetonitrile solution, obtain 5mL mixing solutions.Illumination 16h at 40 DEG C.Probably there is the hydrogen of 1.39mL to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 68%, and the productive rate of coupled product is 55%, and the amounts of hydrogen of emitting is 62% with respect to theoretical value.
Embodiment 14
With embodiment 1, difference is: in 2.0mL water, add 3.6mg catalyzer; In 2.0mL water, add 2.04mg photosensitizers; Catalyst solution and photosensitizers solution mix, and obtain 4.0mL mixed aqueous solution.Get tertiary amine-1 and 0.11mmol indoles-1 is dissolved in 1.0mL acetonitrile, then 4.0mL mixed aqueous solution is joined to this acetonitrile solution, obtain 5mL mixing solutions.Illumination 16h at 40 DEG C.Probably there is the hydrogen of 1.29mL to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 61%, and the productive rate of coupled product is 45%, and the amounts of hydrogen of emitting is 58% with respect to theoretical value.
Embodiment 15
With embodiment 1, difference is: in 2.0mL water, add 3.6mg catalyzer; In 2.0mL water, add 2.04mg photosensitizers; Catalyst solution and photosensitizers solution mix, and obtain 4.0mL mixed aqueous solution.Get tertiary amine-1 and 0.3mmol indoles-1 is dissolved in 1.0mL acetonitrile, then 4.0mL mixed aqueous solution is joined to this acetonitrile solution, obtain 5mL mixing solutions.Illumination 16h at 40 DEG C.Probably there is the hydrogen of 2.03mL to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 82%, and the amounts of hydrogen of emitting is 91% with respect to theoretical value.
Embodiment 16
Taking cobalt complex 2 as catalyzer, in 2.0mL acetonitrile, add this catalyzer of 0.42mg, obtain catalyzer acetonitrile solution; Get 0.1mmol tertiary amine-1 ﹑ and 0.2mmol indoles-1 is dissolved in 1.0mL acetonitrile, obtain substrate solution; The catalyzer acetonitrile solution of 2mL is joined in substrate solution, obtain 3.0mL acetonitrile solution; Taking eosin eosin Y as photosensitizers, in 2.0mL water, add this photosensitizers of 0.68mg; Again this 2.0mL aqueous solution is joined in 3.0mL acetonitrile solution, obtain 5mL mixing solutions.Wherein the concentration of photosensitizers is 2.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-4m.Logical nitrogen deoxygenation 30min, with the mouth of sealing with wax, squeeze into interior mark methane 600 μ L, then use Green LEDs illumination 12h at 40 DEG C of 525nm ± 10nm, by gas-chromatography, (TCD is detector, Shanghai Techcomp Instrument Ltd., day beautiful 7890II type) detect the growing amount of hydrogen, probably there is the hydrogen of 113 μ L to produce.After reaction finishes, add ethyl acetate extraction, use saturated common salt water washing, anhydrous sodium sulfate drying, finally separates after post.Nuclear-magnetism Qing Pu ﹑ Tan Pu ﹑ and Mass Spectrometric Identification product are 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 10%, and the productive rate of coupled product is 3%, and the amounts of hydrogen of emitting is 5% with respect to theoretical value.
Embodiment 17
With embodiment 16, difference is: add 1.4mg photosensitizers, the concentration of photosensitizers is 4.0 × 10
-4m.Probably there is the hydrogen of 213 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 12%, and the productive rate of coupled product is 6%, and the amounts of hydrogen of emitting is 9% with respect to theoretical value.
Embodiment 18
With embodiment 16, difference is: add 2.1mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m.Probably there is the hydrogen of 323 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 17%, and the productive rate of coupled product is 8%, and the amounts of hydrogen of emitting is 15% with respect to theoretical value.
Embodiment 19
With embodiment 16, difference is: add 3.6mg photosensitizers, the concentration of photosensitizers is 1.0 × 10
-3m.Probably there is the hydrogen of 313 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 15%, and the productive rate of coupled product is 7%, and the amounts of hydrogen of emitting is 14% with respect to theoretical value.
Embodiment 20
With embodiment 16, difference is: add 2.1mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m.Probably there is the hydrogen of 463 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 24%, and the productive rate of coupled product is 13%, and the amounts of hydrogen of emitting is 21% with respect to theoretical value.
Embodiment 21
With embodiment 16, difference is: add 2.1mg catalyzer, and 2.1mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 1.0 × 10
-3m.Probably there is the hydrogen of 556 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 25%, and the productive rate of coupled product is 15%, and the amounts of hydrogen of emitting is 25% with respect to theoretical value.
Embodiment 22
With embodiment 16, difference is: add 3.3mg catalyzer, and 2.1mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 1.6 × 10
-3m.Probably there is the hydrogen of 756 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 35%, and the productive rate of coupled product is 17%, and the amounts of hydrogen of emitting is 34% with respect to theoretical value.
Embodiment 23
With embodiment 16, difference is: add 4.2mg catalyzer, and 2.1mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-3m.Probably there is the hydrogen of 934 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 45%, and the productive rate of coupled product is 20%, and the amounts of hydrogen of emitting is 42% with respect to theoretical value.
Embodiment 24
With embodiment 16, difference is: add 8.4mg catalyzer, and 2.1mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 4.0 × 10
-3m.Probably having the hydrogen generation product of 984 μ L is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 45%, and the productive rate of coupled product is 21%, and the amounts of hydrogen of emitting is 44% with respect to theoretical value.
Embodiment 25
With embodiment 16, difference is: add 4.2mg catalyzer, and 2.1mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-3m.Illumination 16h at 40 DEG C.Probably there is the hydrogen of 1.32mL to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 65%, and the productive rate of coupled product is 25%, and the amounts of hydrogen of emitting is 59% with respect to theoretical value.
Embodiment 26
With embodiment 16, difference is: add 4.2mg catalyzer, and 0.11mmol indoles-1,2.1mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-3m.Illumination 16h at 40 DEG C.Probably there is the hydrogen of 960 μ L to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 45%, and the productive rate of coupled product is 15%, and the amounts of hydrogen of emitting is 43% with respect to theoretical value.
Embodiment 27
With embodiment 16, difference is: add 4.2mg catalyzer, and 0.3mmol indoles-1,2.1mg photosensitizers, the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-3m.Illumination 16h at 40 DEG C.Probably there is the hydrogen of 1.37mL to produce.Product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 65%, and the productive rate of coupled product is 26%, and the amounts of hydrogen of emitting is 61% with respect to theoretical value.
Embodiment 28
Taking cobalt complex 1 as catalyzer, in 2mL water, add this catalyzer of 3.6mg; Taking eosin eosinY as photosensitizers, in 2mL water, add this photosensitizers of 2.04mg; Catalyst solution and photosensitizers solution are mixed, obtain 4mL mixed aqueous solution; Getting 0.1mmol tertiary amine-2(X is CH
3, Y is that H) ﹑ and 0.2mmol indoles-1 are dissolved in 1mL acetonitrile, then 4mL mixed aqueous solution is joined to this acetonitrile solution, obtains 5mL mixing solutions.Wherein the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-3m.Logical nitrogen deoxygenation 30min, with the mouth of sealing with wax, squeeze into interior mark methane 600 μ L, then use Green LEDs illumination 16h at 40 DEG C of 525nm ± 10nm, by gas-chromatography, (TCD is detector, Shanghai Techcomp Instrument Ltd., day beautiful 7890II type) detect the growing amount of hydrogen, probably there is the hydrogen of 2.23mL to produce.After reaction finishes, add ethyl acetate extraction, use saturated common salt water washing, anhydrous sodium sulfate drying, finally separates after post.Nuclear-magnetism Qing Pu ﹑ Tan Pu ﹑ and Mass Spectrometric Identification product are 1-(1H-indol-3-yl)-2-p-methylphenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 95%, and the amounts of hydrogen of emitting is 100% with respect to theoretical value.
Embodiment 29
With embodiment 28, difference is: adding tertiary amine-3(X is OCH
3, Y is H) and replacement tertiary amine-2(X is CH
3, Y is H).Probably there is the hydrogen of 1.61mL to produce.Product is 1-(1H-indol-3-yl)-2-p-methoxyphenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 80%, and the productive rate of coupled product is 65%, and the amounts of hydrogen of emitting is 72% with respect to theoretical value.
Embodiment 30
With embodiment 28, difference is: adding tertiary amine-4(X is H, and Y is OCH
3) replacement tertiary amine-2(X is CH
3, Y is H).Probably there is the hydrogen of 1.37mL to produce.Product is 1-(1H-indol-3-yl)-2-o-methoxyphenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 70%, and the productive rate of coupled product is 45%, and the amounts of hydrogen of emitting is 61% with respect to theoretical value.
Embodiment 31
With embodiment 28, difference is: adding tertiary amine-5(X is F, and Y is H) replacement tertiary amine-2(X is CH
3, Y is H).Probably there is the hydrogen of 2.22mL to produce.Product be 1-(1H-indol-3-yl)-2-to fluorophenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 94%, and the amounts of hydrogen of emitting is 99% with respect to theoretical value.
Embodiment 32
With embodiment 28, difference is: adding tertiary amine-6(X is Br, and Y is H) replacement tertiary amine-2(X is CH
3, Y is H).Probably there is the hydrogen of 918 μ L to produce.Product be 1-(1H-indol-3-yl)-2-to bromophenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 45%, and the productive rate of coupled product is 41%, and the amounts of hydrogen of emitting is 41% with respect to theoretical value.
Embodiment 33
With embodiment 28, difference is: adding tertiary amine-7(X is CN, and Y is H) replacement tertiary amine-2(X is CH
3, Y is H).Probably there is the hydrogen of 650 μ L to produce.Product be 1-(1H-indol-3-yl)-2-to cyano-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 40%, and the productive rate of coupled product is 32%, and the amounts of hydrogen of emitting is 29% with respect to theoretical value.
Embodiment 34
Taking cobalt complex 1 as catalyzer, in 2mL water, add this catalyzer of 3.6mg; Taking eosin eosinY as photosensitizers, in 2mL water, add this photosensitizers of 2.04mg; Catalyst solution and photosensitizers solution are mixed, obtain 4mL mixed aqueous solution; Get 0.1mmol tertiary amine-1 ﹑ and 0.2mmol indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H) be dissolved in 1mL acetonitrile, then 4mL mixed aqueous solution is joined to this acetonitrile solution, obtain 5mL mixing solutions.Wherein the concentration of photosensitizers is 6.0 × 10
-4m, the concentration of catalyzer is 2.0 × 10
-3m.Logical nitrogen deoxygenation 30min, with the mouth of sealing with wax, squeeze into interior mark methane 600 μ L, then use Green LEDs illumination 16h at 40 DEG C of 525nm ± 10nm, by gas-chromatography, (TCD is detector, Shanghai Techcomp Instrument Ltd., day beautiful 7890II type) detect the growing amount of hydrogen, probably there is the hydrogen of 1.8mL to produce.After reaction finishes, add ethyl acetate extraction, use saturated common salt water washing, anhydrous sodium sulfate drying, finally separates after post.Nuclear-magnetism Qing Pu ﹑ Tan Pu ﹑ and Mass Spectrometric Identification product are 1-(N-skatole-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 90%, and the productive rate of coupled product is 72%, and the amounts of hydrogen of emitting is 81% with respect to theoretical value.
Embodiment 35
With embodiment 34, difference is: add indoles-3(R
2for CH
3, R
1﹑ R
3﹑ R
4﹑ R
5for H) replacement indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 2.23mL to produce.Product is 1-(2 methyl indole-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 98%, and the amounts of hydrogen of emitting is 100% with respect to theoretical value.
Embodiment 36
With embodiment 34, difference is: add indoles-4(R
4for CH
3, R
1﹑ R
2﹑ R
3﹑ R
5for H) replacement indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 2.15mL to produce.Product is 1-(6-skatole-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 90%, and the amounts of hydrogen of emitting is 96% with respect to theoretical value.
Embodiment 37
With embodiment 34, difference is: add indoles-5(R
4for OCH
3, R
1﹑ R
2﹑ R
3﹑ R
5for H) replacement indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.86mL to produce.Product is 1-(6-methoxy-Indole-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 90%, and the productive rate of coupled product is 78%, and the amounts of hydrogen of emitting is 82% with respect to theoretical value.
Embodiment 38
With embodiment 34, difference is: add indoles-6(R
4for Cl, R
1﹑ R
2﹑ R
3﹑ R
5for H) replacement indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.19mL to produce.Product is 1-(6-chloro-indole-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 60%, and the productive rate of coupled product is 45%, and the amounts of hydrogen of emitting is 53% with respect to theoretical value.
Embodiment 39
With embodiment 34, difference is: add indoles-7(R
4for COOCH
3, R
1﹑ R
2﹑ R
3﹑ R
5for H) replacement indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.7mL to produce.Product is 1-(6-methyl-formiate base indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 81%, and the productive rate of coupled product is 67%, and the amounts of hydrogen of emitting is 76% with respect to theoretical value.
Embodiment 40
With embodiment 34, difference is: add indoles-8(R
3for CH
3, R
1﹑ R
2﹑ R
4﹑ R
5for H) replacement indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 2.15mL to produce.Product is 1-(5-skatole-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 100%, and the productive rate of coupled product is 84%, and the amounts of hydrogen of emitting is 96% with respect to theoretical value.
Embodiment 41
With embodiment 34, difference is: add indoles-9(R
3for OCH
3, R
1﹑ R
2﹑ R
4﹑ R
5for H) replacement indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.95mL to produce.Product is 1-(5-methoxy-Indole-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 90%, and the productive rate of coupled product is 71%, and the amounts of hydrogen of emitting is 87% with respect to theoretical value.
Embodiment 42
With embodiment 34, difference is: add indoles-10(R
3for COOCH
3, R
1﹑ R
2﹑ R
4﹑ R
5for H) replacement indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.3mL to produce.Product is 1-(5-methyl-formiate base indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 60%, and the productive rate of coupled product is 54%, and the amounts of hydrogen of emitting is 58% with respect to theoretical value.
Embodiment 43
With embodiment 34, difference is: add indoles-11(R
3for NO
2, R
1﹑ R
2﹑ R
4﹑ R
5for H) replacement indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 224 μ L to produce.Product is 1-(5-nitroindoline-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 15%, and the productive rate of coupled product is 5%, and the amounts of hydrogen of emitting is 10% with respect to theoretical value.
Embodiment 44
With embodiment 34, difference is: add indoles-12(R
5for CH
3, R
1﹑ R
2﹑ R
3﹑ R
4for H) replacement indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.97mL to produce.Product is 1-(7-skatole-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 95%, and the productive rate of coupled product is 83%, and the amounts of hydrogen of emitting is 88% with respect to theoretical value.
Embodiment 45
With embodiment 34, difference is: add 0.3mmol dimethyl malonate to replace 0.2mmol indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.07mL to produce.Product is 1-(2-dimethyl malonate base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 85%, and the productive rate of coupled product is 33%, and the amounts of hydrogen of emitting is 48% with respect to theoretical value.
Embodiment 46
With embodiment 34, difference is: add 0.1mmol dimethyl malonate to replace 0.2mmol indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 780 μ L to produce.Product is 1-(2-dimethyl malonate base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 80%, and the productive rate of coupled product is 23%, and the amounts of hydrogen of emitting is 35% with respect to theoretical value.
Embodiment 47
With embodiment 34, difference is: add 0.1mmol propanedioic acid dibenzyl ester to replace 0.2mmol indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.0mL to produce.Product is 1-(2-propanedioic acid dibenzyl ester group)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 81%, and the productive rate of coupled product is 43%, and the amounts of hydrogen of emitting is 45% with respect to theoretical value.
Embodiment 48
With embodiment 34, difference is: add 0.1mmol diethyl malonate to replace 0.2mmol indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.34mL to produce.Product is 1-(2-diethyl malonate base)-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 81%, and the productive rate of coupled product is 43%, and the amounts of hydrogen of emitting is 60% with respect to theoretical value.
Embodiment 49
With embodiment 34, difference is: add 0.1mmol dimethylphosphite to replace 0.2mmol indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.79mL to produce.Product is 1-dimethyl phosphite-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 91%, and the productive rate of coupled product is 73%, and the amounts of hydrogen of emitting is 80% with respect to theoretical value.
Embodiment 50
With embodiment 34, difference is: add 0.1mmol diethyl phosphite to replace 0.2mmol indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.79mL to produce.Product is 1-diethyl phosphite-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 90%, and the productive rate of coupled product is 68%, and the amounts of hydrogen of emitting is 76% with respect to theoretical value.
Embodiment 51
With embodiment 34, difference is: add 0.1mmol dibenzyl phosphite to replace 0.2mmol indoles-2(R
1for CH
3, R
2﹑ R
3﹑ R
4﹑ R
5for H).Probably there is the hydrogen of 1.81mL to produce.Product is 1-dibenzyl phosphite-2-phenyl-1,2,3,4-tetrahydroisoquinoline.The transformation efficiency of raw material is 95%, and the productive rate of coupled product is 72%, and the amounts of hydrogen of emitting is 81% with respect to theoretical value.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Everyly belong to apparent variation or the still row in protection scope of the present invention of variation that technical scheme of the present invention extends out.
Claims (8)
1. the method that visible light catalytic cross-coupling is prepared coupled product and put hydrogen, it is characterized in that, comprise the following steps: tertiary amine, nucleophilic reagent, cobalt complex 1 or cobalt complex 2, eosin W or W S are added in solvent, obtain mixing solutions, under protection of inert gas, use radiation of visible light mixing solutions, obtain cross-coupling product the releasing hydrogen gas of tertiary amine and nucleophilic reagent;
Wherein, described nucleophilic reagent is dialkyl malonate, dialkyl phosphite or indole derivatives;
Described solvent is the mixed solvent of water or water and acetonitrile;
The structural formula of described cobalt complex 1 and cobalt complex 2 is as follows respectively:
2. the method that visible light catalytic cross-coupling according to claim 1 is prepared coupled product and put hydrogen, is characterized in that, the structural formula of described tertiary amine is as follows:
In formula, X is H, and Y is OCH
3; Y is H, and X is H, F, Cl, Br, CH
3, OCH
3or CN.
3. the method that visible light catalytic cross-coupling according to claim 1 is prepared coupled product and put hydrogen, is characterized in that, the structural formula of described indole derivatives is:
In formula, R
1﹑ R
2﹑ R
3﹑ R
4﹑ R
5complete is H; Or, R
1﹑ R
2﹑ R
3﹑ R
4﹑ R
5in one be CH
3, all the other are H; Or, R
3﹑ R
4in one be OCH
3, all the other are H; Or, R
3﹑ R
4in one be COOCH
3, all the other are H; Or, R
3for NO
2, all the other are H; Or, R
4for Cl, all the other are H.
4. the method that visible light catalytic cross-coupling according to claim 1 is prepared coupled product and put hydrogen, is characterized in that, described dialkyl malonate is dimethyl malonate, diethyl malonate or propanedioic acid dibenzyl ester.Described dialkyl phosphite is dimethylphosphite, diethyl phosphite or dibenzyl phosphite.
5. the method that visible light catalytic cross-coupling according to claim 1 is prepared coupled product and put hydrogen, is characterized in that, in the time that solvent is the mixed solvent of water and acetonitrile, the volume ratio of water and acetonitrile is not less than 1:9.
6. the method that visible light catalytic cross-coupling according to claim 1 is prepared coupled product and put hydrogen, is characterized in that, described cobalt complex 1 is not less than 0.072mg:1mL with the ratio of solvent; Described cobalt complex 2 is not less than 0.084mg:1mL with the ratio of solvent; The ratio of described eosin W or W S and solvent is not less than 0.136mg:1mL; The ratio of described tertiary amine and solvent is not less than 0.02mmol:1mL; The ratio of described indole derivatives and solvent is not less than 0.022mmol:1mL; The ratio of described dialkyl malonate and solvent is not less than 0.02mmol:1mL; The ratio of described dialkyl phosphite and solvent is not less than 0.02mmol:1mL.
7. the method for preparing coupled product and putting hydrogen according to the visible light catalytic cross-coupling described in claim 1 or 6, is characterized in that, described cobalt complex 1 is 0.072 ~ 1.44mg:1mL with the ratio of solvent; Described cobalt complex 2 is 0.084 ~ 1.68mg:1mL with the ratio of solvent; The ratio of described eosin W or W S and solvent is 0.136 ~ 0.72mg:1mL; The ratio of described tertiary amine and solvent is 0.02mmol:1mL; The ratio of described indole derivatives and solvent is 0.022 ~ 0.06mmol:1mL; The ratio of described dialkyl malonate and solvent is 0.02 ~ 0.06mmol:1mL; The ratio of described dialkyl phosphite and solvent is 0.02mmol:1mL.
8. the method that visible light catalytic cross-coupling according to claim 1 is prepared coupled product and put hydrogen, it is characterized in that, described radiation of visible light is to adopt the Green LEDs of 525nm ± 10nm to irradiate, and illumination temperature is room temperature～40 DEG C, and light application time is 12～16h.
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| CN104829518A (en) * | 2015-04-08 | 2015-08-12 | 同济大学 | Synthesis method of glycine derivatives |
| CN105985290A (en) * | 2015-02-16 | 2016-10-05 | 中国科学院理化技术研究所 | Method for cross-coupling ether compound and isoquinoline derivative |
| CN111056530A (en) * | 2019-12-27 | 2020-04-24 | 武汉大学 | Method for producing hydrogen by photocatalytic nitrogen-containing heterocyclic compound |
| CN114669319A (en) * | 2022-04-19 | 2022-06-28 | 南京航空航天大学 | Nano cobaltosic oxide-carbon nitrogen composite catalyst and preparation method and application thereof |
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| CN104447865A (en) * | 2014-09-15 | 2015-03-25 | 四川理工学院 | Preparation method of alpha-phosphoramidate compound |
| CN105985290A (en) * | 2015-02-16 | 2016-10-05 | 中国科学院理化技术研究所 | Method for cross-coupling ether compound and isoquinoline derivative |
| CN105985290B (en) * | 2015-02-16 | 2019-12-06 | 中国科学院理化技术研究所 | Cross coupling method of ether compound and isoquinoline derivative |
| CN104761485A (en) * | 2015-03-09 | 2015-07-08 | 中国科学院成都生物研究所 | A novel hydrogen storage material and a hydrogen resolving method |
| CN104829518A (en) * | 2015-04-08 | 2015-08-12 | 同济大学 | Synthesis method of glycine derivatives |
| CN111056530A (en) * | 2019-12-27 | 2020-04-24 | 武汉大学 | Method for producing hydrogen by photocatalytic nitrogen-containing heterocyclic compound |
| CN111056530B (en) * | 2019-12-27 | 2021-10-22 | 武汉大学 | Method for producing hydrogen by photocatalytic nitrogen-containing heterocyclic compound |
| CN114669319A (en) * | 2022-04-19 | 2022-06-28 | 南京航空航天大学 | Nano cobaltosic oxide-carbon nitrogen composite catalyst and preparation method and application thereof |
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