CN105440015B - The preparation method of 2 methylquinolines and tetrahydroisoquinoline coupling reaction is catalyzed under copper complex visible ray - Google Patents

The preparation method of 2 methylquinolines and tetrahydroisoquinoline coupling reaction is catalyzed under copper complex visible ray Download PDF

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CN105440015B
CN105440015B CN201510864375.7A CN201510864375A CN105440015B CN 105440015 B CN105440015 B CN 105440015B CN 201510864375 A CN201510864375 A CN 201510864375A CN 105440015 B CN105440015 B CN 105440015B
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王斌
夏中玥
刘鲲
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Tianjin Normal University
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    • 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
    • C07D401/06—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 linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C07D401/14—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 three or more hetero rings

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Abstract

The present invention relates to a kind of method for being catalyzed 2 methylquinoline class compounds and tetrahydroisoquinolicompounds compounds dehydrogenation coupling reaction under visible light with the double diphenylphosphine univalent copper complexs of the phenanthroline carborane of 2,9 dimethyl, 4,7 diphenyl 1,10.Preparation method of the present invention is：By the double diphenylphosphine univalent copper complexs of the phenanthroline carborane of 2,9 dimethyl of photochemical catalyst, 4,7 diphenyl 1,10, corresponding 2 methylquinoline, tetrahydroisoquinoline and m-methyl benzoic acid are according to 0.015：2：1：3 mixed in molar ratio, solvent acetonitrile and methanol are added, acetonitrile and methanol are according to 1:1 volume ratio mixes, and reaction system is full of oxygen, 3.5w white light LED lamp band is placed at reaction bulb 2cm, after 35 hours, reaction system drains solvent, is separated by silica gel column chromatography, obtains corresponding product.Having the beneficial effect that for this method is reacted using visible light catalytic, environmentally friendly low-carbon.

Description

2- methylquinolines and tetrahydroisoquinoline coupling reaction are catalyzed under copper complex visible ray Preparation method
Present patent application obtains state natural sciences fund（21102101,21172173）With Tianjin Natural Science Fund In The Light （15JCYBJC48200）Subsidy.
Technical field
The invention belongs to organic chemical synthesis technical field, is related to a kind of 2,9- dimethyl -4,7- diphenyl -1,10- The double diphenylphosphine univalent copper complexs of phenanthroline carborane are catalyzed 2- methylquinoline class compounds under visible light and tetrahydrochysene is different The preparation method of quinolines dehydrogenation coupling reaction.
Background technology
Quinoline and isoquinoline compound are the basic frameworks of the natural products and medicine that much have bioactivity, therefore are closed Research and development into the quinoline containing various substituents and isoquinoline compound to new drug have great meaning.Yang Luo seminars in The dehydrogenation that report in 2014 can be catalyzed 2- methylquinolines and tetrahydroisoquinoline in a heated condition with copper trifluoromethanesulfcomposite is coupled Reaction（F. F. Wang, C. P. Luo, G.J. Deng and L. Yang, Green Chem., 2014, 16, 2428）.But the reaction still drives reaction, not friendly to the environment using traditional heat energy.
One important direction of organic chemistry development is exactly that to find a kind of mild condition, green and yield higher Synthetic method.Before a general century, Italian Ciamician has found a kind of just rich reserves, it is green simultaneously The sustainable clean energy resource using catalytic reaction（G. Ciamician, Science, 1912, 36, 385）, and photocatalysis The product of reaction, it can not be synthesized at all through commonly using other conventional methods.Since then, photochemistry and light-catalyzed reaction are widely used in Synthetic organic chemical art（N. Hoffmann, Chem. Rev. 2008, 108, 1052； M. Fagnoni, D. Dondi, D. Ravelli and A. Albini, Chem. Rev. 2007, 107, 2725）.But due to organising The major absorbance peak of compound is less in visible region, so using the example of visible light catalytic organic reaction also not at present It is more, this also by be organic chemistry forward position developing direction.Having in nature can much will be seen that light is converted into self-energy Example（D. Gust and T. A. Moore,Science, 1989, 244, 35； T. J. Meyer, Acc. Chem. Res., 1989, 22, 163；D. Gust, T. A. Moore and A. L. Moore,Acc. Chem. Res., 1993, 26,198； V. Balzani, A. Credi andM. Venturi,ChemSusChem, 2008, 1, 26）, This is that chemists provide one it will be seen that a platform of visible light catalytic conversion.
In numerous photochemical catalysts, photoredox agent is most important one kind, and it can be applied to photocatalytic water, too Sun can store, and couple proton translocation, and numerous Disciplinary Frontiers such as solar energy power generating（K. Kalyanasundaram, Coord. Chem. Rev., 1982, 46, 159； A. Juris, V. Balzani, F. Barigelletti, S. Campagna, P. Belser and A. von Zelewsky, Coord. Chem. Rev., 1988, 84, 85；V. Balzani, G. Bergamini, F. Marchioni and P. Ceroni, Coord. Chem. Rev., 2006, 250, 1254； X. Sala, I. Romero, M. Rodriguez, L. Escriche and A. Llobet, Angew. Chem., Int. Ed., 2009, 48, 2842；H. Cano-Yelo and A. Deronzier, J. Chem. Soc., Perkin Trans. 2, 1984, 1093）.
In recent years because copper compound has at a low price, nontoxic, the advantages of abundant mineral resources etc. are incomparable, get over More to cause the concern of people and interest, find, can be obtained by adjusting the part of copper complex by substantial amounts of research The visible absorption frequency and the stability of compound needed, so as to obtain excellent photochemical catalyst.
Therefore, we disclose herein is coordinated with the monovalence copper of phenanthroline class part and the double diphenylphosphine mixtures of carborane Thing is catalyzed the achievement in research of 2- methylquinoline class compounds and tetrahydroisoquinolicompounds compounds dehydrogenation coupling reaction under visible light.
The content of the invention
It is an object of the invention to provide a kind of double with 2,9- dimethyl -4,7- diphenyl -1,10- phenanthrolines carborane Diphenylphosphine univalent copper complex is catalyzed 2- methylquinoline class compounds and tetrahydroisoquinolicompounds compounds dehydrogenation under visible light The preparation method of coupling reaction.
The invention discloses following technology contents to achieve the above object：
It is the double diphenyl of 2,9- dimethyl -4,7- diphenyl -1,10- phenanthrolines carborane to react the photochemical catalyst used The structural formula of phosphine univalent copper complex is（I）：
（I）
The product of 2- methylquinolines class compound of the present invention and tetrahydroisoquinolicompounds compounds dehydrogenation coupling reaction General structure be（Ⅱ）：
（Ⅱ）
Wherein R1-R2：Hydrogen atom；Aliphatic substitution containing 1 to 20 carbon, such as methyl, ethyl, n-propyl, just Butyl, n-pentyl, n-hexyl, n-heptyl, isopropyl, the tert-butyl group, cyclohexyl, vinyl, pi-allyl etc.；Contain 1 to 20 carbon Aromatic substituents, such as：Phenyl, tolyl, ethylbenzene, 2-methyl-2-phenylpropane base, cumenyl, naphthyl, first naphthyl, tertiary fourth naphthyl Deng；Aliphatic substitution containing aerobic, nitrogen, 1 to 20 carbon of sulfur heteroatom, such as methoxyl group, ethyoxyl, positive propoxy, just Butoxy, n-pentyloxy, positive hexyloxy, positive epoxide in heptan, isopropoxy, tert-butoxy, hexamethylene yloxymethyl, methylamino, ethamine Base, n-propylamine base, n-butylamine-based, n-amylamine base, n-hexylamine base, positive heptyl amice base, isopropylamine base, tert-butylamine base, cyclohexylamino, first Sulfydryl, second sulfydryl, positive third sulfydryl, positive fourth sulfydryl, positive penta sulfydryl, just own sulfydryl, positive sulfydryl in heptan, isopropyl sulfydryl, tertiary fourth sulfydryl, ring Own sulfydryl or the aromatic substituents containing aerobic, nitrogen, 1 to 20 carbon of sulfur heteroatom, such as pyridine radicals, substituted pyridinyl, quinoline Quinoline base, substd quinolines base, furyl, substituted furan base, thienyl, substituted thiophene base etc..R1-R2 can with it is identical can not also Together；
It is of the present invention to use the double diphenylphosphine monovalencies of 2,9- dimethyl -4,7- diphenyl -1,10- phenanthrolines carborane The preparation method that copper complex is catalyzed the dehydrogenation coupling reaction of 2- methylquinolines and tetrahydroisoquinoline under visible light is：Light is urged Agent 2, the double diphenylphosphine univalent copper complexs of 9- dimethyl -4,7- diphenyl -1,10- phenanthrolines carborane, corresponding 2- Methylquinoline, tetrahydroisoquinoline and m-methyl benzoic acid are according to 0.015：2：1：3 mixed in molar ratio, add solvent acetonitrile and first Alcohol, acetonitrile and methanol are according to 1:1 volume ratio is mixed, and reaction system is full of oxygen, and 3.5w white light is placed at reaction bulb 2cm LED lamp band, after 35 hours, reaction system drains solvent, is separated by silica gel column chromatography, obtains corresponding product.It is synthesized Route is as follows：
1-24 is the compound synthesized by above-mentioned route, and in embodiment compound structural formula
Wherein 1 chemical name is 2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
Wherein 2 chemical name is 6- methyl -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
Wherein 3 chemical name is the bromo- 2- of 6-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
Wherein 4 chemical name is 6- nitros -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
Wherein 5 chemical name is 6- methoxyl groups -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline Quinoline；
Wherein 6 chemical name is 6- cyclohexyl -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline Quinoline；
Wherein 7 chemical name is N, N- dimethyl -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl） Quinoline -6- amine；
Wherein 8 chemical name is the 6- tert-butyl groups -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline Quinoline；
Wherein 9 chemical name is 6- normal-butyls -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline Quinoline；
Wherein 10 chemical name is 6- first sulfydryls -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline Quinoline；
Wherein 11 chemical name is 6- phenyl -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline Quinoline；
Wherein 12 chemical name is 2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）-6-（Pyridine radicals- 2-）Quinoline；
Wherein 13 chemical name is 2-（（2- p-methylphenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
Wherein 14 chemical name is 2-（（2- (4- bromophenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
Wherein 15 chemical name be 2- (（2- (4- iodophenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
Wherein 16 chemical name be 2- (（2- (4- nitrobenzophenones) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline Quinoline；
Wherein 17 chemical name be 2- (（2- (4- methoxyphenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl） Quinoline；
Wherein 18 chemical name be 2- (（2- (4- tert-butyl-phenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl） Quinoline；
Wherein 19 chemical name be 2- (（2- (4- cyclohexyl phenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl） Quinoline；
Wherein 20 chemical name be 2- (（2- (1,1 '-xenyl -4-) -1,2,3,4- tetrahydro isoquinolyls -1-）First Base）Quinoline；
Wherein 21 chemical name be 2- (（2- (4- n-butylphenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl） Quinoline；
Wherein 22 chemical name is N, N- dimethyl -4-（1-（Quinolyl -2- methyl）- 3,4- dihydro-isoquinoline base -2 （1H）-）Amine；
Wherein 23 chemical name be 2- (（2- (4- first mercaptophenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl） Quinoline；
Wherein 24 chemical name be 2- (（2-(4-（Pyridine -2-) phenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）First Base）Quinoline.
The present invention further discloses, and is coupled using the dehydrogenation that 2- methylquinolines and tetrahydroisoquinoline are catalyzed under visible ray Application of the corresponding product that reaction method for preparing obtains in terms of different type photochemical catalyst is prepared.
Having the beneficial effect that for this method is reacted using visible light catalytic, environmentally friendly low-carbon, and luminous energy deposit enriches in nature, The product species of the dehydrogenation coupling of the 2- methylquinolines and tetrahydroisoquinoline that can prepare are a lot, and typical compound includes：
（1）2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（2）6- methyl -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（3）The bromo- 2- of 6-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（4）6- nitros -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（5）6- methoxyl groups -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（6）6- cyclohexyl -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（7）N, N- dimethyl -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline -6- amine；
（8）The 6- tert-butyl groups -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（9）6- normal-butyls -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（10）6- first sulfydryls -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（11）6- phenyl -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（12）2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）-6-（Pyridine radicals -2-）Quinoline；
（13）2-（（2- p-methylphenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（14）2-（（2- (4- bromophenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（15）2-(（2- (4- iodophenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（16）2-(（2- (4- nitrobenzophenones) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（17）2-(（2- (4- methoxyphenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（18）2-(（2- (4- tert-butyl-phenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（19）2-(（2- (4- cyclohexyl phenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（20）2-(（2- (1,1 '-xenyl -4-) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（21）2-(（2- (4- n-butylphenyls) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（22）N, N- dimethyl -4-（1-（Quinolyl -2- methyl）- 3,4- dihydro-isoquinoline base -2（1H）-）Amine；
（23）2-(（2- (4- first mercaptophenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline；
（24）2-(（2-(4-（Pyridine -2-) phenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline.
Embodiment
Illustrate the present invention with reference to embodiment, the scheme of embodiment described here does not limit the present invention, this area it is special Industry personnel can make improvements and change according to the spirit of the present invention, and described such modifications and variations are regarded as this hair In bright scope, the scope of the present invention and essence all have the right requirement to limit；Wherein described photochemical catalyst 2,9- dimethyl -4, The double diphenylphosphine univalent copper complexs of 7- diphenyl -1,10- phenanthrolines carborane（Bin Wang, Deepak Prakash Shelar, Xian-Zhu Han, Ting-Ting Li, Xiangguo Guan, Wei Lu, Kun Liu, Yong Chen, Wen-Fu Fu, Chi-Ming Che, Chem. Eur. J. 2015, 21, 1184）, various tetrahydroisoquinolines it is former Material（F. Y. Kwong, A. Klapars, S. L. Buchwald,Org. Lett. 2002, 4, 581）According to document It is prepared by method.In addition to particularly pointing out, remaining 2- methylquinoline class compound and various solvents, by commercially available.
Embodiment 1
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg2- methylquinolines（0.4 mmol, 2.0 equiv.）,41.8 mg N- Phenyl tetrahydroisoquinoline（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system are full of oxygen Gas, 3.5W Led white light bands are placed at reaction bulb 2cm, after 35 hours, reaction system reaction system drains solvent, Separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 63.5 mg, yield：90%.（2-（（2- phenyl -1,2,3, 4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1 H NMR (400MHz, CDCl3) δ8.15 (d, J=8.3 Hz, 1H), 7.96 (d, J=8.3 Hz, 1H), 7.77 (m, 2H), 7.52 (t, J=7.6 Hz, 1H), 7.17 (m, 4H), 7.09 (d, J=8.0 Hz, 1H), 7.02 (m, 1H), 6.94 (d, J=8.0 Hz, 2H), 6.89 (d, J=7.5 Hz, 1H), 6.68 (t, J =7.2 Hz, 1H), 5.48 (t, J=6.9 Hz, 1H), 3.83 (m, 1H), 3.71 (m, 1H), 3.37 (m, 1H), 3.16 (m, 1H), 2.96 (m, 1H); HRMS (ESI) exact mass calculated for [M+1] (C25H23N2) requires m/z 351.1861,found m/z 351.1858.
Embodiment 2
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 62.9 mg 2,6- dimethyl quinolines（0.4 mmol, 2.0 equiv.）,41.8 Mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system are filled Full oxygen, places 3.5W Led white light bands, after 35 hours, reaction system reaction system is drained molten at reaction bulb 2cm Agent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 52.1 mg, yield：71%.（6- methyl -2-（（2- Phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1 H NMR (400MHz, CDCl3) δ8.05 (d, J=8.5 Hz, 1H), 7.87 (d, J=8.3 Hz, 1H), 7.57 (m, 2H), 7.19 (m, 4H), 7.04 (m, 2H), 6.95 (d, J=8.3 Hz, 2H), 6.87 (d, J=7.5 Hz, 1H), 6.69 (t, J=7.1 Hz, 1H), 5.46 (t, J=6.9 Hz, 1H), 3.83 (m, 1H), 3.72 (m, 2H), 3.35 (m, 1H), 3.17 (m, 1H), 2.97 (m, 1H); HRMS (ESI) exact mass calculated for [M+1] (C26H25N2) requires m/z 365.2018, found m/z 365.2012.
Embodiment 3
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 88.0 mg 2- methyl -6- bromoquinolines（0.4 mmol, 2.0 equiv.）,41.8 Mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system are filled Full oxygen, places 3.5W Led white light bands, after 35 hours, reaction system reaction system is drained molten at reaction bulb 2cm Agent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 41.9 mg, yield：57%.（The bromo- 2- of 6-（（2- benzene Base -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1 H NMR (400MHz, CDCl3) δ 8.01 (d, J=8.9 Hz, 1H), 7.91 (d, J=2.1 Hz, 1H), 7.86 (d, J=8.4 Hz, 1H), 7.79 (d, J=8.9 Hz, 1H), 7.17 (m, 4H), 7.08 (d, J =8.4 Hz, 1H), 7.02 (m, 1H), 6.91 (d, J=8.1 Hz, 2H), 6.85 (d, J=7.6 Hz, 1H), 6.68 (t, J=7.2 Hz, 1H), 5.44 (t, J=7.0 Hz, 1H), 3.80 (m, 1H), 3.70 (m, 2H), 3.39 (m, 1H), 3.15 (m, 1H), 2.95 (m, 1H); HRMS (ESI) exact mass calculated for [M+1] (C25H22BrN2) requires m/z 429.0966, found m/z 429.0959.
Embodiment 4
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 75.3 mg 2- methyl -6- nitroquinolines（0.4 mmol, 2.0 equiv.）, 41.8 mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reactant System is full of oxygen, 3.5W Led white light bands is placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is taken out Dry solvent, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 62.5 mg, yield：82%.（6- nitros -2- （（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) 8.71 (s, 1H), 8.47 (d, J=8.8 Hz, 1H), 8.23 (d,J=9.2 Hz, 1H), 8.09 (d, J=8.4 Hz, 1H), 7.16 (m, 5H), 7.02 (m, 1H), 6.88 (m, 3H), 6.66 (t, J=7.6 Hz, 1H), 5.47 (t, J=5.6 Hz, 1H), 3.75 (m, 1H), 3.69 (m, 2H), 3.38 (m, 1H), 3.11 (m, 1H), 2.92 (m, 1H); HRMS (ESI) exact mass calculated for [M+1] (C25H22N3O2) requires m/z 396.1712, found m/z 395.1701.
Embodiment 5
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 69.3 mg 2- methyl -6- methoxy quinolines（0.4 mmol, 2.0 equiv.）, 41.8 mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reactant System is full of oxygen, 3.5W Led white light bands is placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is taken out Dry solvent, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 59.4 mg, yield：78%.（6- methoxyl groups- 2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) 8.02 (d, J=9.2 Hz, 1H), 7.84 (d, J=8.4 Hz, 1H), 7.36 (m, 1H), 7.14 (m, 4H), 7.00 (m, 3H), 6.91 (d, J=8.0 Hz, 2H), 6.85 (d, J=8.0 Hz, 1H), 6.66 (t, J=7.2 Hz, 1H), 5.41 (t, J=7.2 Hz, 1H), 3.92 (s, 3H), 3.78 (m, 1H), 3.65 (m, 2H), 3.29 (m, 1H), 3.11 (m, 1H), 2.92 (m, 1H); HRMS (ESI) exact mass calculated for [M+1] (C26H25N2O) requires m/z 381.1967, found m/z 381.1951.
Embodiment 6
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 90.1 mg 2- cyclohexyl -6- methoxy quinolines（0.4 mmol, 2.0 equiv.）, 41.8 mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL first Alcohol, reaction system are full of oxygen, and 3.5W Led white light bands, after 35 hours, reaction system are placed at reaction bulb 2cm Reaction system drains solvent, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 79.6 mg, yield：92%. （6- cyclohexyl -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) 8.00 (d, 1H), 7.84 (d, 1H), 7.77 (d, 1H), 7.62 (d, 1H), 7.16-7.21 (m, 6H), 6.93-7.02 (m, 3H), 6.79-6.81 (m, 1H), 4.29 (t, 1H), 3.52-3.73 (m, 3H), 3.25-3.27 (m, 1H), 2.86-2.91 (m, 2H), 2.69-2.71 (m, 1H), 1.83-1.86 (m, 2H), 1.43-1.61 (m, 8H); HRMS (ESI) exact mass calculated for [M+1] (C31H33N2) requires m/z 433.2644, found m/z 433.2631.
Embodiment 7
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 74.5 mg N, N, 2- trimethylquinoline -6- amine（0.4 mmol, 2.0 equiv.）, 41.8 mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL first Alcohol, reaction system are full of oxygen, and 3.5W Led white light bands, after 35 hours, reaction system are placed at reaction bulb 2cm Reaction system drains solvent, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 60.6 mg, yield：77%. （N, N- dimethyl -2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline -6- amine）
1H NMR (400 MHz, CDCl3) δ 8.45 (d, 1H), 7.86 (d, 1H), 7.53 (d, 1H), 7.21 (m, 5H), 7.01 (m, 1H), 6.94 (t, 2H), 6.91 (m, 1H), 6.80 (d, 1H), 6.53 (t, 1H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 1H), 3.27 (m, 1H), 3.02 (s, 6H), 2.90 (m, 2H); HRMS (ESI) exact mass calculated for [M+1] (C27H28N3) requires m/z 394.2283, found m/z 394.2271.
Embodiment 8
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, the 79.7 mg 6- tert-butyl group -2- methylquinolines（0.4 mmol, 2.0 equiv.）, 41.8 mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reactant System is full of oxygen, 3.5W Led white light bands is placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is taken out Dry solvent, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 74.0 mg, yield：91%.（The 6- tert-butyl groups- 2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.00 (d, 1H), 7.85 (d, 1H), 7.77 (t, 1H), 7.62 (m, 1H), 7.21-7.18 (m, 6H), 7.01 (m, 1H), 6.94 (m, 2H), 6.80 (m, 1H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H), 1.43 (s, 9H); HRMS (ESI) exact mass calculated for [M+1] (C29H31N2)requires m/z 407.2409, found m/ z 407.2414.
Embodiment 9
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 79.7 mg 6- normal-butyl -2- methylquinolines（0.4 mmol, 2.0 equiv.）, 41.8 mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reactant System is full of oxygen, 3.5W Led white light bands is placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is taken out Dry solvent, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 72.3 mg, yield：89%.（6- normal-butyls- 2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.04 (d, 1H), 7.86 (d, 1H), 7.79 (d, 1H), 7.62 (d, 1H), 7.21-7.20 (m, 6H), 7.01 (m, 1H), 6.94 (m, 2H), 6.80 (m, 1H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H), 2.64 (m, 2H), 1.56 (m, 2H), 1.33 (m, 2H), 0.89 (m,3H); HRMS (ESI) exact mass calculated for [M+ 1] (C29H31N2) requires m/z 407.2409, found m/z 407.2412.
Embodiment 10
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 75.6 mg 6- first sulfydryl -2- methylquinolines（0.4 mmol, 2.0 equiv.）, 41.8 mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reactant System is full of oxygen, 3.5W Led white light bands is placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is taken out Dry solvent, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 67.3 mg, yield：85%.（6- first sulfydryl- 2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.04 (d, 1H), 7.83 (d, 1H), 7.53 (t, 1H), 7.46 (d, 1H), 7.21-7.20 (m, 6H), 7.01 (m, 1H), 6.94 (m, 2H), 6.80 (m, 1H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H), 2.45 (s, 3H); HRMS (ESI) exact mass calculated for [M+1] (C26H25N2S) requires m/z 397.1660, found m/z 397.1677.
Embodiment 11
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 87.6 mg 6- phenyl -2- methylquinolines（0.4 mmol, 2.0 equiv.）,41.8 Mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system are filled Full oxygen, places 3.5W Led white light bands, after 35 hours, reaction system reaction system is drained molten at reaction bulb 2cm Agent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 75.0 mg, yield：88%.（6- phenyl -2-（（2- Phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.27 (d, 1H), 8.08 (d, 1H), 7.99 (d, 1H), 7.80 (m, 1H), 7.75 (m, 2H), 7.49 (m, 2H), 7.41 (m, 1H), 7.32 (m, 1H), 7.21- 7.20 (m, 5H), 7.01 (m, 1H), 6.94 (m, 2H), 6.80 (m, 1H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H); HRMS (ESI) exact mass calculated for [M+ 1] (C31H27N2) requires m/z 427.2096, found m/z 427.2087.
Embodiment 12
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 88.0 mg 6- pyridine radicals -2- methylquinolines（0.4 mmol, 2.0 equiv.）, 41.8 mg N- phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reactant System is full of oxygen, 3.5W Led white light bands is placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is taken out Dry solvent, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 73.5 mg, yield：86%.（2-（（2- benzene Base -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）-6-（Pyridine radicals -2-）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.72 (d, 1H), 8.37 (d, 1H), 8.33 (d, 1H), 8.21 (d, 1H), 8.10 (d, 1H), 7.38 (m, 1H), 7.30 (m, 1H), 7.21-7.20 (m, 5H), 7.14 (m, 1H), 7.01 (m, 1H), 6.94 (m, 2H), 6.80 (m, 1H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H); HRMS (ESI) exact mass calculated for [M+ 1] (C30H26N3) requires m/z 428.2049, found m/z 428.2056.
Embodiment 13
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,44.6 mg N- P-methylphenyl tetrahydroisoquinoline（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system are full of Oxygen, 3.5W Led white light bands are placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is drained molten Agent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 65.6 mg, yield：90%.（2-（（2- is to toluene Base -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.14 (d, 1H), 7.97 (d, 1H), 7.77 (m, 2H), 7.52 (t, 1H), 7.14 (m, 3H), 7.03 (m, 1H), 6.97 (d, 2H), 6.91 (d, 1H), 6.84 (d, 2H), 5.41 (t, 1H), 3.79 (m, 1H), 3.71 (m, 2H), 3.37 (m, 1H), 3.15 (m, 1H), 2.89 (m, 1H), 2.19 (s, 3H);HRMS (ESI) exact mass calculated for [M+1] (C26H25N2) requires m/z 365.1939,found m/z 365.1922.
Embodiment 14
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,57.4 mg N- 4- bromophenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system are full of Oxygen, 3.5W Led white light bands are placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is drained molten Agent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 80.5 mg, yield：94%.（2-（（2- (4- bromobenzenes Base) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.16 (d, 1H), 7.96 (d, 1H), 7.77 (m, 2H), 7.53 (t, 1H), 7.20 (m, 4H), 7.04 (d, 2H), 6.90 (d, 1H), 6.81 (d, 2H), 5.44 (t, 1H), 3.78 (m, 1H), 3.65 (m, 1H), 3.36 (m, 1H), 3.13 (m, 1H), 2.96 (m, 1H); HRMS (ESI) exact mass calculated for [M+1] (C25H22 Br N2) requires m/z 429.0888, found m/z 429.0874.
Embodiment 15
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,67.0 mg N- 4- iodophenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system are full of Oxygen, 3.5W Led white light bands are placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is drained molten Agent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 83.8 mg, yield：88%.（2-(（2- (4- iodobenzenes Base) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.10 (d, 1H), 8.01 (d, 1H), 7.81 (t, 1H), 7.64 (m, 1H), 7.48 (m, 1H), 7.36 (d, 2H), 7.30 (m, 1H), 7.20 (m, 3H), 7.01 (m, 1H), 6.50 (m, 2H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H); HRMS (ESI) exact mass calculated for [M+1] (C25H22IN2) requires m/z 477.0749, found m/z 477.0754.
Embodiment 16
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,50.8 mg N- 4- nitrobenzophenone tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system are filled Full oxygen, places 3.5W Led white light bands, after 35 hours, reaction system reaction system is drained molten at reaction bulb 2cm Agent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 64.0 mg, yield：81%.（2-(（2- (4- nitros Phenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.10 (d, 1H), 8.04 (d, 1H), 8.01 (d, 1H), 7.81 (t, 1H), 7.64 (m, 1H), 7.48 (m, 1H), 7.30 (d, 1H), 7.20 (m, 3H), 7.01 (m, 3H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H); HRMS (ESI) exact mass calculated for [M+1] (C25H22N3O2) requires m/z 396.1634, found m/z 396.1628.
Embodiment 17
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,47.8 mg N- 4- methoxyphenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system Full of oxygen, 3.5W Led white light bands are placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is drained Solvent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 65.4 mg, yield：86%.（2-(（2- (4- first Phenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.10 (d, 1H), 8.01 (d, 1H), 7.81 (t, 1H), 7.64 (m, 1H), 7.48 (m, 1H), 7.30 (m, 1H), 7.20 (m, 3H), 7.01 (m, 1H), 6.73 (m, 2H), 6.55 (m, 2H), 4.29 (t, 1H), 3.81 (s, 3H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H); HRMS (ESI) exact mass calculated for [M+1] (C26H25N2O) requires m/z 381.1889, found m/z 381.1897.
Embodiment 18
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,53.0 mg N- 4- tert-butyl-phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system Full of oxygen, 3.5W Led white light bands are placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is drained Solvent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 69.1 mg, yield：85%.（2-(（2- (uncles 4- Butyl phenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.10 (d, 1H), 8.01 (d, 1H), 7.81 (t, 1H), 7.64 (m, 1H), 7.48 (m, 1H), 7.30 (m, 1H), 7.20 (m, 3H), 7.01 (m, 1H), 6.96 (d, 2H), 6.60 (m, 2H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H), 1.33 (s, 9H); HRMS (ESI) exact mass calculated for [M+1] (C29H31N2) requires m/z 407.2409, found m/z 407.2413.
Embodiment 19
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,58.2 mg N- 4- cyclohexyl phenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system Full of oxygen, 3.5W Led white light bands are placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is drained Solvent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 76.1 mg, yield：88%.（2-(（2- (4- rings Hexyl phenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.10 (d, 1H), 8.01 (d, 1H), 7.81 (t, 1H), 7.64 (m, 1H), 7.48 (m, 1H), 7.30 (m, 1H), 7.20 (m, 3H), 7.01 (m, 1H), 6.92 (m, 2H), 6.68 (m, 2H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H), 2.72 (m, 1H), 1.86 (m, 4H), 1.53 (m, 4H), 1.46 (m, 2H); HRMS (ESI) exact mass calculated for [M+1] (C31H33N2) requires m/z 433.2566, found m/z 433.2574.
Embodiment 20
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,58.2 mg 2- (1,1 '-xenyl -4-) -1,2,3,4- tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL Methanol, reaction system are full of oxygen, and 3.5W Led white light bands, after 35 hours, reactant are placed at reaction bulb 2cm It is that reaction system drains solvent, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 76.7 mg, yield： 90%.（2-(（2- (1,1 '-xenyl -4-) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.10 (d, 1H), 8.01 (d, 1H), 7.81 (t, 1H), 7.75 (m, 2H),7.64 (m, 1H), 7.49-7.41 (m, 6H), 7.30 (m, 1H), 7.20 (m, 3H), 7.01 (m, 1H), 6.92 (m, 2H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H); HRMS (ESI) exact mass calculated for [M+1] (C31H27N2) requires m/z 427.2096, found m/z 427.2087.
Embodiment 21
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,53.0 mg N- 4- n-butylphenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system Full of oxygen, 3.5W Led white light bands are placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is drained Solvent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 67.4mg, yield：83%.（2-(（2- (the positive fourths of 4- Base phenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.10 (d, 1H), 8.01 (d, 1H), 7.81 (t, 1H), 7.64 (m, 1H), 7.48 (m, 1H), 7.30 (m, 1H), 7.20 (m, 3H), 7.01 (m, 1H), 6.89 (m, 2H), 6.68 (m, 2H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H), 2.55 (m, 2H), 1.56 (m, 2H), 1.33 (m, 2H), 0.89 (m, 3H); HRMS (ESI) exact mass calculated for [M+1] (C29H31N2) requires m/z 407.2409, found m/z 407.2414.
Embodiment 22
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,50.4 mg N, N- dimethyl -4- (3,4- dihydro-isoquinolines -2 (1H) -)-amine（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 ML methanol, reaction system are full of oxygen, and 3.5W Led white light bands are placed at reaction bulb 2cm, after 35 hours, reaction System reaction system drains solvent, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 68.4mg, yield： 87%.（N, N- dimethyl -4-（1-（Quinolyl -2- methyl）- 3,4- dihydro-isoquinoline base -2（1H）-）Amine）
1H NMR (400 MHz, CDCl3) δ7.35 (d, 1H), 7.20 (m, 3H), 7.01 (m, 1H), 6.97 (d, 1H), 6.84 (m, 1H), 6.62 (m, 4H), 6.50 (d, 1H), 5.71 (m, 1H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 3.02 (s, 6H), 2.90 (m, 2H), 2.39 (s, 3H); HRMS (ESI) exact mass calculated for [M+1] (C26H30N3) requires m/z 384.2361, found m/z 384.2357.
Embodiment 23
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,51.0 mg N- 4- first mercaptophenyl tetrahydroisoquinolines（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction system Full of oxygen, 3.5W Led white light bands are placed at reaction bulb 2cm, after 35 hours, reaction system reaction system is drained Solvent, separated by silica gel column chromatography, obtain corresponding dehydrogenation coupled product, 72.1mg, yield：91%.（2-(（2- (4- first mercaptos Base phenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.10 (d, 1H), 8.01 (d, 1H), 7.81 (m, 1H), 7.64 (m, 1H), 7.48 (m, 1H), 7.35 (m, 2H), 7.30 (m, 1H), 7.20 (m, 3H), 7.01 (m, 1H), 6.63 (m, 2H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H), 2.38 (s, 3H); HRMS (ESI) exact mass calculated for [M+1] (C26H25N2S) requires m/z 397.1660, found m/z 397.1653.
Embodiment 24
2.8 mg photochemical catalysts 2,9- dimethyl -4,7- diphenyl -1,10- are added in 25mL Schlenk bottles The double diphenylphosphine univalent copper complexs of phenanthroline carborane（3 μmol, 0.015 equiv.）, methylbenzene first between 82.0 mg Acid（0.6 mmol, 3.0 equiv.）, 57.3 mg 2- methylquinolines（0.4 mmol, 2.0 equiv.）,57.2 mg N- 4-（Pyridine -2-) phenyl) tetrahydroisoquinoline（0.2 mmol, 1.0 equiv.）, 1.0 mL acetonitriles and 1.0 mL methanol, reaction System is full of oxygen, and 3.5W Led white light bands, after 35 hours, reaction system reaction system are placed at reaction bulb 2cm Solvent is drained, is separated by silica gel column chromatography, obtains corresponding dehydrogenation coupled product, 76.0mg, yield：89%.（2-(（2-(4- （Pyridine -2-) phenyl) -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline）
1H NMR (400 MHz, CDCl3) δ8.37 (d, 1H), 8.10 (d, 1H), 8.01 (d, 1H), 7.98 (m, 2H), 7.81 (m, 1H), 7.64 (m, 1H), 7.48 (m, 1H), 7.38 (m, 1H), 7.30 (m, 1H), 7.20 (m, 3H), 7.14 (m, 1H), 7.01 (m, 1H), 6.92 (m, 2H), 4.29 (t, 1H), 3.73 (m, 2H), 3.52 (m, 2H), 2.90 (m, 2H); HRMS (ESI) exact mass calculated for [M+1] (C30H26N3) requires m/z 428.2049, found m/z 428.2053。

Claims (1)

1. one kind is using the double diphenylphosphine univalent copper complexs of 2,9- dimethyl -4,7- diphenyl -1,10- phenanthrolines carborane The preparation method of the dehydrogenation coupling reaction of 2- methylquinolines and tetrahydroisoquinoline is catalyzed under visible light, it is characterised in that by as follows The step of carry out：By photochemical catalyst 2, the double diphenylphosphine monovalencies of 9- dimethyl -4,7- diphenyl -1,10- phenanthrolines carborane Copper complex, corresponding 2- methylquinolines, tetrahydroisoquinoline and m-methyl benzoic acid are according to mol ratio 0.015：2：1：3 it is mixed Close, add solvent acetonitrile and methanol, acetonitrile and methanol are according to 1:1 volume ratio mixes, and reaction system is full of oxygen, apart from reaction bulb 3.5w white light LED lamp band is placed at 2cm, after 35 hours, reaction system drains solvent, is separated by silica gel column chromatography, obtains To 2-（（2- phenyl -1,2,3,4- tetrahydro isoquinolyls -1-）Methyl）Quinoline product；The structural formula of described photochemical catalyst is （I）：
（I）.
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