CN106496114A - A kind of preparation method of aromatic aza cycle compound - Google Patents

A kind of preparation method of aromatic aza cycle compound Download PDF

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CN106496114A
CN106496114A CN201610907862.1A CN201610907862A CN106496114A CN 106496114 A CN106496114 A CN 106496114A CN 201610907862 A CN201610907862 A CN 201610907862A CN 106496114 A CN106496114 A CN 106496114A
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CN106496114B (en
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傅尧
尚睿
成万民
付明臣
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University of Science and Technology of China USTC
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    • 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
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    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract

The invention provides a kind of preparation method of aromatic aza cycle compound, by formula (I) compound, nitrogen-containing heterocycle compound are carried out illumination reaction under photochemical catalyst, organic phosphoric acid and solvent existence condition, the compound with formula (II) structure is obtained；Wherein, the present invention excites photochemical catalyst that electron transition occurs by using illumination, so as to the active carboxylic acid's ester decarboxylation being catalyzed in the compound with formula (I) structure, and minisci reaction introducing azacyclo-s occurs with nitrogen-containing heterocycle compound.Reacted by minisci with the tradition that reports before compared with introducing the method for azacyclo-, this method is using the use for avoiding equivalent strong oxidizer, and substrate spectrum and functional group compatibility have more universality；The decarboxylation that the active acid acid esters of polypeptide can be successfully applied to introduces azacyclo-, and the decarboxylation of amino acid active carboxylate introduces gram level scale reaction of azacyclo-, and high conversion rate, is worth prospect with commercial synthesis.

Description

A kind of preparation method of aromatic aza cycle compound
Technical field
A kind of the present invention relates to compound synthesis field, more particularly to preparation method of aromatic aza cycle compound.
Background technology
Heteroaromatic compound is extremely important construction unit in medicinal chemistry art, miscellaneous by selective catalysis fragrance Ring sense dough is to find one of important means of new drug.The main method for realizing the sense dough of aromatic heterocycle is known Minisci reacts, such as it has been reported that have：Use of N-Protected Amino Acids in the Minisci Radical Alkylation, Cameron J.Cowden, Org.Lett., 2003,5, pp 4497-4499；Unprotected Amino Acids as Stable Radical Precursors for Heterocycle C-H Functionalization, Duy N.Mai and Ryan D.Baxter, Org.Lett., 2016,18, pp 3738-3741. But these it has been reported that method in generally require to add excessive oxidant realize sense dough, and functional group is compatible Property is poor, and the substrate scope of application is more limited to.
Content of the invention
In view of this, the technical problem to be solved is to provide a kind of preparation side of aromatic aza cycle compound Method, the method that the present invention is provided need not only add the oxidant of equivalent, and reaction condition is gentle, substrate wide accommodation, Preferable to functional group compatibility.
The invention provides a kind of preparation method of aromatic aza cycle compound, including：
Formula (I) compound, nitrogen-containing heterocycle compound are carried out light under photochemical catalyst, organic phosphoric acid and solvent existence condition According to reaction, the compound with formula (II) structure is obtained；
Wherein, the R1Alkyl for the alkoxy carbonyl group of C2～C20, the acyl group of C2～C25 or C7～C30；
The R2For hydrogen atom, the alkyl without functional group of C1～C30, the alkyl containing functional group of C1～C30, C5～ The heteroaryl of the aryl or C5～C30 of C30；
Or R1、R2And the nitrogen that is connected with them and carbon form five-membered ring or hexatomic ring；The R3For formula (I-c),
Wherein, R is hydrogen or chlorine.
Preferably, the photochemical catalyst is formula (cat-1), formula (cat-2), formula (cat-3) or formula (cat-4)；
Preferably, the organic phosphoric acid is formula (PA-1), formula (PA-1) or formula (PA-3)；
Preferably, the R1For benzyloxycarbonyl group, tertbutyloxycarbonyl, fluorenylmethyloxycarbonyl, allyloxycarbonyl, trimethyl silicane ethoxy Carbonyl, methoxycarbonyl group, carbethoxyl group, phthalyl, p-toluenesulfonyl, trifluoroacetyl group, ortho-nitrophenyl sulfonyl, right Nitrobenzenesulfonyl, pivaloyl group, benzoyl, trityl, 2,4- dimethoxy-benzyls, to methoxy-benzyl or benzyl.
Preferably, described formula (I) compound by the hydrogen on amino acid or polypeptide carboxyl by R3Replaced and carboxyl α-carbon On amino hydrogen by R2Replaced formation.
Preferably, described formula (I) compound is formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5), formula (I- 6), formula (I-7), formula (I-8), formula (I-9), formula (I-10, formula (I-11) formula (I-12), formula (I-12), formula (I-13), formula (I- 14), formula (I-15), formula (I-16), formula (I-17) or formula (I-18)；
Preferably, the nitrogen-containing heterocycle compound is formula (Het-a), formula (Het-b), formula (Het-c), formula (Het-d), formula (Het-e), formula (Het-f), formula (Het-g), formula (Het-h), formula (Het-i) or formula (Het-j)；
Wherein, R is selected from hydrogen, halogen, amino, the alkyl for not conforming to functional group of C1～C8, the alkane containing functional group of C1～C8 The heterocyclic radical of base, the aryl of C6～C30, sulfonyl or C3～C15.
Preferably, the nitrogen-containing heterocycle compound is formula (Het-a-1), formula (Het-b-2), formula (Het-b-3), formula (Het-a-4), formula (Het-a-5), formula (Het-c-6), formula (Het-d-7), formula (Het-a-8), formula (Het-g-9), formula (Het- F-10), formula (Het-e-11), formula (Het-g-12), formula (Het-b-13), formula (Het-i-14) or formula (Het-j-15),
Preferably, described formula (I) compound is 1 with the mol ratio of nitrogen-containing heterocycle compound: (1.0～2.5).
Preferably, the light source of the illumination is ultraviolet light or blue light.
Compared with prior art, the invention provides a kind of preparation method of aromatic aza cycle compound, by by formula (I) Compound, nitrogen-containing heterocycle compound carry out illumination reaction under photochemical catalyst, organic phosphoric acid and solvent existence condition, are had The compound of formula (II) structure；Wherein, the present invention excites photochemical catalyst that electron transition occurs by using illumination, so as to be catalyzed tool The active carboxylic acid's ester decarboxylation having in the compound of formula (I) structure, and there is minisci reaction introducing nitrogen with nitrogen-containing heterocycle compound Heterocycle.Reacted by minisci with the tradition that reports before compared with introducing the method for azacyclo-, this method is utilized and avoids equivalent The use of strong oxidizer, meets the requirement of the friendly chemistry of development green environment, and substrate spectrum and functional group compatibility have more Plus universality；And the method can be successfully applied to the decarboxylation introducing azacyclo- of the active acid acid esters of polypeptide, amino acid active carboxylic Acid esters decarboxylation introduces gram level scale reaction of azacyclo-, and high conversion rate, is worth prospect with commercial synthesis.
Description of the drawings
Fig. 1 is compound prepared by the embodiment of the present invention 11H NMR scheme；
Fig. 2 is compound prepared by the embodiment of the present invention 113C NMR scheme.
Specific embodiment
The invention provides a kind of preparation method of aromatic aza cycle compound, including：
Formula (I) compound, nitrogen-containing heterocycle compound are carried out light under photochemical catalyst, organic phosphoric acid and solvent existence condition According to reaction, the compound with formula (II) structure is obtained；
Wherein, the R1Alkyl for the alkoxy carbonyl group of C2～C20, the acyl group of C2～C25 or C7～C30；
The R2For hydrogen atom, the alkyl without functional group of C1～C30, the alkyl containing functional group of C1～C30, C5～ The heteroaryl of the aryl or C5～C30 of C30；
Or R1、R2And the nitrogen that is connected with them and carbon form five-membered ring or hexatomic ring；
The R3For formula (I-c),
Wherein, R is hydrogen or chlorine.
Wherein, in formula (II)For the abbreviation that nitrogen-containing heterocycle compound removes the later group of hydrogen, i.e.,Abbreviation for nitrogen-containing heterocycle compound；Can be bromo isoquinolin, 2- chloro-quinoxalines, pyridine, piperidines etc. Compound containing azacyclo-.
According to the present invention, in formula (I) compound, the R1For the protection group of amino, amino well known in the art Protection group, its are preferably benzyloxycarbonyl group, tertbutyloxycarbonyl, fluorenylmethyloxycarbonyl, allyloxycarbonyl, trimethyl silicane ethoxy carbonyl Base, methoxycarbonyl group, carbethoxyl group, phthalyl, p-toluenesulfonyl, trifluoroacetyl group, ortho-nitrophenyl sulfonyl, to nitre Base benzenesulfonyl, pivaloyl group, benzoyl, trityl, 2,4- dimethoxy-benzyls, to methoxy-benzyl or benzyl；Institute State R2Preferably hydrogen atom, the alkyl without functional group of C4～C20, the alkyl containing functional group of C4～C20, C8～C20 Aryl or the heteroaryl of C8～C20；Functional group in the alkyl containing functional group is ester group, thioether group, oxygen ether or acid amides Base；The aryl can also be the aryl containing functional group or the aryl for not conforming to functional group, wherein, official in the aryl containing functional group Can roll into a ball as halogen, ester group, thioether group, oxygen ether or amide groups；The heteroaryl can also be the heteroaryl containing functional group or not Heteroaryl containing functional group, wherein, the functional group in the heteroaryl containing functional group is halogen, ester group, thioether group, oxygen ether or acyl Amido；In formula (I) compound, the R1、R2Can with and the nitrogen that is connected with them and carbon form five-membered ring or hexatomic ring； Specifically, described formula (I) compound is that amino acid or the hydrogen on a carboxyl in polypeptide change R into3And on carboxyl α-carbon A hydrogen on amino changes R into2Compound afterwards；The present invention is not particularly limited to the selection of amino acid, well known in the art Amino acid, the present invention is to the selection of polypeptide it is not also specifically limited, by any two or plural amino acid condensation Into polypeptide.More specifically, described formula (I) compound is formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I- 5), formula (I-6), formula (I-7), formula (I-8), formula (I-9), formula (I-10, formula (I-11) formula (I-12), formula (I-12), formula (I- 13), formula (I-14), formula (I-15), formula (I-16), formula (I-17) or formula (I-18)；
The present invention does not have particular/special requirement to the nitrogen-containing heterocycle compound, and those skilled in the art can be according to the mesh for preparing The needs of mark compound select suitable nitrogen-containing heterocycle compound；Preferably, the nitrogen-containing heterocycle compound be formula (Het-a), Formula (Het-b), formula (Het-c), formula (Het-d), formula (Het-e), formula (Het-f), formula (Het-g), formula (Het-h), formula (Het- Or formula (Het-j) i)；
Wherein, R is selected from hydrogen, halogen, amino, the alkyl without functional group of C1～C8, the alkane containing functional group of C1～C8 The heterocyclic radical of base, the aryl of C6～C30, sulfonyl or C3～C15.Wherein, the functional group in the alkyl containing functional group is Ester group, amino or ether；The R is preferably hydrogen, Cl, Br, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, phenyl, naphthalene Base, containing ester group C1～C5 alkyl or isoquinolinesulfonylcompounds；More specifically, the nitrogen-containing heterocycle compound is formula (Het-a- 1), formula (Het-b-2), formula (Het-b-3), formula (Het-a-4), formula (Het-a-5), formula (Het-c-6), formula (Het-d-7), formula (Het-a-8), formula (Het-g-9), formula (Het-f-10), formula (Het-e-11), formula (Het-g-12), formula (Het-b-13), formula (Het-i-14) or formula (Het-j-15),
According to the present invention, the photochemical catalyst is preferably the Ir [dF (CF with formula (cat-1) structure3)ppy]2 (dtbbpy)PF6, have formula (cat-2) structure Ir (ppy)3, have formula (cat-3) structure Ru (bpy)3(PF6)2Or have The Mes-Acr of formula (cat-4) structure, more preferably Ir [dF (CF3)ppy]2(dtbbpy)PF6；
According to the present invention, the present invention does not have particular/special requirement to the organic phosphoric acid, organic phosphoric acid well known in the art, It is formula (PA-1), formula (PA-1) or formula (PA-3) for the organic phosphoric acid that the present invention preferably makes the organic phosphoric acid；
According to the present invention, the organic solvent be preferably DMF, DMA, toluene, One or more in diethylene glycol dimethyl ether and Isosorbide-5-Nitrae-dioxane, more preferably DMA.
According to the present invention, the mol ratio of formula (I) compound and nitrogen-containing heterocycle compound is preferably 1: (1.0～2.5), More preferably 1: (1.5～2)；The mol ratio of formula (I) compound and the photochemical catalyst is preferably 1: (0.001～ 0.05), more preferably 1: (0.02～0.03)；The mol ratio of formula (I) compound and the organic phosphoric acid is preferably 1: (0.01～0.5), more preferably 1: (0.1～0.3)；The light source of the illumination reaction is preferably ultraviolet light or blue light, more preferably For ultraviolet light 254nm, ultraviolet light 365nm or, more preferably blue light (LEDs, 36W)；It is little that the time of the illumination is preferably 1～5 When, more preferably 3～4 hours.
More specifically, the compound of the formula (II) structure that the present invention is obtained is preferably formula (II-1), formula (II-2), formula (II-3), formula (II-4), formula (II-5), formula (II-6), formula (II-7), formula (II-8), formula (II-9), formula (II-10, formula (II- 11) formula (II-12), formula (II-12), formula (II-13), formula (II-14), formula (II-15), formula (II-16), formula (II-17), formula (II-18), formula (II-19), formula (II-20), formula (II-21), formula (II-22), formula (II-23), formula (II-24), formula (II- 25), formula (II-26), formula (II-27), formula (II-28), formula (II-29), formula (II-30) or formula (II-31).
A kind of preparation method of aromatic aza cycle compound that the present invention is provided, by by formula (I) compound, nitrogen heterocyclic ring Compound carries out illumination reaction under photochemical catalyst, organic phosphoric acid and solvent existence condition, obtains the change with formula (II) structure Compound；Wherein, the present invention excites photochemical catalyst that electron transition occurs by using illumination, so as to be catalyzed with formula (I) structure Active carboxylic acid's ester decarboxylation in compound, and there is minisci reaction introducing azacyclo-s with nitrogen-containing heterocycle compound.With report before The tradition in road is compared by the method that minisci reacts introducing azacyclo-, and this method is utilized and avoids making for equivalent strong oxidizer With, meeting the requirement of the friendly chemistry of development green environment, substrate spectrum and functional group compatibility have more universality；And should Method can be successfully applied to the decarboxylation of the active acid acid esters of polypeptide and introduce azacyclo-, and the decarboxylation of amino acid active carboxylate introduces nitrogen Gram level scale reaction of heterocycle, and high conversion rate, are worth prospect with commercial synthesis.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described enforcement Example is only a part of embodiment of the invention, rather than whole embodiment.Embodiment in based on the present invention, this area are common The every other embodiment obtained under the premise of creative work is not made by technical staff, belongs to the model of present invention protection Enclose.
Active carboxylic acid's ester decarboxylation in the following embodiments of the present invention for photocatalysis amino acid or polypeptide introduces azacyclo- institute Bought in following Reagent Company using the medicine for arriving respectively：
Diethylene glycol dimethyl ether (C6H14O3, 99.5%), toluene (C7H8, 99.5%), Isosorbide-5-Nitrae-dioxane (C4H8O2, 99.8%), buy from lark prestige chemical reagents corporation.
DMF (C3H7NO, 99.5%), DMA (C4H9NO, 99.0%), Ir (ppy)3(C33H24IrN3, 90.0%) buy from TCI companies.
Ru(bpy)3(PF6)2(C30H24F12N6P2Ru, 97.0%), Ir [dF (CF3)ppy]2(dtbbpy)PF6 (C42H34F16IrN4P, 90.0%) buys from Sigma-Aldrich companies.
Embodiment 1, preparation N- (2- phenyl -1- (4- phenyl -2- quinolyls) ethyl) t-butyl carbamate
Reaction equation：
Concrete grammar is as follows：
Schlenk reaction tubes (Beijing Xin Weier glass apparatus Co., Ltd, F891410 reaction tubes, capacity in 10mL 10mL, ground is 14/20) middle to add photochemical catalyst (Ir [dF (CF3) ppy] 2 (dtbbpy) PF6) (1mol%, 2.2mg), dinaphthalene Phenol phosphate (PA-1) (10mol%, 7.0mg) and phenylalanine NHPI esters (0.3mmol, 123mg) of boc protections.Use argon gas Displacement inner air tube three times, then adds 2mL DMAs (DMA), 4- phenylchinolines under argon atmosphere completely (0.2mmol, 41mg).The reaction system is continuously stirring 3 hours (using IKA magnetic force under room temperature under the irradiation of 36W blue LED lamps Agitator, RCT basic models, 500 revs/min of mixing speed).After completion of the reaction, reaction is quenched with H2O, and with ethyl acetate (3* 10mL) extractive reaction liquid, then the mode of the organic phase rotary evaporation of merging is concentrated (Bu Qi Co., Ltds of Switzerland, BUCHI rotations Turn evaporimeter R-3).Concentrated residue is by chromatographic column (Beijing Xin Weier glass apparatus Co., Ltd, C383040C tool sand plate storages Ball chromatographic column, 35/20, φ 30mm are effectively long：500ml) chromatography obtains product.(product is white solid, totally 73 milligrams, Yield 84%, eluant ethyl acetate: petroleum ether=1: 10～1: 5)
Structural Identification is carried out to the product for obtaining, as a result sees that Fig. 1～Fig. 2, Fig. 1 are chemical combination prepared by the embodiment of the present invention 1 Thing1H NMR scheme；Fig. 2 is compound prepared by the embodiment of the present invention 113C NMR scheme；Nuclear magnetic data is as follows：
1H NMR (400MHz, CDCl3) δ 8.14 (d, J=8.3Hz, 1H), 7.89-7.82 (m, 1H), 7.73-7.65 (m, 1H), 7.48-7.41 (m, 4H), 7.33-7.27 (m, 2H), 7.20-7.18 (m, 3H), 7.03-7.02 (m, 2H), 6.83 (s, 1H), 6.26 (d, J=6.8Hz, 1H), 5.20-5.15 (m, 1H), 3.41-3.36 (m, 1H), 3.16-3.11 (m, 1H), 1.46 (s, 9H).13C NMR (101MHz, CDCl3) δ 159.3,155.4,148.4,148.0,137.9,137.58,129.7,129.5, 129.4,128.5,128.4,128.3,126.4,126.3,125.9,125.8,120.9,79.4,57.2,43.1,28.5. (its In signal peak be capped)
Embodiment 2, preparation N- (2- phenyl -1- (4- phenyl -2- quinolyls) ethyl) benzyq carbamate
Reaction equation：
With example 1, yield is 81% to method.Nuclear magnetic spectrogram data are：1H NMR (400MHz, CDCl3) δ 8.10 (d, J= 8.4Hz, 1H), 7.86 (d, J=8.4Hz, 1H), 7.69 (t, J=7.5Hz, 1H), 7.51-7.40 (m, 4H), 7.40-7.24 (m, 7H), 7.21-7.14 (m, 3H), 7.04-6.95 (m, 2H), 6.82 (s, 1H), 6.58 (d, J=7.4Hz, 1H), 5.27- 5.19 (m, 1H), 5.19-5.01 (m, 2H), 3.41 (dd, J=13.2,5.6Hz, 1H), 3.14 (dd, J=13.2,7.9Hz, 1H).13C NMR (101MHz, CDCl3) δ 158.8,155.9,148.4,147.9,137.9,137.3,136.7,129.7, 129.5,129.4,128.5,128.5,128.4,128.3,128.2,128.1,128.0,126.5,126.4,125.9, 125.8,120.8,66.7,57.6,43.0.
Embodiment 3, preparation N- (2- phenyl -1- (4- phenyl -2- quinolyls) ethyl) benzamide
Reaction equation：
With example 1, yield is 83% to method.Nuclear magnetic spectrogram data are：1H NMR (400MHz, CDCl3)δ8.27-8.18 (m, 1H), 8.15 (d, J=8.5Hz, 1H), 7.95-7.86 (m, 3H), 7.76-7.69 (m, 1H), 7.55-7.43 (m, 7H), 7.36-7.29 (m, 2H), 7.22-7.17 (m, 3H), 7.07-7.01 (m, 2H), 6.89 (s, 1H), 5.70-5.62 (m, 1H), 3.58 (dd, J=13.1,5.1Hz, 1H), 3.24 (dd, J=13.1,8.3Hz, 1H)；13C NMR (101MHz, CDCl3)δ 166.7,158.5,148.7,147.6,137.7,137.2,134.8,131.5,129.8,129.6,129.5,129.3, 128.6,128.6,128.3,127.2,126.6,126.0,125.9,121.2,56.0,42.6. (two of which signal peak be coated to Lid).
Embodiment 4, preparation N- ((4- phenyl -2- quinolyls) methyl) t-butyl carbamate
Reaction equation：
With example 1, yield is 80% to method.Nuclear magnetic spectrogram data are：1H NMR (400MHz, CDCl3) δ 8.13 (d, J= 8.3Hz, 1H), 7.88 (dd, J=8.4,0.8Hz, 1H), 7.73-7.69 (m, 1H), 7.55-7.45 (m, 6H), 7.30 (s, 1H), 6.01 (s, 1H), 4.67 (d, J=4.9Hz, 2H), 1.50 (s, 9H)；13C NMR (101MHz, CDCl3) δ 155.7, 155.1,148.3,146.8,136.8,128.6,128.5,128.1,127.6,127.5,125.4,124.9,124.8, 118.9,78.5,45.1,27.4.
Embodiment 5, preparation N- (1- (4- phenyl -2- quinolyls) ethyl) t-butyl carbamate
Reaction equation：
With example 1, yield is 78% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.14 (d, J=8.4Hz, 1H), 7.88 (dd, J=8.4,0.7Hz, 1H), 7.71 (ddd, J=8.3,6.9,1.3Hz, 1H), 7.57-7.41 (m, 6H), 7.28 (s, 1H), 6.27 (br, s, 1H), 5.14-4.93 (m, 1H), 1.58 (d, J=6.8Hz, 3H), 1.48 (s, 9H).
13C NMR (101MHz, CDCl3) δ 161.1,155.4,149.3,147.8,138.0,129.5,129.5,129.4, 128.6,128.5,126.3,125.9,125.7,119.6,79.3,51.5,28.5,22.9.
Embodiment 6, preparation 2- (4- phenyl -2- quinolyls)-N- pyrroles's tert-butyl acrylates
Reaction equation：
With example 1, yield is 92% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3(70: 30 rotational isomers) δ 8.11 (d, J=8.5Hz, 1H), 7.88 (d, J= 8.0Hz, 1H), 7.73-7.65 (m, 1H), 7.55-7.43 (m, 6H), 7.25 (s, 1H), 5.25-5.16 (m, 0.3H) *, 5.11- 5.02 (m, 0.7H), 3.80-3.57 (m, 2H), 2.61-2.43 (m, 1H), 2.17-1.90 (m, 3H), 1.47 (s, 2.7H) *, 1.13 (s, 6.3H).
13C NMR (101MHz, CDCl3) δ 163.9,154.6,149.1,147.9,138.2,129.6,129.4,129.2, 128.6,128.4,126.1,125.7,125.6,117.9,79.4,63.7,47.3,34.7,28.2,23.7.
Embodiment 7, preparation N- (3- phenyl -1- (4- phenyl -2- quinolyls) propyl group) t-butyl carbamate
Reaction equation：
With example 1, yield is 79% to method.Nuclear magnetic spectrogram data are：1H NMR (400MHz, CDCl3) δ 8.14 (d, J= 8.4Hz, 1H), 7.88 (dd, J=8.4,0.8Hz, 1H), 7.70 (ddd, J=8.4,6.9,1.4Hz, 1H), 7.54-7.42 (m, 6H), 7.24-7.18 (m, 3H), 7.16-7.10 (m, 3H), 6.19 (d, J=7.6Hz, 1H), 5.11-5.01 (m, 1H), 2.76- 2.62 (m, 2H), 2.41-2.27 (m, 1H), 2.23-2.11 (m, 1H), 1.48 (s, 9H).
13C NMR (101MHz, CDCl3) δ 160.1,155.7,149.2,148.0,141.8,138.0,129.6,129.5, 129.5,128.6,128.5,128.4,128.4,126.4,125.9,125.8,120.3,79.4,55.6,38.5,32.0, 28.5. (one of signal peak is capped).
Embodiment 8, preparation N- (2- (4- iodophenyls) -1- (4- phenyl -2- quinolyls) ethyl) t-butyl carbamate
Reaction equation：
With example 1, yield is 95% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.13 (d, J=8.4Hz, 1H), 7.87 (dd, J=8.4,0.8Hz, 1H), 7.71 (ddd, J=8.3,6.9,1.3Hz, 1H), 7.58-7.42 (m, 6H), 7.30 (d, J=6.8Hz, 2H), 6.89-6.67 (m, 3H), 6.28 (d, J=6.8Hz, 1H), 5.18-4.98 (m, 1H), 3.34 (dd, J=12.9,5.4Hz, 1H), 3.06 (dd, J= 13.1,8.1Hz, 1H), 1.47 (s, 9H).
13C NMR (101MHz, CDCl3) δ 158.6,155.3,148.4,147.9,137.7,137.6,137.3,131.8, 129.4,128.6,128.5,126.9,126.5,125.9,125.8,120.8,91.8,79.5,56.9,42.5,28.4. (One single is covered).
Embodiment 9, preparation N, bis- tert-butoxycarbonyl -2- of N- (1- isoquinolyls) -1,5- pentanediamines
Reaction equation：
With example 1, yield is 93% to method.
1H NMR (400MHz, CDCl3) δ 8.44 (d, J=5.7Hz, 1H), 8.20 (d, J=8.3Hz, 1H), 7.84 (d, J =8.1Hz, 1H), 7.70 (t, J=7.4Hz, 1H), 7.63 (t, J=7.6Hz, 1H), 7.57 (d, J=5.7Hz, 1H), 6.28 (d, J=7.8Hz, 1H), 5.78-5.61 (m, 1H), 4.74 (s, 1H), 3.17-2.98 (m, 2H), 2.02-1.91 (m, 1H), 1.86-1.76 (m, 1H), 1.62-1.39 (m, 22H).
13C NMR (101MHz, CDCl3) δ 160.0,156.0,155.9,141.0,136.4,130.3,127.7,127.5, 125.4,124.4,120.3,79.3,78.9,50.5,40.4,36.9,29.5,28.5,28.4,22.9.
Embodiment 10, preparation N- (2- (3-1H- indyls) -1- (1- isoquinolyls) ethyl) t-butyl carbamate
Reaction equation：
With example 1, yield is 91% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.35 (d, J=5.6Hz, 1H), 8.05 (s, 1H), 8.00 (d, J=8.4Hz, 1H), 7.75 (d, J=8.1Hz, 1H), 7.58 (t, J=7.5Hz, 1H), 7.51 (d, J=5.6Hz, 1H), 7.40 (t, J= 7.5Hz, 1H), 7.19 (t, J=9.1Hz, 2H), 7.06 (t, J=7.4Hz, 1H), 6.93 (t, J=7.3Hz, 1H), 6.63 (s, 1H), 6.29 (d, J=8.0Hz, 1H), 6.02-5.97 (m, 1H), 3.48-3.43 (m, 2H), 1.43 (s, 9H).
13C NMR (101MHz, CDCl3) δ 159.7,155.6,141.0,136.2,135.9,130.1,128.0,127.2, 127.2,125.9,124.5,122.9,121.6,120.3,119.2,118.7,111.3,110.9,79.3,51.5,32.4, 28.5.
Embodiment 11, preparation 3- (tertbutyloxycarbonylamino) -3- (1- isoquinolyls) cyclohexyl propionate
Reaction equation：
With example 1, yield is 92% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.42 (d, J=5.4Hz, 1H), 8.38 (d, J=7.8Hz, 1H), 7.82 (d, J =7.7Hz, 1H), 7.73-7.61 (m, 2H), 7.57 (d, J=5.6Hz, 1H), 6.18-6.04 (m, 1H), 5.93 (d, J= 7.8Hz, 1H), 4.75-4.59 (m, 1H), 3.08 (dd, J=14.8,6.6Hz, 1H), 2.91 (dd, J=14.9,6.0Hz, 1H), 1.73-1.57 (m, 4H), 1.44 (s, 9H), 1.33-1.14 (m, 6H).
13C NMR (101MHz, CDCl3) δ 170.4,158.7,155.1,141.2,136.5,130.2,127.7,127.3, 125.8,124.8,120.7,79.6,72.8,48.3,41.0,31.3,28.4,25.3,23.6.
Embodiment 12, preparation 4- (Benzyoxycarbonylamino) -4- (1- isoquinolyls) methyl butyrate
Reaction equation：
With example 1, yield is 90% to method.Nuclear magnetic spectrogram data are：1H NMR (400MHz, CDCl3) δ 8.42 (d, J= 5.5Hz, 1H), 8.35 (d, J=7.8Hz, 1H), 7.82 (d, J=7.6Hz, 1H), 7.72-7.63 (m, 2H), 7.56 (d, J= 5.6Hz, 1H), 7.38-7.28 (m, 5H), 6.74 (d, J=7.9Hz, 1H), 5.90-5.78 (m, 1H), 5.16-5.10 (m, 2H), 3.63 (s, 3H), 2.61-2.49 (m, 1H), 2.45-2.30 (m, 2H), 2.09-1.95 (m, 1H).
13C NMR (101MHz, CDCl3) δ 173.7,158.8,156.4,141.0,136.6,136.5,130.4,128.5, 128.1,128.0,127.8,127.4,125.3,124.5,120.6,66.8,51.6,50.7,31.9,29.9.
Embodiment 13, preparation N- (1- (1- isoquinolyls) -3- methylthios) benzyq carbamate
Reaction equation：
With example 1, yield is 92% to method.
1H NMR (400MHz, CDCl3) δ 8.42 (d, J=5.7Hz, 1H), 8.28 (d, J=8.3Hz, 1H), 7.83 (d, J =7.7Hz, 1H), 7.73-7.60 (m, 2H), 7.57 (d, J=5.6Hz, 1H), 7.38-7.29 (m, 5H), 6.61 (d, J= 8.1Hz, 1H), 5.95-5.85 (m, 1H), 5.17-5.09 (m, 2H), 2.68-2.59 (m, 1H), 2.50-2.40 (m, 1H), 2.32-2.22 (m, 1H), 2.15-2.02 (m, 4H).
13C NMR (101MHz, CDCl3) δ 159.0,156.3,140.9,136.6,136.5,130.5,128.5,128.1, 128.1,127.9,127.5,125.4,124.4,120.6,66.8,50.6,36.5,30.4,15.6.
Embodiment 14, preparation (2- (4- tert .- butoxyphenyls) -1- (1- isoquinolyls) ethyl) t-butyl carbamate
Reaction equation：
With example 1, yield is 96% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.42 (d, J=5.6Hz, 1H), 7.95 (d, J=8.5Hz, 1H), 7.74 (d, J =8.2Hz, 1H), 7.57 (t, J=7.5Hz, 1H), 7.52 (d, J=5.6Hz, 1H), 7.43 (t, J=7.6Hz, 1H), 6.76 (d, J=8.2Hz, 2H), 6.69 (d, J=8.3Hz, 2H), 6.26 (d, J=8.3Hz, 1H), 5.89-5.84 (m, 1H), 3.29- 3.08 (m, 2H), 1.43 (s, 9H), 1.22 (s, 9H).
13C NMR (101MHz, CDCl3) δ 159.4,155.3,153.7,141.3,136.1,132.4,129.9,127.2, 127.1,125.9,124.5,123.9,120.2,79.2,78.1,52.2,42.7,28.7,28.5. (wherein, signal peaks Capped (One single is covered)).
Embodiment 15, preparation 4- (Benzyoxycarbonylamino) -4- (1- isoquinolyls) butyramide
Reaction equation：
With example 1, yield is 82% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.41 (d, J=4.6Hz, 1H), 8.23 (d, J=7.8Hz, 1H), 7.84 (d, J =7.4Hz, 1H), 7.77-7.64 (m, 2H), 7.60 (d, J=5.2Hz, 1H), 7.49-7.29 (m, 5H), 6.94 (d, J= 5.4Hz, 1H), 6.52 (br, s, 1H), 5.87-5.69 (m, 1H), 5.48 (br, s, 1H), 5.18-5.11 (m, 2H), 2.52- 2.28 (m, 2H), 2.03-1.86 (m, 2H).
13C NMR (101MHz, CDCl3) δ 175.1,158.6,157.1,140.7,136.5,136.5,130.6,128.5, 128.2,128.1,127.5,125.1,124.3,120.8,67.0,50.9,33.8,32.2. (One single is covered).
Embodiment 16, preparation N- (2- tert-butoxy -1- (1- isoquinolyls) ethyl) t-butyl carbamate
Reaction equation：
With example 1, yield is 89% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.42 (d, J=5.6Hz, 1H), 7.95 (d, J=8.5Hz, 1H), 7.74 (d, J =8.2Hz, 1H), 7.57 (t, J=7.5Hz, 1H), 7.52 (d, J=5.6Hz, 1H), 7.43 (t, J=7.6Hz, 1H), 6.76 (d, J=8.2Hz, 2H), 6.69 (d, J=8.3Hz, 2H), 6.26 (d, J=8.3Hz, 1H), 5.89-5.84 (m, 1H), 3.29- 3.08 (m, 2H), 1.43 (s, 9H), 1.22 (s, 9H).
13C NMR (101MHz, CDCl3) δ 159.4,155.3,153.7,141.3,136.1,132.4,129.9,127.2, 127.1,125.9,124.5,123.9,120.2,79.2,78.1,52.2,42.7,28.7,28.5. (wherein, signal peaks Capped (One single is covered)).
Embodiment 17, preparation N- (1- (the bromo- 1- isoquinolyls of 6-) -2- phenylethyls) t-butyl carbamate
Reaction equation：
With example 1, yield is 90% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.42 (d, J=5.6Hz, 1H), 7.92 (s, 1H), 7.83 (d, J=9.0Hz, 1H), 7.52 (d, J=8.9Hz, 1H), 7.42 (d, J=5.2Hz, 1H), 7.12-7.04 (m, 3H), 6.92-6.82 (m, 2H), 6.15 (br, s, 1H), 5.85-5.80 (m, 1H), 3.28-3.12 (m, 2H), 1.42 (s, 9H).
13C NMR (101MHz, CDCl3) δ 158.5,154.2,141.4,136.2,136.0,129.7,128.5,128.2, 127.0,125.4,125.2,123.8,123.3,118.1,78.3,51.1,41.9,27.4.
Embodiment 18, preparation N- (1- (the chloro- 2- quinolyls of 4-) -2- phenylethyls) t-butyl carbamate
Reaction equation：
With example 1, yield is 51% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.18 (d, J=8.2Hz, 1H), 8.08 (d, J=8.4Hz, 1H), 7.75 (t, J =7.1Hz, 1H), 7.61 (t, J=7.6Hz, 1H), 7.24-7.14 (m, 3H), 7.10 (s, 1H), 7.07-6.95 (m, 2H), 5.98 (d, J=5.7Hz, 1H), 5.20-5.04 (m, 1H), 3.29 (dd, J=13.0,5.6Hz, 1H), 3.17 (dd, J= 13.2,7.5Hz, 1H), 1.44 (s, 9H).
13C NMR (101MHz, CDCl3) δ 160.1,155.3,148.2,142.6,137.0,130.5,129.6,129.4, 128.3,127.3,126.6,125.5,124.1,120.5,79.6,57.0,42.5,28.4.
Embodiment 19, preparation N- (1- (4- methyl -2- quinolyls) -2- phenylethyls) t-butyl carbamate
Reaction equation：
With example 1, yield is 88% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.04 (d, J=8.4Hz, 1H), 7.92 (d, J=8.2Hz, 1H), 7.67 (t, J =7.5Hz, 1H), 7.51 (t, J=7.6Hz, 1H), 7.22-7.11 (m, 3H), 7.07-6.95 (m, 2H), 6.80 (s, 1H), 6.17 (d, J=7.1Hz, 1H), 5.16-5.03 (m, 1H), 3.29 (dd, J=13.1,5.6Hz, 1H), 3.16 (dd, J= 13.2,7.6Hz, 1H), 2.55 (s, 3H), 1.44 (s, 9H).
13C NMR (101MHz, CDCl3) δ 159.4,155.4,147.3,144.4,137.6,129.7,129.6,129.2, 128.2,127.4,126.4,126.1,123.8,121.3,79.3,57.0,42.7,28.5,18.7.
Embodiment 20, preparation N- (1- (3- chloro-2-quinoxaline bases) -2- phenylethyls) t-butyl carbamate
Reaction equation：
With example 1, yield is 53% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.06-7.98 (m, 2H), 7.81-7.74 (m, 2H), 7.23-7.12 (m, 3H), 7.08-6.95 (m, 2H), 5.83-5.66 (m, 2H), 3.40-3.30 (m, 1H), 3.15-3.04 (m, 1H), 1.41 (s, 9H).
13C NMR (101MHz, CDCl3) δ 155.0,153.7,146.0,141.3,140.4,136.3,130.8,130.4, 129.6,128.7,128.3,126.7,79.7,53.3,41.2,28.4. (One single is covered).
Embodiment 21, preparation N, bis- tert-butoxycarbonyl -2- of N- (1- (2,3- phthalazinyl)) -1,5- pentanediamines
Reaction equation：
With example 1, yield is 58% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 9.46 (s, 1H), 8.22 (d, J=7.7Hz, 1H), 8.05-7.91 (m, 3H), 6.25 (d, J=7.5Hz, 1H), 5.76-5.66 (m, 1H), 4.66 (d, J=6.8Hz, 1H), 3.18-2.99 (m, 2H), 2.07- 1.83 (m, 2H), 1.61-1.37 (m, 22H).
13C NMR (101MHz, CDCl3) δ 159.3,156.0,155.9,151.1,133.2,132.6,127.3,126.7, 124.4,123.4,79.6,79.0,49.9,40.3,36.6,29.6,28.4,28.4,23.0.
Embodiment 22, preparation N- (2- phenyl -1- (4- quinolyls) ethyl) t-butyl carbamate
Reaction equation：
Schlenk reaction tubes (Beijing Xin Weier glass apparatus Co., Ltd, F891410 reaction tubes, capacity in 10mL 10mL, ground is 14/20) middle to add photochemical catalyst (Ir [dF (CF3) ppy] 2 (dtbbpy) PF6) (1mol%, 2.2mg), dinaphthalene Phenol phosphate (PA-1) (10mol%, 7.0mg) and phenylalanine NHPI esters (0.2mmol, 82mg) of boc protections.Complete with argon gas Total replacement inner air tube three times, then under argon atmosphere plus 2mL DMAs (DMA), quinoline (0.4mmol, 52mg).The reaction system is continuously stirring 3 hours (using IKA magnetic stirring apparatus, RCT under room temperature under the irradiation of 36W blue LED lamps Basic model, 500 revs/min of mixing speed).After completion of the reaction, reaction is quenched with H2O, and is extracted with ethyl acetate (3*10mL) Reactant liquor, then the mode of the organic phase rotary evaporation of merging is concentrated (Bu Qi Co., Ltds of Switzerland, BUCHI Rotary Evaporators R-3).Concentrated residue is by chromatographic column (Beijing Xin Weier glass apparatus Co., Ltd, C383040C tool sand plate storage layers of balls analysis Post, 35/20, φ 30mm are effectively long：500ml) chromatography obtains product.(product is colourless liquid, totally 51.6 milligrams, yield 74%, eluant ethyl acetate: petroleum ether=1: 10～1: 5).Nuclear magnetic data data are：1H NMR (400MHz, CDCl3)δ 8.87 (d, J=4.2Hz, 1H), 8.20 (d, J=8.4Hz, 1H), 8.16 (d, J=8.1Hz, 1H), 7.74 (t, J=7.7Hz, 1H), 7.60 (t, J=7.7Hz, 1H), 7.38-7.23 (m, 4H), 7.12-6.94 (m, 2H), 5.82 (br, s, 1H), 5.19- 5.05 (m, 1H), 3.36-3.23 (m, 1H), 3.18-2.92 (m, 1H), 1.37 (s, 9H).
13C NMR (101MHz, CDCl3) δ 154.9,149.6,149.5,147.8,136.3,129.9,129.6,129.3, 128.6,127.1,127.0,126.0,122.8,117.6,80.2,51.0,41.8,28.3.
Embodiment 23, preparation N- (1- (6- phenanthridinyls) ethyl) t-butyl carbamate
Reaction equation：
With example 1, yield is 89% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.64 (d, J=8.3Hz, 1H), 8.54 (dd, J=8.3,1.1Hz, 1H), 8.25 (d, J=8.2Hz, 1H), 8.15 (d, J=7.9Hz, 1H), 7.89-7.79 (m, 1H), 7.75-7.68 (m, 2H), 7.64 (ddd, J=8.3,7.1,1.4Hz, 1H), 6.74 (d, J=6.2Hz, 1H), 5.85-5.69 (m, 1H), 1.63 (d, J=6.6Hz, 3H), 1.52 (s, 9H).
13C NMR (101MHz, CDCl3) δ 160.4,155.4,142.9,133.2,130.7,129.8,128.7,127.5, 126.9,125.4,123.9,123.3,122.6,122.0,79.2,47.6,28.5,23.1.
Embodiment 24, preparation N- (1- (2- amino -4- pyrimidine radicals) -2- (4- tert .- butoxyphenyls) ethyl) carbamic acid uncle Butyl ester
Reaction equation：
With example 22, yield is 56% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 8.07 (d, J=4.8Hz, 1H), 6.92 (d, J=8.2Hz, 2H), 6.85 (d, J =8.1Hz, 2H), 6.21 (d, J=4.7Hz, 1H), 5.58 (d, J=7.2Hz, 1H), 5.21 (s, 2H), 4.83-4.70 (m, 1H), 3.07 (dd, J=13.3,5.9Hz, 1H), 2.95 (dd, J=13.1,7.8Hz, 1H), 1.42 (s, 9H), 1.31 (s, 9H).
13C NMR (101MHz, CDCl3) δ 169.6,162.7,157.7,155.1,154.0,131.7,129.8,124.1, 109.7,79.6,78.3,56.2,41.3,28.8,28.4.
Embodiment 25, preparation N- (2- phenyl -1- (4- quinazolyls) ethyl) t-butyl carbamate
Reaction equation：
With example 1, yield is 50% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 9.22 (s, 1H), 8.04 (d, J=8.3Hz, 1H), 7.97 (d, J=8.4Hz, 1H), 7.86 (t, J=7.6Hz, 1H), 7.54 (t, J=7.5Hz, 1H), 7.19-7.04 (m, 3H), 6.97-6.84 (m, 2H), 6.05 (d, J=7.7Hz, 1H), 5.96-5.85 (m, 1H), 3.32-3.15 (m, 2H), 1.42 (s, 9H).
13C NMR (101MHz, CDCl3) δ 168.7,155.2,154.0,150.0,136.4,133.9,129.5,128.9, 128.2,127.9,126.7,124.0,122.5,79.7,52.0,42.6,28.4.
Embodiment 26, preparation N- (1- (2- (3,4,7,8 tetramethyl -1,10- phenanthrolines)) ethyl) the tertiary fourth of carbamic acid Ester
Reaction equation：
Schlenk reaction tubes (Beijing Xin Weier glass apparatus Co., Ltd, F891410 reaction tubes, capacity in 10mL 10mL, ground is 14/20) middle to add photochemical catalyst (Ir [dF (CF3) ppy] 2 (dtbbpy) PF6) (2mol%, 4.4mg), dinaphthalene Phenol phosphate (PA-1) (20mol%, 14mg), alanine NHPI esters (0.4mmol, 134mg) and 3,4,7,8- of boc protections Tetramethyl-1,10-phenanthroline (0.2mmol, 47mg).Inner air tube three time is replaced completely with argon gas, then Add 2mLN, N- dimethyl acetamides (DMA) under argon atmosphere.The reaction system is connecting under room temperature under the irradiation of 36W blue LED lamps 4 hours (using IKA magnetic stirring apparatus, RCT basic models, 500 revs/min of mixing speed) of continuous stirring.After completion of the reaction, H2O is used It is quenched reaction, and with ethyl acetate (3*10mL) extractive reaction liquid, then the mode of the organic phase rotary evaporation of merging is concentrated (Bu Qi Co., Ltds of Switzerland, BUCHI Rotary Evaporators R-3).By chromatographic column, (Beijing Xin Weier glass apparatus has concentrated residue Limit company, C383040C tool sand plate storage ball chromatographic columns, 35/20, φ 30mm are effectively long：500ml) chromatography obtains product. (product is white solid, totally 54.6 milligrams, yield 72%, eluant ethyl acetate: petroleum ether=1: 5～1: 3)
1H NMR (400MHz, CD2Cl2) δ 8.85 (s, 1H), 8.01-7.93 (m, 2H), 7.35 (d, J=7.4Hz, 1H), 5.41-5.33 (m, 1H), 2.66 (s, 3H), 2.64 (s, 3H), 5.39-5.33 (m, 6H), 1.49-1.46 (m, 12H).
13C NMR (101MHz, CD2Cl2) δ 159.8,155.4,150.8,144.0,143.1,142.6,142.1, 130.7,127.4,127.0,126.0,122.2,121.5,78.6,48.6,28.3,22.2,17.2,14.8,14.7,14.3.
Embodiment 27, preparation N, bis- tert-butoxycarbonyl -1- of N- (5- ((1- (Isosorbide-5-Nitrae-Diazesuberane base)) sulfonyl) Isoquinolyl) -1,5- pentanediamines
Reaction equation：
Schlenk reaction tubes (Beijing Xin Weier glass apparatus Co., Ltd, F891410 reaction tubes, capacity in 10mL 10mL, ground is 14/20) middle to add photochemical catalyst (Ir [dF (CF3) ppy] 2 (dtbbpy) PF6) (1mol%, 2.2mg), boc to protect Lysine NHPI esters (0.3mmol, 143mg) and fasudil hydrochloride (0.2mmol, 65mg) of shield.Replaced with argon gas completely Inner air tube three times, then adds 2mL DMAs (DMA) and 0.2mL H2O under argon atmosphere.The reactant Tying up to, 5 hours are continuously stirred under the lower room temperature of 36W blue LED lamps irradiation (using IKA magnetic stirring apparatus, RCT basic models, stirring speed 500 revs/min of degree).After completion of the reaction, reaction is quenched with H2O, and with ethyl acetate (3*10mL) extractive reaction liquid, then will close And the mode of organic phase rotary evaporation concentrate (Bu Qi Co., Ltds of Switzerland, BUCHI Rotary Evaporators R-3).Concentrated residue By chromatographic column (Beijing Xin Weier glass apparatus Co., Ltd, C383040C tool sand plate storage ball chromatographic columns, 35/20, φ 30mm, effectively long：500ml) chromatography obtains product.(product is weak yellow liquid, and totally 108 milligrams, yield is 91%)
1H NMR (400MHz, CDCl3) δ 8.60 (d, J=6.0Hz, 1H), 8.47 (d, J=8.3Hz, 1H), 8.38 (d, J =6.0Hz, 1H), 8.32 (d, J=7.3Hz, 1H), 7.71 (t, J=8.0Hz, 1H), 6.13 (d, J=7.9Hz, 1H), 5.80- 5.63 (m, 1H), 4.74 (br, s, 1H), 3.57-3.45 (m, 4H), 3.36-3.22 (m, 2H), 3.15-2.94 (m, 6H), 2.07-1.73 (m, 5H), 1.57-1.37 (m, 20H).
13C NMR (101MHz, CDCl3) δ 161.2,156.0,155.8,143.3,135.3,132.5,132.3,129.8, 126.2,126.0,116.9,79.5,79.0,50.8,50.4,50.1,47.3,40.3,36.7,30.5,29.7,29.6, 28.4,22.9. (one of signal peak is capped).
Embodiment 28, preparation N, bis- tert-butoxycarbonyl -1- of N- (8- (1,3,7- trimethyl -2,6- dioxo -2,3,6, 7- tetrahydrochysene -1H- purine radicals)) -1,5- pentanediamines
Reaction equation：
With example 1, yield is 24% to method.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 5.24 (d, J=6.6Hz, 1H), 4.90-4.80 (m, 1H), 4.59 (br, s, 1H), 4.02 (s, 3H), 3.56 (s, 3H), 3.40 (s, 3H), 3.17-3.04 (m, 2H), 2.05-1.97 (m, 1H), 1.93- 1.84 (m, 3H), 1.56-1.48 (m, 2H), 1.46-1.39 (m, 18H).
13C NMR (101MHz, CDCl3) δ 156.1,155.5,155.3,153.6,151.7,147.7,107.4,80.3, 79.2,46.3,40.0,34.2,32.0,29.9,29.3,28.4,28.3,27.9,22.7..
Embodiment 29, preparation 2- (2- (2- amino -6- (2- (4- (tert-butoxy) phenyl) -1- ((tert-butoxycarbonyl) ammonia Base) ethyl) -9H- purine -9- bases) ethyl) propane -1,3- diyl diacetate esters
Reaction equation：
Method with example 23, be shown in for 62% by yield.Nuclear magnetic spectrogram data are：
1H NMR (400MHz, CDCl3) δ 7.70 (s, 1H), 6.91 (d, J=7.6Hz, 2H), 6.79 (d, J=7.7Hz, 2H), 6.09 (d, J=7.7Hz, 1H), 5.51-5.42 (m, 1H), 5.09 (s, 2H), 4.28-4.08 (m, 6H), 3.32-3.21 (m, 1H), 3.19-3.09 (m, 1H), 2.07 (s, 6H), 2.03-1.97 (m, 1H), 1.96-1.88 (m, 2H), 1.40 (s, 9H), 1.28 (s, 9H).
13C NMR (101MHz, CDCl3) δ 170.9,160.6,159.2,155.1,153.7,153.2,141.2,132.0, 130.0,125.3,123.8,79.2,78.1,63.7,53.6,40.9,40.7,34.9,28.9,28.8,28.4,20.8.
Embodiment 30, preparation N- (2- ((isoquinolyl-1 (phenyl) methyl) amino) -2- oxoethyls) benzamide
Reaction equation：
Method with example 1, yield is：94%.
1H NMR (400MHz, CDCl3) δ 8.36 (d, J=5.7Hz, 1H), 8.06 (d, J=8.4Hz, 1H), 7.89-7.76 (m, 4H), 7.66 (dd, J=8.0,7.0Hz, 1H), 7.60-7.46 (m, 3H), 7.42 (t, J=7.6Hz, 2H), 7.22 (d, J =4.2Hz, 1H), 7.10-7.01 (m, 3H), 6.87-6.76 (m, 2H), 6.29-6.16 (m, 1H), 4.17 (d, J=4.9Hz, 2H), 3.36-3.21 (m, 2H).
13C NMR (101MHz, CDCl3) δ 168.0,167.5,158.1,141.0,136.7,136.3,133.9,131.7, 130.3,129.6,128.5,128.1,127.6,127.4,127.2,126.5,125.7,124.2,120.6,51.0,43.5, 42.2.
Embodiment 31, prepare benzyl (2- ((2- (1H- indol-3-yls) -1- (isoquinolyl-1) ethyl) amino) -2- oxygen For ethyl) t-butyl carbamate
Reaction equation：
With example 1, yield is 90% to method.
1H NMR (400MHz, CDCl3) δ 8.26 (d, J=5.5Hz, 1H), 8.05 (d, J=8.4Hz, 1H), 7.97 (s, 1H), 7.80 (d, J=8.2Hz, 1H), 7.75 (d, J=6.1Hz, 1H), 7.65 (t, J=7.5Hz, 1H), 7.54 (d, J= 5.6Hz, 1H), 7.51-7.45 (m, 1H), 7.41-7.28 (m, 5H), 7.21 (d, J=8.1Hz, 1H), 7.06 (t, J= 7.5Hz, 1H), 7.00 (d, J=8.1Hz, 1H), 6.90 (t, J=7.5Hz, 1H), 6.60 (s, 1H), 6.28 (dd, J=12.6, 6.4Hz, 1H), 5.54 (s, 1H), 5.12 (s, 2H), 3.92 (d, J=5.6Hz, 2H), 3.57-3.35 (m, 2H).
13C NMR (101MHz, CDCl3) δ 168.1,158.5,156.5,140.6,136.4,136.3,135.8,130.3, 128.5,128.1,128.1,127.9,127.5,127.3,125.8,124.4,123.1,121.7,120.6,119.3, 118.3,111.0,110.6,67.0,50.3,44.5,31.8.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out Some improvement and modification, these improvement and modification are also fallen in the protection domain of the claims in the present invention.

Claims (10)

1. a kind of preparation method of aromatic aza cycle compound, including：
By formula (I) compound, that nitrogen-containing heterocycle compound carries out illumination under photochemical catalyst, organic phosphoric acid and solvent existence condition is anti- Should, obtain the compound with formula (II) structure；
Wherein, the R1Alkyl for the alkoxy carbonyl group of C2～C20, the acyl group of C2～C25 or C7～C30；
The R2For hydrogen atom, the alkyl without functional group of C1～C30, the alkyl containing functional group of C1～C30, C5～C30 Aryl or the heteroaryl of C5～C30；
Or R1、R2And the nitrogen that is connected with them and carbon form five-membered ring or hexatomic ring；The R3For formula (I-c),
Wherein, R is hydrogen or chlorine.
2. preparation method according to claim 1, it is characterised in that the photochemical catalyst is formula (cat-1), formula (cat- 2), formula (cat-3) or formula (cat-4)；
3. preparation method according to claim 1, it is characterised in that the organic phosphoric acid is formula (PA-1), formula (PA-1) Or formula (PA-3)；
4. preparation method according to claim 1, it is characterised in that the R1For benzyloxycarbonyl group, tertbutyloxycarbonyl, fluorenes first Oxygen carbonyl, allyloxycarbonyl, trimethylsilyl ethoxycarbonyl, methoxycarbonyl group, carbethoxyl group, phthalyl, tolysulfonyl Base, trifluoroacetyl group, ortho-nitrophenyl sulfonyl, p-nitrophenyl sulfonyl, pivaloyl group, benzoyl, trityl, 2,4- bis- Methoxy-benzyl, to methoxy-benzyl or benzyl.
5. preparation method according to claim 1, it is characterised in that formula (I) compound is by amino acid or polypeptide carboxylic Hydrogen on base is by R3Amino hydrogen on replaced and carboxyl α-carbon is replaced to be formed by R2.
6. preparation method according to claim 1, it is characterised in that formula (I) compound is formula (I-1), formula (I- 2), formula (I-3), formula (I-4), formula (I-5), formula (I-6), formula (I-7), formula (I-8), formula (I-9), formula (I-10, formula (I-11) formula (I-12), formula (I-12), formula (I-13), formula (I-14), formula (I-15), formula (I-16), formula (I-17) or formula (I-18)；
7. preparation method according to claim 1, it is characterised in that the nitrogen-containing heterocycle compound is formula (Het-a), formula (Het-b), formula (Het-c), formula (Het-d), formula (Het-e), formula (Het-f), formula (Het-g), formula (Het-h), formula (Het-i) Or formula (Het-j)；
Wherein, R is selected from hydrogen, halogen, amino, the alkyl without functional group of C1～C8, the alkyl containing functional group of C1～C8, C6 The heterocyclic radical of the aryl of～C30, sulfonyl or C3～C15.
8. preparation method according to claim 1, it is characterised in that the nitrogen-containing heterocycle compound be formula (Het-a-1), Formula (Het-b-2), formula (Het-b-3), formula (Het-a-4), formula (Het-a-5), formula (Het-c-6), formula (Het-d-7), formula (Het-a-8), formula (Het-g-9), formula (Het-f-10), formula (Het-e-11), formula (Het-g-12), formula (Het-b-13), formula (Het-i-14) or formula (Het-j-15),
9. preparation method according to claim 1, it is characterised in that formula (I) compound and nitrogen-containing heterocycle compound Mol ratio be 1：(1.0～2.5).
10. preparation method according to claim 1, it is characterised in that the light source of the illumination is ultraviolet light or blue light.
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