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Preparation method of aromatic nitrogen heterocyclic compound

A technology of nitrogen heterocyclic compounds and compounds, which is applied in the field of preparation of aromatic nitrogen heterocyclic compounds, can solve the problems of poor compatibility of functional groups and limited scope of application of substrates, etc., and achieve the effect of high conversion rate

Active Publication Date: 2017-03-15
UNIV OF SCI & TECH OF CHINA
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

However, these reported methods often require the addition of excess oxidants to achieve functionalization, and the functional group compatibility is poor, and the scope of substrate application is relatively limited.

Method used

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  • Preparation method of aromatic nitrogen heterocyclic compound
  • Preparation method of aromatic nitrogen heterocyclic compound
  • Preparation method of aromatic nitrogen heterocyclic compound

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preparation example Construction

[0030] The present invention provides a kind of preparation method of aromatic nitrogen heterocyclic compound, comprising:

[0031] The compound of formula (I) and the nitrogen-containing heterocyclic compound are subjected to light reaction in the presence of photocatalyst, organic phosphoric acid and solvent to obtain the compound with the structure of formula (II);

[0032]

[0033] where the R 1 C2-C20 alkoxycarbonyl, C2-C25 acyl or C7-C30 alkyl;

[0034] The R 2 It is a hydrogen atom, a C1-C30 alkyl group without a functional group, a C1-C30 alkyl group with a functional group, a C5-C30 aryl group or a C5-C30 heteroaryl group;

[0035] or R 1 , R 2 Form five-membered or six-membered rings with the nitrogen and carbon attached to them;

[0036] The R 3 For formula (I-c),

[0037] Wherein, R is hydrogen or chlorine.

[0038] Among them, in the formula (II) It is the abbreviation of the group after removing one hydrogen from the nitrogen-containing heterocycli...

Embodiment 1

[0062] Embodiment 1, preparation N-(2-phenyl-1-(4-phenyl-2-quinolyl) ethyl) tert-butyl carbamate

[0063] Reaction formula:

[0064]

[0065] The specific method is as follows:

[0066] Add photocatalyst (Ir[dF(CF3)ppy]2(dtbbpy)PF6) (1mol% , 2.2mg), binaphthol phosphate (PA-1) (10mol%, 7.0mg) and boc-protected phenylalanine NHPI ester (0.3mmol, 123mg). The air in the tube was completely replaced with argon three times, and then 2 mL of N,N-dimethylacetamide (DMA), 4-phenylquinoline (0.2 mmol, 41 mg) was added under argon atmosphere. The reaction system was continuously stirred for 3 hours at room temperature under the irradiation of a 36W blue LED lamp (IKA magnetic stirrer, RCT basic type, stirring speed 500 rpm). After the reaction was completed, the reaction was quenched with H2O, and the reaction solution was extracted with ethyl acetate (3*10mL), and then the combined organic phase was concentrated by rotary evaporation (BUCHI Co., Ltd., BUCHI Rotary Evaporator R-3)...

Embodiment 2

[0069] Embodiment 2, preparation N-(2-phenyl-1-(4-phenyl-2-quinolyl) ethyl) benzyl carbamate

[0070] Reaction formula:

[0071]

[0072] Method is the same as example 1, and the productive rate is 81%. The NMR data are: 1 H NMR (400MHz, CDCl 3 )δ8.10(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). 13 C NMR (101MHz, CDCl 3 )δ158.8, 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, 125.4, 71.8, 125.9, 125.5 , 43.0.

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Abstract

The invention provides a preparation method of an aromatic nitrogen heterocyclic compound. According to the preparation method, a compound represented by formula I, and a nitrogen-containing heterocyclic compound are subjected to illumination reaction in the presence of a photocatalyst, an organic phosphoric acid, and a solvent so as to obtain a compound with a structure represented by formula II, wherein electron transition of the photocatalyst is excited by illumination so as to catalyze decarboxylation of active carboxylic esters in the compound with the structure represented by formula I, and minisci reaction with the nitrogen-containing heterocyclic compound is realized so as to introduce nitrogen heterocyclic rings. Compared with a reported conventional method wherein nitrogen heterocyclic rings are introduced via minisci reaction, the preparation method comprises following steps: equivalent weight strong oxidant application is avoided; the universality of substrate range and functional group compatibility is increased; the preparation method can be applied in gram-grade scale reaction of decarboxylation and nitrogen heterocyclic ring introduction of active carboxylic esters of polypeptides, and decarboxylation and nitrogen heterocyclic ring introduction of active carboxylic esters of amino acids; conversion rate is high; and industrial synthesis value prospect is promising.

Description

technical field [0001] The invention relates to the field of compound synthesis, in particular to a preparation method of an aromatic nitrogen heterocyclic compound. Background technique [0002] Aromatic heterocyclic compounds are extremely important structural units in the field of medicinal chemistry, and functionalization of aromatic heterocyclic rings through selective catalysis is one of the important means to discover new drugs. The main method to achieve the functionalization of aromatic heterocycles is the known Minisci reaction, as already reported: 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-HFunctionalization, Duy N. Mai and Ryan D. Baxter, Org. Lett., 2016, 18, pp 3738-3741. However, these reported methods often require the addition of excessive oxidants to achieve functionalization, and the functional group compatib...

Claims

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Application Information

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IPC IPC(8): C07D215/12C07D401/04C07D401/06C07D217/14C07D217/16C07D217/20C07D215/18C07D221/12C07D237/30C07D239/42C07D241/44C07D239/74C07D401/12C07D471/04C07D473/32C07D473/12
CPCC07D215/12C07D215/18C07D217/14C07D217/16C07D217/20C07D221/12C07D237/30C07D239/42C07D239/74C07D241/44C07D401/04C07D401/06C07D401/12C07D471/04C07D473/12C07D473/32
Inventor 傅尧尚睿成万民付明臣
Owner UNIV OF SCI & TECH OF CHINA
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