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Iron catalyst system for preparation of pyridine derivatives and its application

A technology for iron catalysts and derivatives, which is applied in the field of iron catalysts for the preparation of pyridine derivatives, can solve the problems of slow development of catalytic systems, restrictions on the application of iron catalytic systems, and difficulty in preparation, and achieves simple and practical reaction operations, high yields, Easy to prepare

Inactive Publication Date: 2013-01-16
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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Problems solved by technology

However, the development of its catalytic system is very slow for iron, a metal that is rich in sources, non-toxic, cheap, and environmentally friendly [Documents: Ferré, K.; Toupet, L.; Guerchais, V.Organometallics, 2002, 21 , 2578; Schmidt, U.; Zenneck, U.J.Organomet.Chem.1992, 440, 187; Knoch, F.; Kremer, F.; Schmidt, U.; Zenneck, U.; Floch, P.L.; , 1996, 15, 2713.], only two cases were reported by Zenneck and Guerchais, and the catalysts used were iron-phosphine heteroaromatic complexes and Cp * Fe +1 (CH 3 EN) 3 Complexes are also not easy to prepare, which greatly limits the application of iron-catalyzed systems in the synthesis of pyridine compounds

Method used

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  • Iron catalyst system for preparation of pyridine derivatives and its application
  • Iron catalyst system for preparation of pyridine derivatives and its application
  • Iron catalyst system for preparation of pyridine derivatives and its application

Examples

Experimental program
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example 1

[0020] Example 1: Preparation and screening of iron catalyst

[0021] Add iron metal precursor (0.05mmol) and bisphosphine ligand (0.10mmol) into the reaction flask, add 1mL tetrahydrofuran after argon replacement, and stir at room temperature for 0.5 hours. Then add reducing agent Zn (0.10mmol) and stir, then add diyne 1a (0.25mmol) and nitrile 2a (2.5mmol), react at room temperature for 24h. After the reaction, the solvent was removed, and the pure product was obtained by direct column chromatography separation, and its structure was confirmed by nuclear magnetic resonance. The reaction formula and ligand structure are shown in formula 4:

[0022]

[0023] Conversion rate and productive rate are determined (internal standard method) by gas chromatography, and part result is listed in Table 1:

[0024] Table 1. Screening of iron catalysts

[0025]

example 2

[0026] Example 2: Synthesis of pyridine derivatives by iron-catalyzed [2+2+2] cycloaddition of diynes and nitriles

[0027] Add FeI to the reaction flask 2 (0.05mmol) and dppp (0.10mmol), after argon replacement, 2mL tetrahydrofuran was added, and stirred at room temperature for 0.5 hours. Then the reducing agent Zn (0.10mmol), diyne 1 (0.5mmol) and nitrile 2 (2.5mmol) were added, and the reaction was stirred at room temperature for 24h. After the reaction, the solvent was removed, and the pure product 3 was obtained by direct column chromatography separation, and its structure was confirmed by nuclear magnetic resonance. The reaction formula and the yield of some products were as shown in formula 5:

[0028] The NMR data of some products are as follows:

[0029] 3a: 1 H NMR (400MHz, Acetone) δ7.57-7.30(m, 5H), 3.76(s, 6H), 3.62(s, 2H), 3.61(s, 2H), 2.40(s, 3H), 2.23(s, 3H); 13 C NMR (100MHz, Acetone) δ172.4, 157.2, 151.0, 150.3, 141.9, 133.3, 130.1, 128.6, 128.2, 124.8, ...

example 3

[0034] Example 3: Iron-catalyzed [2+2+2] cycloaddition reaction of monoalkynes and nitriles to synthesize pyridine derivatives

[0035] Add FeI to the reaction flask 2 (0.05mmol) and dppp (0.10mmol), after argon replacement, 2mL tetrahydrofuran was added, and stirred at room temperature for 0.5 hours. Then adding reducing agent Zn (0.10mmol), monoalkyne 4 (1mmol) and nitrile 2 (2.5mmol), the reaction was stirred at room temperature for 24h. After the reaction, the solvent was removed, and the pure products 5 and 6 were obtained by direct column chromatography separation, and its structure was confirmed by nuclear magnetic resonance. The reaction formula and the yield of some products were as shown in formula 6:

[0036]

[0037] The NMR data of some compounds are as follows:

[0038] 5: 1 H NMR (500MHz, Acetone) δ8.18 (dt, J=8.3, 1.7Hz, 2H), 7.83 (d, J=7.9Hz, 1H), 7.67 (d, J=8.0Hz, 1H), 7.53-7.47 (m, 4H), 7.47-7.40(m, 4H), 2.54(s, 3H); 13 C NMR (125MHz, Acetone) δ156.1...

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Abstract

The invention provides an iron catalyst system for preparation of pyridine derivatives and its application. The catalyst is composed of a cheap and easily available iron salt, a diphosphine ligand and a reducing agent. Application of the catalyst in synthesis of pyridine derivatives can be carried out under the conditions that: a substrate diyne or monoyne and the catalyst are in a molar ratio of 20-1:1, and the diyne or monoyne and nitrile are in a molar ratio of 1:1-40; the temperature is maintained in a range from room temperature to 100DEG C; tetrahydrofuran, 1, 4-dioxane or the reactant nitrile is adopted as the solvent; the reaction time is 6-48h. The iron catalyst can well catalyze a [2+2+2] cycloaddition reaction of the diyne or monoyne and the nitrile so as to obtain various pyridine derivatives. The iron catalyst system provided in the invention has the advantages of high reaction activity, complete reaction, single product, simple and practical operation, easily available raw materials as well as high yield, and has the characteristics of green atom economy and environment friendliness.

Description

technical field [0001] The invention relates to an iron catalyst for preparing pyridine derivatives, which is applied to the [2+2+2] cycloaddition reaction of diynes or monoynes and nitriles to synthesize pyridine derivatives. Background technique [0002] Pyridine and its derivatives are widely used as organic synthesis reagents, or as intermediates for the production and synthesis of medicines, pesticides, and various materials [Document: Jones, G. Comprehensive Heterocyclic Chemistry II, Vol.5 (Eds.: Katritzky, A.R.; Rees, C.W.; Scriven, E.F.V.; McKillop, A.), Pergamon, Oxford, 1996, pp.167-243; Joule, J.A.; Mills, K. Heterocyclic Chemistry, 4th ed., Blackwell Science, Cambridge, 2000; p. 63-120; Michael, J.P. Nat. Prod. Rep. 2005, 22, 627-646.]. Some natural products such as cholestane rearrangement derivatives Diploclidine, alkaloid Nakinadine A, drugs that have been successfully marketed such as anti-AIDS drug Atazanavir, anti-cancer drug Gleevec, blood sugar regulati...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07D221/04C07D471/04C07D491/048C07D217/02
Inventor 万伯顺王春翔吴凡
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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