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A kind of synthetic method of optically active 2-(2-nitro-ethyl)-pyrrole

A nitroethyl and pyrrole technology, applied in the field of 2-pyrrole compounds, achieves the effects of simple operation, mild reaction conditions and high enantioselectivity

Inactive Publication Date: 2011-12-07
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There are still relatively few effective reports on the asymmetric addition reaction of nitroalkenes and pyrroles in the current literature, and several of the better structures have used metal complex catalysts [(a) B.M.Trost, C.Müller, J. Am.Chem.Soc.2008, 130, 2438.(b) H.Liu, S.-F.Lu, J.Xu, D.-M.Du, Chem.Asian J.2008, 3, 1111]

Method used

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  • A kind of synthetic method of optically active 2-(2-nitro-ethyl)-pyrrole
  • A kind of synthetic method of optically active 2-(2-nitro-ethyl)-pyrrole

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Experimental program
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Effect test

Embodiment 1

[0020] Embodiment 1: the preparation of chiral phosphoric acid

[0021] Under the protection of argon at room temperature, dissolve the derivative of BINOL (0.5mmol) in 1mL of dry pyridine in a dry reaction tube, and slowly drop (1.0mmol) of phosphorus oxychloride under the condition of rapid stirring Added to the system, stirred at room temperature for 3 hours. 1 mL of water was slowly added dropwise to the system, and stirred at room temperature for 30 minutes. Dichloromethane was added to dissolve, washed with 1N hydrochloric acid aqueous solution (10mL×3), the organic layer was dried over anhydrous sodium sulfate, the solvent was spun off under reduced pressure, and the residue was separated by column chromatography to obtain the product.

[0022] (S)-3,3'-[3,5-bis(trifluoromethyl)phenyl]2-1,1'-binaphthol phosphate

[0023] (S)-3,3′-[3,5-Bis(trifluoromethyl)phenyl]2-1,1′-binaphthyl phosphate

[0024]

[0025] Solid, 89% yield. IR (lamination method) 1620, 1501, 1474...

Embodiment 2

[0026] Example 2: Chiral phosphoric acid catalyzed addition reaction of pyrroles to nitroalkenes

[0027] Add (chiral) phosphoric acid compound (0.0015mmol), pyrrole compound (0.45mmol), benzene / dichloromethane 0.6mL and Molecular sieves (50-100 mg), under stirring at room temperature, slowly add nitroalkene compound (0.30 mmol) (dissolved in 0.6 mL benzene / dichloromethane) dropwise for 2 hours, and the product was separated by column chromatography.

[0028] P1: 2-(2-nitro-1-phenylethyl)-pyrrole

[0029] P1: 2-(2-nitro-1-phenylethyl)-1H-pyrrole

[0030] R f =0.40 (dichloromethane / petroleum ether=1 / 1, v / v); brown solid; 94% yield, 89% ee; 1 H NMR (400MHz, CDCl 3 )δ4.78(dd, J=11.9Hz, 7.6Hz, 1H), 4.86-4.89(m, 1H), 4.96(dd, J=11.9Hz, 7.3Hz, 1H), 6.06-6.08(m, 1H) , 6.14-6.17(m, 1H), 6.65-6.67(m, 1H), 7.20-7.24(m, 2H), 7.27-7.36(m, 3H), 7.82(br, 1H); 13 C NMR (100MHz, CDCl 3 )δ42.9, 79.2, 105.8, 108.6, 118.2, 127.9 (2C), 128.1, 128.9, 129.2 (2C), 137.9; IR (press film met...

Embodiment 3

[0082] Example 3: Conversion of 2-(2-nitroethyl)-pyrrole compounds

[0083] In an egg-shaped bottle, 2-(2-nitroethyl)-pyrrole compound (1mmol) was dissolved in acetonitrile (7mL), and NaIO was added at room temperature 4 Aqueous solution (0.06mmol / 21mL), stirred for 15 minutes after addition. Ruthenium trichloride compound was added and stirred for 2 hours, and the reaction was completed and extracted with ethyl acetate (3x10 mL). The combined organic layers were added with diethyl ether (15 mL) and stirred for several minutes. Anhydrous magnesium sulfate was added for drying, and the solvent was removed under reduced pressure, and the residue was separated by column chromatography to obtain a crude product. It was dissolved in tetrahydrofuran (0.5 mL), and oxalyl chloride (0.3 mmol) was added at zero temperature. After the addition, it was stirred at room temperature for 1 hour, and the solvent and excess oxalyl chloride were removed under reduced pressure. The obtained cr...

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Abstract

The invention relates to a 2-(2-nitro-ethyl)-pyrrole compound, a synthesis method and use thereof. Using chiral phosphoric acid as a catalyst, 2-(2-nitroethyl)-pyrrole compounds can be synthesized from nitroalkenes and pyrrole compounds with high efficiency and high enantioselectivity. The method is applicable to many different types of pyrrole compounds and nitroalkene compounds, and has mild reaction conditions and simple operation. In addition, there is no need to add any metal salt compounds in the reaction, which is beneficial to the production and treatment of medicines. And the yield of the reaction is also good (generally 85%-98%), and the enantioselectivity is high (generally 87%-97%).

Description

technical field [0001] The invention relates to a 2-(2-nitro-ethyl)pyrrole compound, which is to synthesize 2-(2- Nitro-ethyl)-pyrrole compound. Background technique [0002] In recent years, organic small molecule catalysis has attracted widespread attention from academia and industry all over the world due to its advantages of easy synthesis, convenient structure modification, and no heavy metal residue [(a) Seayad, J.; List, B.Org .Biomol.Chem.2005,3,719-724.(b) Dalko, P.I.; Moisan, L.Angew.Chem.Int.Ed.2004,43,5138-5175.], wherein by chiral phosphoric acid as catalyst The achieved asymmetric catalysis has achieved rapid development in the past three years [(a) Q.Kang, Z.-A.Zhao, S.-L.You, J.Am.Chem.Soc.2007, 129, 1484-1485.(b) Q.Kang, X.-J.Zheng, S.-L.You, Chem.Eur.J.2008, 14, 3539-3542.(c)J.Itoh, K.Fuchibe, T.Akiyama, Angew.Chem.2008, 120, 4080-4082; Angew.Chem.Int.Ed.2008, 47, 4016-4018.(d) X.-W.Wang, C.M. .Am.Chem.Soc.2008, 130, 6070-6071.(e)Q.-S.Guo, D.-M.Du, J.-X...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D207/33C07D207/333C07D409/06C07D405/06C07D207/337C07F7/10B01J31/24
Inventor 游书力盛益飞
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI