Cyanoalkyl substituted tetra-substituted olefin derivatives and synthesis thereof

A tetra-substituted, cyanoalkyl technology, applied in the preparation of sulfides, organic chemistry, etc., can solve the problems of high cost and poor atom economy, and achieve the effects of simple operation, low cost, and easy availability of raw materials

Active Publication Date: 2020-06-09
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, these methods basically require the pre-functionalization of raw materials, such as halogenation, siliconation, boronation, trifluoromethylsulfonylation, etc.,

Method used

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  • Cyanoalkyl substituted tetra-substituted olefin derivatives and synthesis thereof
  • Cyanoalkyl substituted tetra-substituted olefin derivatives and synthesis thereof
  • Cyanoalkyl substituted tetra-substituted olefin derivatives and synthesis thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032]

[0033] In a 25mL schlenk tube, add 3,3-dialkylthio-2-propene-1-one compound 2a (0.3mmol), cyclobutanone oxime ester 3a (0.6mmol), iron trichloride ( 10mol%) and 1.5 mL of benzotrifluoride at 110°C for 24 hours. After cooling to room temperature, the volatile components were removed under reduced pressure, and then separated by silica gel column chromatography (eluent was petroleum ether (60-90°C) / ethyl acetate, v / v=50:1) to obtain the target product 1a (69mg, 79% yield). The target product was confirmed by nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry.

[0034] Compound characterization data

[0035] Cyano-substituted tetra-substituted olefin derivative (1a), yellow liquid. 1 H NMR(400MHz, CDCl 3 )δ7.86,7.57and 7.47(m each,2:1:2H,aromatic CH),2.79(dd,J=8.6and 6.9Hz,2H,(C=O)CCH 2 ),2.39(m,5H,CH 2 CN and SMe),2.07(s,3H,SMe),1.84(m,2H,CH 2 CH 2 CN). 13 C{ 1 H)NMR(100MHz,CDCl 3 )δ196.59(Cq,C=O),144.7,136.8and 136.5(Cq),133.5,129.0and128.8(arom...

Embodiment 2

[0037]

[0038] In a 25mL schlenk tube, add 3,3-dialkylthio-2-propene-1-one compound 2b (0.3mmol), cyclobutanone oxime ester 3a (0.6mmol), iron trichloride ( 10mol%) and 1.5 mL of benzotrifluoride at 110°C for 24 hours. After cooling to room temperature, the volatile components were removed under reduced pressure, and then separated by silica gel column chromatography (eluent: petroleum ether (60-90°C) / ethyl acetate, v / v=50:1) to obtain the target product 1b (73mg, yield 76%). The target product was confirmed by nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry.

[0039] Compound characterization data

[0040] Cyano-substituted tetra-substituted olefin derivative (1b), yellow liquid. 1 H NMR(400MHz, CDCl 3 )δ7.84, 7.57 and 7.45 (m each, 2:1: 2H, aromatic CH), 2.82 (m, 4H, SCH 2 and(C=O)CCH 2 ), 2.62(q,J=7.4Hz,2H,SCH 2 ), 2.38(t,J=7.2Hz,2H,CH 2 CN),1.84(m,2H,CH 2 CH 2 CN),1.30(t,J=7.3Hz,3H,CH 2 CH 3 ),1.02(t,J=7.4Hz,3H,CH 2 CH 3 ). 13 C{ 1 H)NMR(100MHz,...

Embodiment 3

[0042]

[0043] The reaction steps and operations are the same as in Example 1, and the difference from Example 1 is that the 3,3-dialkylthio-2-propene-1-one compound is 2c. The reaction was stopped, and the target product 1c (66 mg, yield 76%) was obtained after post-treatment. The target product was confirmed by nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry.

[0044] Cyano-substituted tetra-substituted olefin derivative (1c), yellow liquid. 1 H NMR(400MHz, CDCl 3 )δ7.44 (m, 5H, aromatic CH), 3.38 (m, 4H, SCH 2 CH 2 S), 2.73(dd,J=8.6and 6.9Hz,2H,(C=O)CCH 2 ),2.21(t,J=7.2Hz,2H,CH 2 CN),1.75(m,2H,CH 2 CH 2 CN). 13 C{ 1 H)NMR(100MHz,CDCl 3 )δ193.6(C q ,C=O),162.3,139.4and 122.9(C q ),130.9,128.4and 127.5(aromatic CH),119.2(CN),39.1,36.5,33.8,24.2and 16.8(CH 2 ).HRMS Calcd for C 15 H 15 NOS 2 [M+H] + :290.0673; Found:290.0672.

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Abstract

The invention discloses a method for synthesizing a cyanoalkyl substituted tetra-substituted olefin derivative with potential biological activity. According to the method, 3,3-dialkylthio-2-propylene-1-one and cyclobutanone oxime ester which are easy to prepare and have structural diversity and multiple reaction centers are used as raw materials, free radicals are generated through cyclobutanone oxime ester to carry out olefin addition, and the cyanoalkyl-substituted tetra-substituted olefin derivative is generated in one step. The method has the advantages of easily available raw materials, simple operation, mild synthesis reaction conditions, high reaction efficiency, and diversity of functional groups.

Description

Technical field [0001] The invention relates to a method for synthesizing a cyanoalkyl substituted tetra-substituted olefin derivative with potential biological activity. Background technique [0002] Multi-substituted olefins are important structural units in organic functional materials, drug molecules, and natural products. They are the core framework of many natural products and physiologically active compounds. They are also important organic synthesis intermediates. Recent studies have shown that cyanoalkyl substituted compounds have good applications in medicinal chemistry and enzyme chemistry (J.Med.Chem.2010,53,7902-7917; ACSMed.Chem.Lett.2014,5,937-941 ; Catal.Sci.Technol.2014,4,2871-2876). [0003] At present, the method for synthesizing polysubstituted olefins is mainly through the synthesis of carbon-carbon bonds catalyzed or promoted by different transition metals. However, these methods basically require pre-functionalization of the raw materials, such as halogenat...

Claims

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Application Information

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IPC IPC(8): C07C319/20C07C323/56C07D339/06C07D339/08C07D231/20
CPCC07C319/20C07C323/56C07D231/20C07D339/06C07D339/08
Inventor 余正坤娄江
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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