(Z)-4-difluoroalkyl-5-sulfanyl-4-pentenone derivative and preparation method thereof

A technology of difluoroalkyl and sulfanyl, applied in the field of -4-difluoroalkyl-5-sulfanyl-4-pentenone derivatives and its preparation, can solve the problem of not obtaining olefin addition products and other problems, to achieve the effects of wide application range of substrates, large theoretical innovation value, and mild reaction conditions

Active Publication Date: 2019-12-31
ZHEJIANG NORMAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the long-range C-H functionalization initiated by the free radical addition of alkynes has been realized. However, this reaction often undergoes migration of the free radical addition atom and then is cyclized to form a ring instead of an alkene addition product.

Method used

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  • (Z)-4-difluoroalkyl-5-sulfanyl-4-pentenone derivative and preparation method thereof
  • (Z)-4-difluoroalkyl-5-sulfanyl-4-pentenone derivative and preparation method thereof
  • (Z)-4-difluoroalkyl-5-sulfanyl-4-pentenone derivative and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Take a dry reaction tube, add hi-tris(2-phenylpyridine)iridium (2.6mg, 0.004mmol), silver carbonate (110.3mg, 0.4mmol), ethyl bromodifluoroacetate under nitrogen atmosphere (81.2 mg, 0.40 mmol), alkyne sulfide represented by structural formula 1a (38 mg, 0.2 mmol) were then added to 2 mL of dry dimethyl sulfoxide to form a reaction system. The system was stirred under a 15W blue light lamp at room temperature 25°C for 12h, quenched by adding 15mL of water, extracted three times with ethyl acetate (10mL), combined, the organic phase was washed with saturated edible water, and dried over anhydrous sodium sulfate. After the organic phase was concentrated, it was separated by silica gel (300-400 mesh) column chromatography to obtain 50 mg of a light yellow liquid represented by structural formula 2a, with a yield of 78%.

[0028] Product Spectrum Analysis 1 H NMR (600MHz, CDCl 3 )δ7.98–7.97(m,2H),7.59(t,J=7.4Hz,1H),7.48(t,J=7.7Hz,2H),6.44(s,1H),4.33(q,J=7.1 Hz, 2H), 3.21...

Embodiment 2

[0032] Except that the alkyne thioether derivative shown in structural formula 1b was used instead of the alkyne thioether derivative shown in structural formula 1a in Example 1, the rest of the operation steps were the same as in Example 1, yield: 67%, light yellow liquid shown in structural formula 2b.

[0033] Product Spectrum Analysis 1 H NMR (600MHz, CDCl 3 )δ7.96(d, J=7.3Hz, 2H), 7.57(t, J=7.4Hz, 1H), 7.47(t, J=7.7Hz, 2H), 6.47(s, 1H), 4.30(q, J=7.1Hz, 2H), 3.20(t, J=7.3Hz, 2H), 2.73–2.67(m, 4H), 1.30(t, J=7.1Hz, 3H), 1.27(t, J=7.4Hz, 3H); 13 C NMR (151MHz, CDCl 3 )δ198.8, 163.4(t, J=35.4Hz), 136.7, 133.4(t, J=6.0Hz), 133.1, 128.6, 128.1(t, J=23.4Hz), 127.9, 113.9(t, J=251.6Hz) ,63.0,37.9,29.2,27.6(t,J=3.6Hz),15.3,13.8; 19 F NMR (565MHz, CDCl 3 )δ-100.4; HRMS (ESI) calcd for C 17 h 20 f 2 o 3SNa(M+Na) + 365.0993, found 365.1002.

[0034] The reaction formula is as follows:

[0035]

Embodiment 3

[0037] Except that the alkyne thioether derivative shown in structural formula 1c was used to replace the alkyne thioether derivative shown in structural formula 1a in Example 1, the rest of the operation steps were the same as in Example 1, yield: 83%, light yellow liquid shown in structural formula 2c.

[0038] Product Spectrum Analysis 1 H NMR (600MHz, CDCl 3 )δ7.86(d, J=8.2Hz, 2H), 7.26(d, J=7.8Hz, 2H), 6.41(s, 1H), 4.32(q, J=7.1Hz, 2H), 3.16(t, J=7.3Hz, 2H), 2.68(t, J=7.4Hz, 2H), 2.41(s, 3H), 2.29(s, 3H), 1.32(t, J=7.1Hz, 3H); 13 C NMR (151MHz, CDCl 3 )δ198.4, 163.4(t, J=35.0Hz), 143.9, 135.0(t, J=5.8Hz), 134.3, 129.3, 128.1, 127.6(t, J=23.4Hz), 114.0(t, J=252.0Hz) ,63.0,37.8,27.6(t,J=3.6Hz),21.6,18.4,13.9; 19 F NMR (565MHz, CDCl 3 )δ-100.7; HRMS (ESI) calcd for C 17 h 20 f 2 o 3 SNa(M+Na) + 365.0993, found 365.0995.

[0039] The reaction formula is as follows:

[0040]

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Abstract

The invention discloses a (Z)-4-difluoroalkyl-5-sulfanyl-4-pentenone derivative and a preparation method thereof. The preparation method comprises following steps: an alkyne thioether with a structureshown in formula II, monobromo difluoroacetate, fac-Ir(ppy)3, an alkali and a solvent are mixed, a reaction system is formed under blue light irradiation, and the (Z)-4-difluoroalkyl-5-sulfanyl-4-pentenone derivative with a structure shown in formula I is obtained through aftertreatment. According to the invention, the addition-hydrogen migration-noncyclization cascade reaction of free radicalson non-terminal alkyne is realized for the first time, and the stereoselective synthesis of the (Z)-4-difluoroalkyl-5-sulfanyl-4-pentenone derivative is realized in one step. The reaction conditions are mild, the substrate application range is wide, the reaction yield is good, the operation is simple, and a new way is provided for synthesis of fluorine-containing pentenone compounds.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and specifically relates to a (Z)-4-difluoroalkyl-5-sulfanyl-4-pentenone derivative and a preparation method thereof. Background technique [0002] The C-H bond is the simplest and most common functional group in organic compounds. The selective oxidation of hydrocarbons to synthesize oxygen-containing organic chemical products occupies an extremely important position in industrial synthesis, especially in petrochemicals. However, the selective oxidation of hydrocarbons faces many problems. First of all, due to the high activation energy of the C-H bond of saturated hydrocarbons, it is difficult to oxidize, and usually requires the addition of high temperature and high pressure or an equivalent strong oxidant. Secondly, target products such as alcohols, ketones, aldehydes, and acids are mostly thermodynamically unstable intermediate compounds, which are easily further deeply oxidized. These no...

Claims

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Application Information

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IPC IPC(8): C07C319/20C07C323/56C07F7/18
CPCC07B2200/09C07C319/20C07C323/56C07F7/1804C07F7/1892
Inventor 朱钢国商甜波周雨露
Owner ZHEJIANG NORMAL UNIVERSITY
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