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Chiral benzodihydrothiapyran-4-one compound as well as preparation method and application thereof

A technology for chroman and ketone compounds, which is applied in the field of chiral compound synthesis, can solve problems such as unreported synthesis, and achieve the effects of less photocatalyst dosage, mild reaction conditions, and less metal-free participation.

Active Publication Date: 2021-05-07
HENAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, so far, no one has reported the synthesis of 2-(2-(2´-pyridine) ethyl) chroman-4-ones

Method used

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  • Chiral benzodihydrothiapyran-4-one compound as well as preparation method and application thereof
  • Chiral benzodihydrothiapyran-4-one compound as well as preparation method and application thereof
  • Chiral benzodihydrothiapyran-4-one compound as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] ( R )-2-(2-(2′-pyridine) ethyl) chroman-4-ketone III-1 The specific preparation steps are as follows:

[0034]

[0035] Preparation procedure: Take a dry 25 mL schlenk tube and add 24.3 mg (0.15 mmol) of 4H -Benzothiopyran-4-one I-1, 10.5 mg (0.1 mmol) vinylpyridine II-1, DPZ (0.7 mg, 0.002 mmol), chiral phosphoric acid catalyst BA (13.3 mg, 0.02 mmol), Hans Esters HE 55.6 mg (0.18 mmol), then add 1 mL of dichloromethane, cover the bottle cap, degas with a vacuum pump 2-3 times at no higher than -78°C, 5-10 min each time, and inject Protected by argon, then placed at -25°C, after standing still for half an hour, irradiated with a 3 W blue light with a wavelength of 410-510 nm at a distance of about 3 cm from the schlenk tube, and reacted for 60 hours. After the reaction, the column layer Analysis and separation (petroleum ether / ethyl acetate = 10~3:1, volume ratio), concentration by rotary evaporation, and vacuum drying (drying at 25°C for 1 hour) yielded 23.4 mg of...

Embodiment 2

[0042] ( R )-2-(2-(2´-pyridine) ethyl)-6-fluorochroman-4-one III-2 The specific preparation steps are as follows:

[0043]

[0044] In this embodiment, the 4 in embodiment 1 H -benzothiopyran-4-one I-1 is replaced with 6-fluorobenzothiopyran-4-one I-2, and other steps are the same as in Example 1 to obtain 20.7 mg yellow oil ( R )-2-(2-(2´-pyridine) ethyl)-6-fluorochroman-4-one III-2, yield 72%, enantiomeric excess 94%. NMR and mass spectrometry data are: 1 H NMR (300 MHz, CDCl 3 ) δ 8.51 (d, J = 4.3 Hz, 1H), 8.02 (d, J = 2.0 Hz, 1H), 7.59 (t, J = 7.6Hz, 1H), 7.33 (dd, J = 8.4, 2.1 Hz, 1H), 7.21 (d, J = 8.5 Hz, 1H), 7.13 (dd, J = 11.9, 7.5 Hz, 2H), 3.50 (dd, J = 10.6, 6.5 Hz, 1H), 3.04 (m, 2H), 2.87(m, 2H), 2.15 (m, 2H); 13 C NMR (75 MHz, CDCl 3 ) δ 193.24 (s, 1H), 159.96 (s,1H), 149.39 (s, 2H), 139.51 (s, 1H), 136.56 (s, 2H), 133.42 (s, 3H), δ 131.3(d, J = 34.1 Hz), 128.9 (d, J = 48.9 Hz), 123.0, 121.5, 45.7, 41.0, 34.9,33.7; HRMS (ESI) m / z 310.0672 (M+Na + ...

Embodiment 3

[0046] ( R )-2-(2-(2'-pyridine) ethyl)-8-bromochroman-4-one III-3 The specific preparation steps are as follows:

[0047]

[0048] In this embodiment, the 4 in embodiment 1 H -Bromothiopyran-4-ketone I-1 is replaced with 8-bromobenzothiopyran-4-ketone I-3, and other steps are the same as in Example 1 to obtain 18.0 mg yellow oil ( R )-2-(2-(2´-pyridine)ethyl)-8-bromochroman-4-one III-3, yield 52%, enantiomeric excess 98%. NMR and mass spectrometry data are: 1 H NMR (300 MHz, CDCl 3 ) δ 8.52 (d, J = 4.3 Hz, 1H), 8.05 (d, J = 7.9 Hz, 1H), 7.62 (m, 2H),7.14 (m, 2H), 7.04 (t, J = 7.8 Hz, 1H), 3.50 (dt, J = 14.0, 5.2 Hz, 1H), 2.93(m, 4H), 2.21 (dd, J = 14.8, 7.0 Hz, 2H); 13 C NMR (75 MHz, CDCl 3 ) δ 193.8,160.0, 149.4, 142.5, 137.3, 136.6, 132.4, 127.9, 125.2, 123.1, 121.6, 44.7,40.3, 34.8, 33.8; HRMS (ESI) m / z 348.0056 (M+H + ), calc. for C 16 h 15 NOSBr348.0052.

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Abstract

The invention discloses a chiral benzodihydrothiapyran-4-one compound and a preparation method and application thereof. The preparation method comprises the following steps of: dispersing 4H-benzothiapyran-4-one with different substituent groups, 2-vinylpyridine, a photosensitizer DPZ, a reducing agent Hanus ester HE and a chiral phosphoric acid catalyst BA in an organic solvent, degassing the solution at the temperature not higher than -78 DEG C, placing the solution at the temperature of (-15)-(-35) DEG C, irradiating by using a 3-10W blue lamp, reacting for 60-80 hours, and after the reaction is finished, separating and purifying to obtain the (R)-2-(2-(2'-pyridine) ethyl) benzodihydrothiapyran-4-one and derivatives thereof. The yield of the obtained target product is medium or above, the reaction does not need heavy metals, and the product is green and pollution-free.

Description

technical field [0001] The invention belongs to the technical field of chiral compound synthesis, in particular to a class of optically pure ( R )-2-(2-(2´-pyridine) ethyl) chroman-4-one compound, its preparation method and application. Background technique [0002] Nitrogen heterocyclic structural units are widely found in the molecular structures of biologically active medicines, pesticides, natural and non-natural products, etc. According to statistics, nearly half of the top 200 commercially available chemical drugs in the world contain azaaryl groups Structural units. The sulfhydryl structural unit is the basic element of living organisms such as DNA, enzymes and proteins, and the carbonyl functional group is an important structural fragment of a variety of physiologically active molecules. The combination of these three types of structural units is important in drug development and active molecule modification. has potential application value. Such as pyridinium[2,3...

Claims

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Application Information

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IPC IPC(8): C07D409/06A61P35/00
CPCC07D409/06A61P35/00
Inventor 乔保坤江智勇赵筱薇
Owner HENAN UNIVERSITY
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