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A visible-light asymmetric catalyzed olefin cross-coupling method to construct pyridine derivatives containing γ-chiral centers

A chiral center and cross-coupling technology, applied in organic chemistry methods, organic chemistry, etc., can solve problems such as unrealized, and achieve the effects of good selectivity, mild reaction conditions, and less catalyst consumption

Active Publication Date: 2022-06-28
HENAN UNIVERSITY OF TECHNOLOGY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although the reductive cyclization of diketene substrates by photoredox catalysis was achieved by Yoon's group, the intermolecular coupling of two different electron-deficient alkenes as an important complementary method for alkene cross-couplings remains elusive.

Method used

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  • A visible-light asymmetric catalyzed olefin cross-coupling method to construct pyridine derivatives containing γ-chiral centers
  • A visible-light asymmetric catalyzed olefin cross-coupling method to construct pyridine derivatives containing γ-chiral centers
  • A visible-light asymmetric catalyzed olefin cross-coupling method to construct pyridine derivatives containing γ-chiral centers

Examples

Experimental program
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Effect test

Embodiment 1

[0019] A method for the construction of a γ-chiral center-containing pyridine derivative by asymmetric catalyzed olefin cross-coupling with visible light, the reaction formula is as follows. The specific preparation steps of (R)-2-(2-(pyridin-2-yl)ethyl)chroman-4-one are as follows:

[0020]

[0021]35.5 μL (0.0005 mmol, 0.005 equiv) of a solution of DPZ (prepared with 1.0 mg of DPZ in 200 uL toluene) was added to a 25 mL Schlenk tube and the solvent was removed in vacuo. Subsequently, 21.9 mg (0.15 mmol) of 4H-chroman-4-one, 10.5 mg (0.10 mmol) of 2-vinylpyridine, 113.3 mg (0.02 mmol) of chiral spirocyclic phosphonic acid, and 55.6 mg (0.02 mmol) of chiral spirophosphonic acid were added. 0.18mmol), then 2 ml of purified and dried dichloromethane were added, followed by vacuuming, freezing at -80°C for 3-5min, returning to room temperature, and argon protection (generally the entire process was carried out three times), the reaction flask was placed in - In a 25°C incubat...

Embodiment 2

[0023] The reaction formula for the synthesis of (R)-8-bromo-6-chloro-2-(2-(pyridin-2-yl)ethyl)chroman-4-one is shown below.

[0024]

[0025] In this example, the 4H-chroman-4-one in Example 1 was replaced with 8-bromo-6-chloro-4H-chroman-4-one, and other steps were the same as in Example 1 to obtain (R) -8-Bromo-6-chloro-2-(2-(pyridin-2-yl)ethyl)chroman-4-one 22.8 mg as yellow oil, yield 62%, optical purity 95% ee. The NMR data are: 1 H NMR (300MHz, CDCl 3 )δ8.50(d, J=4.1Hz, 1H), 7.64(m, 3H), 7.21(d, J=7.7Hz, 1H), 7.09(m, 1H), 4.47(td, J=12.6, 8.6 Hz, 1H), 3.08(m, 2H), 2.72(d, J=7.3Hz, 2H), 2.28(m, 2H); 13 C NMR (75MHz, CDCl 3 )δ190.2, 160.1, 156.4, 149.3, 138.2, 136.4, 126.8, 125.6, 123.2, 122.3, 121.3, 112.6, 77.9, 42.3, 34.0, 33.2; high-resolution data: HRMS(ESI)m / z 365.9894(M+H + ),calc.for C 16 H 164 NO 2 BrCl365.9891.

Embodiment 3

[0027] The reaction formula for the synthesis of (R)-6-methyl-2-(2-(pyridin-2-yl)ethyl)chroman-4-one is shown below.

[0028]

[0029] In this example, 4H-chroman-4-one in Example 1 was replaced with 6-methyl-4H-chroman-4-one, and other steps were the same as in Example 1 to obtain (R)-6- Methyl-2-(2-(pyridin-2-yl)ethyl)chroman-4-one 16.3 mg, yellow oil, yield 61%, optical purity 92% ee. The NMR data are: 1 H NMR (300MHz, CDCl 3 )δ8.22(d,J=4.3Hz,1H),7.30(dd,J=16.3,8.6Hz,2H),6.97(d,J=9.0Hz,1H),6.88(d,J=7.8Hz, 1H), 6.81(m, 1H), 6.57(d, J=8.4Hz, 1H), 4.14(dt, J=8.9, 4.9Hz, 1H), 2.74(m, 2H), 2.39(m, 2H), 1.92(m,5H); 13 C NMR (75MHz, CDCl 3 )δ192.6, 160.7, 159.6, 149.4, 137.0, 136.5, 130.6, 126.5, 123.0, 121.3, 120.6, 117.7, 43.0, 34.5, 33.5, 20.4; high-resolution data: HRMS(ESI)m / z268.1333(M+ H + ),calc.for C 17 H 18 NO 2 268.1332.

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Abstract

The invention discloses a method for constructing pyridine derivatives containing γ-chiral center by asymmetric catalytic olefin cross-coupling under visible light, which belongs to the technical field of organic synthesis. The vinylpyridine compounds shown are in dichloromethane with Hans ester (HE) as reducing agent, DPZ as visible light redox catalyst, spiro chiral phosphonic acid CPA (CPA‑1 or CPA‑2) as chiral catalyst , reacted completely at -20~-30°C under visible light irradiation, separated and purified to obtain the γ-chiral center-containing pyridine derivative shown in formula III,

Description

technical field [0001] The invention belongs to the technical field of synthesis of pyridine derivatives containing a γ-chiral center, in particular to a method for constructing a pyridine derivative containing a γ-chiral center by asymmetrically catalyzing olefin cross-coupling with visible light. Background technique [0002] Pyridine azaarenes are widely found in natural products, drugs and functional material molecules. For example, 12 of the top 200 drugs by world sales in 2012 contain pyridine structures (http: / / www.pharmacytimes.com / publications / issue / 2013 / July2013 / Top-200-Drugs-of-2012 ( accessed Oct 29, 2014)). In addition, many pyridine derivatives are widely used as ligands in asymmetric catalysis (Chelucci, G. Coord. Chem. Rev. 2013, 257, 1887.). Therefore, the methodological research on the synthesis of chiral derivatives of pyridine has always attracted the attention of chemists. [0003] Based on the electron-withdrawing properties of pyridines containing i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D405/06C07D409/06C07D213/50
CPCC07D405/06C07D409/06C07D213/50C07B2200/07
Inventor 尹艳丽江智勇王乐王金荣
Owner HENAN UNIVERSITY OF TECHNOLOGY
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