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A kind of method utilizing saturated aldehyde to synthesize chiral tetrahydroquinoline

A technology of tetrahydroquinoline and saturated aldehydes, applied in organic chemistry methods, organic chemistry, etc., to achieve high yield and high ee value

Active Publication Date: 2022-06-28
上海泰坦科技股份有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method is only to prepare tetrahydroquinoline by hydrogenation reaction, and does not introduce chiral tetrahydroquinoline

Method used

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  • A kind of method utilizing saturated aldehyde to synthesize chiral tetrahydroquinoline
  • A kind of method utilizing saturated aldehyde to synthesize chiral tetrahydroquinoline
  • A kind of method utilizing saturated aldehyde to synthesize chiral tetrahydroquinoline

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] The present embodiment provides a method for synthesizing chiral tetrahydroquinoline

[0044]

[0045] The mass of 1.00g of compound a-1, 0.37g of diarylprolinol silicon ether, 0.25g of triphenylphosphine rhodium chloride, 0.21g of tri-n-butylamine, at 30 ° C, in 30mL volume ratio of 1 : 1.2 in a mixed solvent of dimethyl sulfoxide and 1,2-dichloroethane, react under an oxygen atmosphere for 80h, filter after the reaction, wash with water, wash with saturated sodium bicarbonate, wash with water again, and extract with dichloromethane, After silica gel column chromatography, 0.81 g of compound a-2 was obtained with a yield of 83.25% and an ee value of 99%.

[0046] 1 H NMR (400MHz, DMSO-d 6 )δ9.74(d,1H),7.14–6.39(m,4H),5.86(s,1H),3.31(p,1H),2.97(ddd,1H),2.81(ddd,1H),2.65–2.34 (m, 1H), 1.00 (d, 3H).

Embodiment 2

[0048] The present embodiment provides a method for synthesizing chiral tetrahydroquinoline

[0049]

[0050] Compound b-1 with a mass of 1.00 g, 0.33 g of diarylprolinol silyl ether, 0.22 g of triphenylphosphine rhodium chloride, 0.18 g of tri-n-butylamine, were dissolved in 40 mL of dimethylmethylene at 20°C. In the sulfone, react under an oxygen atmosphere for 90h, filter after the reaction, wash with water, saturated sodium bicarbonate, and then with water, extract with dichloromethane, and obtain 0.78g of compound b-2 after silica gel column chromatography, with a yield of 79.35%, ee value 98%.

[0051] 1 H NMR (400MHz, DMSO-d 6 )δ10.21–9.85(m,1H),7.19–6.22(m,3H),3.20–2.82(m,3H),2.81–2.52(m,4H),2.22(d,3H),1.09(d, 3H).

Embodiment 3

[0053] The present embodiment provides a method for synthesizing chiral tetrahydroquinoline

[0054]

[0055] Compound c-1 with a mass of 1.00 g, 0.24 g of diarylprolinol silyl ether, 0.35 g of palladium acetate, and 0.25 g of tri-n-butylamine were reacted in 30 mL of dichloromethane at 50 °C under an oxygen atmosphere 100h, filter after the reaction, wash with water, saturated sodium bicarbonate, and water again, extract with dichloromethane, and obtain 0.76 g of compound c-2 after silica gel column chromatography, yield 76.35%, ee value 98%.

[0056] 1 H NMR (400MHz, DMSO-d 6 )δ9.77(d,1H),6.86–6.36(m,2H),3.02(ddd,1H),2.88–2.45(m,6H),2.25(dd,6H),1.88(ddt,1H),1.41 (ddt, 1H), 0.79 (t, 3H).

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Abstract

The present invention provides a kind of method utilizing saturated aldehyde to synthesize chiral tetrahydroquinoline, and described method comprises: with the compound shown in formula I, in the presence of diaryl prolinol silicon ether and catalyst, react under oxygen atmosphere Obtain chiral tetrahydroquinoline; the method provided by the invention, through the coordination of diaryl prolinol silicon ether and catalyst, can well control the stereoselectivity of the cyclization process, can make chiral tetrahydroquinoline The product has a very high ee value, which can reach more than 99%, and the yield is relatively high, which can reach more than 75%, and the highest can reach more than 80%. It has an important application for the synthesis of downstream products of chiral tetrahydroquinoline value.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and relates to a method for synthesizing chiral tetrahydroquinoline by utilizing saturated aldehyde. Background technique [0002] Tetrahydroquinoline is an important pharmaceutical intermediate, which can be used to synthesize many related drugs. The synthesis of tetrahydroquinoline and derivatives of related chiral structures are the key steps for the application of downstream products. [0003] CN102993094A discloses a method for synthesizing tetrahydroquinoline derivatives, using Lewis acid SnCl 2 After the oxidation-reduction reaction with the oxidant, the generated oxidation product SnCl 4 In situ promoted aza-Diels-Alder cycloaddition of anilines, aldehydes and alkenes to obtain 1,2,3,4-tetrahydroquinoline derivatives. This method can successfully use fatty aldehydes to participate in the reaction, which expands the range of aldehyde substrates in the Povarov reaction. The accelerator ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D215/14C07D215/20C07D221/08C07D471/04
CPCC07D215/14C07D215/20C07D221/08C07D471/04C07B2200/07
Inventor 谢应波张庆张华徐肖冰罗桂云张维燕
Owner 上海泰坦科技股份有限公司
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