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Use of aryloxy-functionalized prolinol chiral ligand as catalyst

A technology for synthesizing prolinol and chiral ligands, which is applied in the application field of aryloxy-functionalized prolinol chiral ligands as catalysts, can solve problems such as rising enantioselectivity of products, and achieve good enantioselectivity , Universal effect

Active Publication Date: 2019-06-07
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] In summary, most of the asymmetric addition reactions between chalcones and benzotriazoles are realized by the catalysis of small organic molecules, and only moderate yields can be obtained at high catalyst dosages and the enantiotropic reactions of the products There is still a lot of room for improvement in selectivity

Method used

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  • Use of aryloxy-functionalized prolinol chiral ligand as catalyst
  • Use of aryloxy-functionalized prolinol chiral ligand as catalyst
  • Use of aryloxy-functionalized prolinol chiral ligand as catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Example 1: Aryloxy functionalized chiral prolinol ligands combined with rare earth metal amides catalyze the asymmetric reaction of chalcones and benzotriazoles:

[0054] Under argon protection, add 0.0179g (0.03×10 -3 mol) Sc[N(SiMe 3 ) 2 ] 3 , and then adding the aryloxy functionalized chiral prolinol ligand H 2 L 4 0.0249g (0.03×10 -3 mol), add 1 mL of chloroform solvent to dissolve it, stir for 0.5 h, add chalcone 0.0624 (0.3×10 -3 mol), continue to stir the reaction for 30min, then add 0.0429g (0.36×10 -3 mol) benzotriazole, sealed the bottle and stirred for 24 hours, terminated the reaction with water, added 3mL ethyl acetate for extraction, took the upper organic phase, added silica gel and spin-dried, column chromatography (EA:PE=1:10), obtained hand The sum of the reaction conversions of the obtained products 3(a) and 4(a) is 87%. The yield ratio of 3(a) and 4(a) was close to 7:2, and the ee value of 3(a) reached 75%.

[0055] The structure of product...

Embodiment 2

[0062] Example 2: Aryloxy-functionalized chiral prolinol ligands and rare earth metal amides jointly catalyze the asymmetric reaction of 4-chlorochalcone and benzotriazole:

[0063] Under argon protection, add 0.0179g (0.03×10 -3 mol) Sc[N(SiMe 3 ) 2 ] 3 , and then adding the aryloxy functionalized chiral prolinol ligand H 2 L 4 0.0249g (0.06×10 -3 mol), add 1 mL of chloroform solvent to dissolve it, stir the reaction for 0.5 h, add 0.0726 g of 4-chlorochalcone (0.3×10 -3 mol), continue to stir the reaction for 30min, then add 0.0429g (0.36×10 -3 mol) of benzotriazole, sealed the bottle and stirred for 24 hours, terminated the reaction with water, added 3 mL of ethyl acetate for extraction, took the upper organic phase, added silica gel and spin-dried, column chromatography (EA:PE=1:10), obtained The chiral addition product has a conversion rate of 84%, the yield ratio of product 3(b) and 4(b) is close to 64:20, and the ee value of product 3(b) reaches 61%.

[0064] Th...

Embodiment 3

[0070]Example 3: Aryloxy-functionalized chiral prolinol ligands and rare earth metal amides jointly catalyze the asymmetric reaction of 4-fluorochalcone and benzotriazole:

[0071] Under argon protection, add 0.0179g (0.03×10 -3 mol) Sc[N(SiMe 3 ) 2 ] 3 , and then adding the aryloxy functionalized chiral prolinol ligand H 2 L 4 0.0249g (0.06×10 -3 mol), add 1 mL of chloroform solvent to dissolve it, stir the reaction for 0.5 h, add 0.0678 g of 4-fluorochalcone (0.3×10 -3 mol), continue to stir the reaction for 30min, then add 0.0429g (0.36×10 -3 mol) of benzotriazole was sealed and stirred for 24 hours, terminated the reaction with water, added 3mL of ethyl acetate for extraction, took the upper organic phase, added silica gel and spin-dried, column chromatography (EA:PE=1:10), obtained hand The reaction conversion rate is 95%, the yield ratio of product 3(c) and 4(c) is close to 67:28, and the ee value of product 3(c) reaches 71%.

[0072] The structure of product 3(c...

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Abstract

The invention relates to use of an aryloxy-functionalized prolinol chiral ligand for catalyzing the asymmetric addition reaction of chalcone compounds with benzotriazole. In the water-free and oxygen-free conditions containing protective atmosphere, alpha, beta-unsaturated ketones in the formula (1) and benzotriazoles react in the organic solvent at 40-20 DEG C under the catalyst action of the aryloxy-functionalized prolinol chiral ligand and rare earth metal amines, so as to obtain compounds shown in the formula (3) and the formula (4) which are described in the description, wherein R1 is selected from the group consisting of hydrogen, alkyl, halogen, methoxy, nitro or CF3; R2 is selected from the group consisting of phenyl, C1-C4 alkyl substitute phenyl, C1-C4 alkoxy substitute phenyl, halophenyl, furyl or thienyl; H2Ln is that aryloxy-functionalized prolinol chiral ligand; the structural formula of H2Ln is as shown in the formula (2), wherein R3, R4 are independently selected from C1-C4 alkyl, cumyl, hydrogen or halogen; RE[N(SiMe3)2]3 is the rare earth metal amine compound, wherein RE represents a rare earth metal and RE is selected from the group consisting of scandium, lanthanum, neodymium, samarium, yttrium or ytterbium.

Description

technical field [0001] The invention relates to the field of catalysts, in particular to the application of an aryloxy functionalized prolinol chiral ligand as a catalyst. Background technique [0002] Nitrogen-containing heterocyclic compounds and their derivatives have been widely used in organic synthetic chemistry, medicinal chemistry and material science. At present, there are few reports on the asymmetric addition reaction of unsaturated ketones and benzotriazoles. Most of the catalysts involved in this type of reaction are small organic molecules, and only a few are chiral metal catalysts. [0003] At present, there are several reports on the asymmetric addition reaction of nitrogen-containing heterocyclic rings and unsaturated ketones catalyzed by small organic molecules as follows: [0004] (1) Utilize small organic molecules of cinchona alkaloid derivatives as chiral catalysts to realize the asymmetric aza-Michael addition reaction of nitroalkenes and N-heterocycl...

Claims

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Application Information

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IPC IPC(8): C07D207/08B01J31/18C07D249/18C07D405/06C07D409/06
Inventor 陆澄容赵蓓夏学秀
Owner SUZHOU UNIV
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