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Compound containing chiral chromanone skeletons and asymmetric synthetic method thereof

A technology for dihydrochromone and chiral compounds, which is applied in the field of chiral dihydrochromone skeleton compounds and asymmetric synthesis, achieving the effects of mild reaction conditions, simple operation and wide application range of substrates

Inactive Publication Date: 2012-06-27
SICHUAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the preparation of chiral dihydrochromone tricyclic compounds by asymmetric catalysis of such electron-deficient dienes has hardly been reported in the literature, especially through the green and environmentally friendly organic small molecule catalysis method.

Method used

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  • Compound containing chiral chromanone skeletons and asymmetric synthetic method thereof
  • Compound containing chiral chromanone skeletons and asymmetric synthetic method thereof
  • Compound containing chiral chromanone skeletons and asymmetric synthetic method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Example 1: asymmetric anti-electron demand Diels-Alder reaction and series reaction of chromone electron-deficient diene compound and alkenal catalyzed by a, a-diarylprolinol silyl ether.

[0022] In a clean reaction tube, add chiral prolinol silyl ether catalyst (0.02 mmol), chromone electron-deficient diene compound (0.1 mmol), enal (0.2 mmol), acidic additive (0.02 mmol) and 1,4-Dioxane (1 mL) at 25 o The reaction time was stirred under C, and after the reaction was monitored by TLC, the solvent was recovered under reduced pressure, and the residue was separated by column chromatography to obtain the target product.

[0023] P1, 89% yield, 94% ee , Chiral test conditions: HPLC analysis on Chiralpak IC column (20% 2-propanol / n -hexane, 1 mL / min), UV 220 nm, t major = 23.47 min, t minor = 25.67 min. [α] D 20 = -21.3 ( c = 0.79 in CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ): 8.01 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.52 (td, J = 8.0 Hz, J = 1.6 Hz, ...

Embodiment 2

[0047] Example 2: Transformation with multifunctional functional groups (application example 1)

[0048]

[0049] P22 (37 mg, 0.1 mmol) was weighed into a dry reaction tube, dissolved in 1 mL of chloroform, and then the carbene catalyst (7.3 mg, 0.02 mmol) and sodium acetate (9.8 mg, 0.12 mmol), heated to 40°C and stirred until P22 disappeared as detected by thin layer chromatography. Column chromatography separated petroleum ether / ethyl acetate: 8 / 1) to obtain the title compound, 92% yield, 90% ee , Chiral test conditions: HPLC analysis on Chiralpak OD column (20% 2-propanol / n -hexane, 1 mL / min), UV 220 nm, t minor = 11.96 min, t major = 17.04 min. [α] D 20 = +128.8 ( c = 0.90 in CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ): 7.92 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.50 (td, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.27-7.25 (m, 2H), 7.07 (t, J = 8.0 Hz, 1H), 6.95-6.92 (m, 3H), 4.79-4.78 (m, 1H), 3.10 (t, J = 3.6 Hz, 1H), 2.99 (br s, 2H), 2.71 (d, J = 18.4 Hz, 1H),...

Embodiment 3

[0050] Example 3: Transformation with multifunctional functional groups (application example 2)

[0051]

[0052] P22 (33 mg, 0.09 mmol) was weighed into a dry reaction tube, dissolved in 1 mL of dichloromethane, and organic base DBU (15.2 mg, 0.1 mmol), stirred at room temperature until P22 disappeared as detected by thin layer chromatography. Column chromatography separated petroleum ether / ethyl acetate: 10 / 1) to obtain the title compound as a semi-solid, 88% yield, 94% ee , Chiral test conditions: HPLC analysis on Chiralpak AD column (20% 2-propanol / n -hexane, 1 mL / min), UV 254 nm, t major = 11.14 min, t minor = 19.03 min. [α] D 20 = -17.0 ( c = 0.50 in CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ): 8.03 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.52 (td, J = 8.4 Hz, J = 1.6 Hz, 1H), 7.31 (d, J = 8.4 Hz, 2H), 7.12-7.07 (m, 3H), 6.99 (d, J = 8.4 Hz, 1H), 6.33 (s, 1H), 4.60 (t, J = 6.0 Hz, 1H), 4.48 (dd, J = 10.0 Hz, J = 2.8 Hz, 1H), 2.30 (dd, J = 13.6 Hz,...

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Abstract

The invention provides a synthetic method for preparing a compound containing multiple-chiral center chromanone skeletons, which can effectively utilize chiral amine-in particular a, a-diaryl prolinol O-silyl ether--catalytic chromone electron-deficient diene compound and olefine aldehyde to generate Diels-Alder reaction required by asymmetric anti-electrons with high regioselectivity and high stereoselectivity and series vinylogy Aldol or series hemiacetal reaction under the mild reaction conditions and can also be used for synthesizing the compound with the multiple-chiral center dihydro-chromogenic ketone skeletons. The asymmetric synthetic method is reported for the first time and has the various advantages of cheap and easily-obtained catalyst, high catalytic activity, mild reaction condition, simplicity in operation, wide substrate application scope and high product area and enantioselectivity; and more importantly, the compound containing the various multiple-chiral center dihydro-chromogenic ketone skeletons prepared by the method possibly has special physiological activity or becomes an important synthetic intermediate body of a natural product.

Description

technical field [0001] The present invention designs a Diels-Alder reaction and series connection of chromone electron-deficient diene compound and alkenal with high regioselectivity and high stereoselectivity asymmetric anti-electron demand under mild reaction conditions catalyzed by chiral amine Aldol or tandem hemiacetalization reactions for the synthesis of a class of compounds with polychiral central dihydrochromone skeletons. Such chiral compounds may have a variety of special physiological activities or become important synthetic intermediates of natural products. Background technique [0002] Dihydrochromone skeletons, especially tricyclic and polycyclic compounds based on such skeletons, are widely found in natural products and pharmaceutical intermediates. In view of the important role of such compounds in medicine, more and more of interest to chemists. In recent years, the research on the modification of substituents, the synthesis of structural analogues and t...

Claims

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Application Information

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IPC IPC(8): C07D311/00C07D311/86C07D405/04
CPCY02P20/55
Inventor 陈应春李俊龙蕫琳
Owner SICHUAN UNIV
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