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Method for preparing axial chirality diaromatic compound with optical activity

A compound and aromatic technology, which is applied in the field of preparation of optically active axial chiral aromatic compounds, can solve problems such as immature methods, inability to realize asymmetric self-coupling reaction of high-steric hindrance substrates, simple and practical reaction system, etc. , to achieve the effect of good applicability, simple reaction and high atom economy

Inactive Publication Date: 2009-09-16
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
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  • Application Information

AI Technical Summary

Problems solved by technology

Asymmetric catalytic reaction is the most efficient, economical and practical method. However, the currently developed method is relatively immature, and cannot realize the asymmetric self-coupling reaction of highly hindered substrates, and the reaction system is not simple and practical.

Method used

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  • Method for preparing axial chirality diaromatic compound with optical activity
  • Method for preparing axial chirality diaromatic compound with optical activity
  • Method for preparing axial chirality diaromatic compound with optical activity

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Synthesis of 2a

[0033] Pass high-purity argon into a dry 10-1000 milliliter (ml) reaction bottle, add NiCl 2 (PPh 3 ) 2 (0.02~20mmol), chiral monodentate phosphoramidite ligand (0.02~20mmol), activated zinc powder (0.4~400mmol), Bu 4 NI (0.1~100mmol), after pumping twice, add 0.5~500mL of anhydrous DMA, stir at room temperature for 10min, then add substrate 3,4,5-trimethoxy 2- Bromobenzaldehyde (0.2 ~ 200mmol), under the protection of argon, stirred at a certain temperature for a certain period of time, then cooled to room temperature, filtered with diatomaceous earth, and then filtered with CH 2 Cl 2 Wash the filter residue three times (3×15mL), wash the organic phase (3×20mL) with water, remove DMA as much as possible, wash the organic phase with saturated brine, dry over anhydrous sodium sulfate, concentrate, and purify by flash silica gel column chromatography to obtain the coupled product 2a. See Table 1 for rate and ee values ​​(negative values ​​indicate o...

Embodiment 2

[0039] Synthesis of 2a

[0040] Pass high-purity argon into the dry 10-1000ml reaction flask, add NiCl 2 (PPh 3 ) 2 (0.02~20mmol), chiral monodentate phosphoramidite ligand (S)-11 (0.02~20mmol), activated zinc powder (0.4~400mmol), Bu 4 NI (0.1~100mmol), after pumping twice, add 0.5~500mL of anhydrous DMA, stir at room temperature for 10min, then add substrate 3,4,5-trimethoxy 2- Bromobenzaldehyde (0.2 ~ 200mmol), under the protection of argon, stirred at a certain temperature for a certain period of time, then cooled to room temperature, filtered with diatomaceous earth, and then filtered with CH 2 Cl 2 Wash the filter residue three times (3×15mL), wash the organic phase with water (3×20mL), remove DMA as much as possible, wash the organic phase with saturated saline, dry over anhydrous sodium sulfate, concentrate, and purify by flash silica gel column chromatography to obtain the corresponding coupling product 2a, yield 67%, ee value 67%.

[0041]

[0042] (EA: calc...

Embodiment 3

[0044] Synthesis of 2b

[0045] The operation is the same as in Example 2, the yield is 55%, and the ee is 58%.

[0046] mL / min, detected at 254nm, t R1 = 11.4min(minor), t R2 =15.5min(major).

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Abstract

The invention relates to a method for preparing an axial chirality diaromatic compound with optical activity, which is realized by an asymmetric Ullmann-type coupling reaction catalyzed by chiral monophosphine ligand and nickel composition. The method has the advantages of mild reacting condition, simple and convenient operation and good zymolyte applicability, can prepare the axial chirality diaromatic compound in high stereoselectivity and high yield, and has application prospect of mass synthesis of natural products with axial chirality.

Description

technical field [0001] The invention relates to a method for preparing an optically active axial chiral biaromatic compound. Background technique [0002] Biaromatic compounds containing chiral axes have been widely used in asymmetric reactions as chiral ligands and are important components of many natural products with important physiological activities. One of the focuses of chemists' research. The chiral axes of biaryl compounds widely exist in various natural product structures with different types, different physiological activities, and different biosynthetic sources, such as coumarin, flavonoid body, tannin, lignin, and alkaloid ( (a) Torssell, K.G.B. Natural Product Chemistry, Wiley, Chichester 1983; (b) Minitto, P. Biosynthesis of Natural Products, Ellis Horwood, Chichester 1981; (c) Thomson, R.H. The Chemistry of Natural Products, 1985; (d) Cordell , G.A. Introduction to Alkaloids, A Biogenetic Appoach, Wiely, New York 1981.). [0003] Many natural biaromatic co...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C47/575C07C45/72B01J31/24A61P31/20A61P1/16
Inventor 林国强徐明华陈雯雯
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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